Molecules doi: 10.3390/molecules29061352
Authors: Carlos F. G. C. Geraldes
Magnetic nanoparticles (MNPs), either paramagnetic or superparamagnetic depending on their composition and size, have been thoroughly studied as magnetic resonance imaging (MRI) contrast agents using in vitro and in vivo biomedical preclinical studies, while some are clinically used. Their magnetic properties responsible in some cases for high magnetization values, together with large surface area-to-volume ratios and the possibility of surface functionalization, have been used in MRI-based diagnostic and theranostics applications. MNPs are usually used as positive (T1) or negative (T2) MRI contrast agents, causing brightening or darkening of selected regions in MRI images, respectively. This review focusses on recent developments and optimization of MNPs containing Gd, Mn, Fe and other lanthanide ions which may function as dual-mode T1–T2 MRI contrast agents (DMCAs). They induce positive or negative contrast in the same MRI scanner upon changing its operational mode between T1-weighted and T2-weighted pulse sequences. The type of contrast they induce depends critically on their r2/r1 relaxivity ratio, which for DMCAs should be in the 2–10 range of values. After briefly discussing the basic principles of paramagnetic relaxation in MNPs, in this review, the basic strategies for the rational design of DMCAs are presented and typical examples are discussed, including in vivo preclinical applications: (1) the use of NPs with a single type of contrast material, Gd- or Mn-based NPs or superparamagnetic NPs with appropriate size and magnetization to provide T2 and T1 contrast; and (2) inclusion of both types of T1 and T2 contrast materials in the same nanoplatform by changing their relative positions.
]]>Molecules doi: 10.3390/molecules29061351
Authors: Elez Garofulić Repajić Cegledi Dobroslavić Dobrinčić Zorić Pedisić Franković Breški Dragović-Uzelac
The aim of the present study was to evaluate microwave-assisted (MAE) and pressurized liquid extraction (PLE) for the recovery of polyphenols from blackcurrant and bilberry leaves and the preservation of their antioxidant activity. The extractions were carried out varying the solvent/solid (SS) ratio, temperature and time. During MAE, increasing the SS ratio increased the polyphenol concentration in the extracts from blackcurrant and bilberry leaves, while increasing the temperature had a positive effect only on bilberry polyphenols. During PLE, only a temperature increase was a determining factor for the isolation of blackcurrant leave polyphenols. Based on polyphenol recovery, optimal extraction parameters were established resulting in a yield of 62.10 and 56.06 mg/g dw in the blackcurrant and bilberry MAE extracts and 78.90 and 70.55 mg/g dw in the PLE extracts. The optimized extracts were profiled by UPLC ESI MS2, and their antioxidant capacity was evaluated through FRAP, DPPH, ABTS and ORAC assays. The characterization of the extracts by UPLC ESI MS2 confirmed flavonols as the predominant compounds in both blackcurrant and bilberry leaves, while flavan-3-ols and procyanidins were the main compounds responsible for high antioxidant capacity as confirmed by the ABTS and ORAC assays. Due to the extract composition and antioxidant capacity, PLE proved to be a technique of choice for the production of blackcurrant and bilberry leave extracts with high potential for use as value-added ingredients in the food and nutraceutical industry.
]]>Molecules doi: 10.3390/molecules29061350
Authors: Masfer Alkahtani Yahya A. Alzahrani Abdulaziz Alromaeh Philip Hemmer
In this work, we successfully integrated fluorescent nanodiamonds (FNDs) and lanthanide ion-doped upconversion nanoparticles (UCNPs) in a nanocomposite structure for simultaneous optical temperature sensing. The effective integration of FND and UCNP shells was confirmed by employing high-resolution TEM imaging, X-ray diffraction, and dual-excitation optical spectroscopy. Furthermore, the synthesized ND@UCNP nanocomposites were tested by making simultaneous optical temperature measurements, and the detected temperatures showed excellent agreement within their sensitivity limit. The simultaneous measurement of temperature using two different modalities having different sensing physics but with the same composite nanoparticles inside is expected to greatly improve the confidence of nanoscale temperature measurements. This should resolve some of the controversy surrounding nanoscale temperature measurements in biological applications.
]]>Molecules doi: 10.3390/molecules29061348
Authors: Jarosław Ostrowski Alicja Drozd Rafał Olchowski Agnieszka Chałabis-Mazurek Andrzej Sienkiewicz Agnieszka Kierys Kinga Morlo Ryszard Dobrowolski
Newly synthesized cerium oxide was successfully obtained by the hard templating route. The optimal As(III) and As(V) adsorption onto the studied adsorbent was reached for the initial pH of 4.0 and a contact time of 10 h. The highest static adsorption capacities for As(III) and As(V) were 92 mg g−1 and 66 mg g−1, respectively. The pseudo-second-order model was well fitted to the As(III) and As(V) experimental kinetics data. The Langmuir model described the As(III) and As(V) adsorption isotherms on synthesized material. The adsorption mechanism of the studied ions onto the synthesized cerium oxide was complex and should be further investigated. The optimal solid–liquid ratio during the proposed aqueous extraction of inorganic As from the Fucus vesiculosus algae was 1:50. The optimal dosage of the synthesized cerium oxide (0.06 g L−1) was successfully applied for the first time for inorganic As removal from the aqueous algal extract.
]]>Molecules doi: 10.3390/molecules29061349
Authors: Chong Shi Xian-Yong Wei
The fluorescent nitrogen-doped carbon dots (N-CDs) were synthesized via a facile one-pot solvothermal process using coal (Jin 15 Anthracite and Shaerhu lignite) as raw materials and dimethyl formamide (DMF) as the solvent, employing a microwave pyrolysis method. This approach demonstrates remarkable efficacy in the development of nitrogen-doped carbon dots (N-CDs) with a high quantum yield (QY). The N-CDs prepared have strong photoluminescence properties. Moreover, the obtained N-CDs emit blue PL and are easily dispersed in polymethyl methacrylate (PMMA), preserving the inherent advantages of N-CDs and the PMMA matrix. The JN-CDs exhibit a high quantum yield (QY) of 49.5% and a production yield of 25.7%, respectively. In contrast, the SN-CDs demonstrate a quantum yield of 40% and a production yield of 35.1%. It is worth noting that the production yield and quantum yield of coal-based carbon dots are inversely related indices. The lower metamorphic degree of subbituminous coal favors an enhanced product yield, while the higher metamorphic degree of anthracite promotes an improved quantum yield in the product, which may be attributed to the presence of amorphous carbon within it. Consequently, we propose and discuss potential mechanisms underlying N-CD formation.
]]>Molecules doi: 10.3390/molecules29061347
Authors: Xiang Qiu Yanghui Ou Shengjia Lu Yibin Liang Yali Zhang Mengjie Li Gang Li Hongwei Ma Yanting Wu Zhaoyu He Zhensheng Zhang Hongliang Yao Wen-Hua Chen
The polysaccharides from Stemona tuberosa Lour, a kind of plant used in Chinese herbal medicine, have various pharmacological activities, such as anti-inflammatory and antioxidant properties. However, the effects of the extraction methods and the activity of polysaccharides from different parts are still unknown. Therefore, this study aimed to evaluate the effects of different extraction methods on the yields, chemical compositions, and bioactivity of polysaccharides extracted from different parts of Stemona tuberosa Lour. Six polysaccharides were extracted from the leaves, roots, and stems of Stemona tuberosa Lour through the use of hot water (i.e., SPS-L1, SPS-R1, and SPS-S1) and an ultrasound-assisted method (i.e., SPS-L2, SPS-R2, and SPS-S2). The results showed that the physicochemical properties, structural properties, and biological activity of the polysaccharides varied with the extraction methods and parts. SPS-R1 and SPS-R2 had higher extraction yields and total sugar contents than those of the other SPSs (SPS-L1, SPS-L2, SPS-S1, and SPS-S2). SPS-L1 had favorable antioxidant activity and the ability to downregulate MUC5AC expression. An investigation of the anti-inflammatory properties showed that SPS-R1 and SPS-R2 had greater anti-inflammatory activities, while SPS-R2 demonstrated the strongest anti-inflammatory potential. The results of this study indicated that SPS-L1 and SPS-L2, which were extracted from non-medicinal parts, may serve as potent natural antioxidants, but further study is necessary to explore their potential applications in the treatment of diseases. The positive anti-inflammatory effects of SPS-R1 and SPS-R2 in the roots may be further exploited in drugs for the treatment of inflammation.
]]>Molecules doi: 10.3390/molecules29061346
Authors: Lajos Attila Papp Zoltán István Szabó Gabriel Hancu Lénárd Farczádi Eleonora Mircia
This comprehensive review explores the utilization of chiral stationary phases (CSPs) in the context of single-column simultaneous chiral–achiral high-performance liquid chromatography (HPLC) separation methods. While CSPs have traditionally been pivotal for enantioselective drug analysis, contemporary CSPs often exhibit notable chemoselective properties. Consequently, there is a discernible trend towards the development of methodologies that enable simultaneous enantio- and chemoselective separations utilizing a single CSP-based chromatographic column. This review provides an exhaustive overview of reported HPLC methods in this domain, with a focus on four major CSP types: cyclodextrin-, glycopeptide antibiotic-, protein-, and polysaccharide-based CSPs. This article delves into the diverse applications of CSPs, encompassing various chromatographic modes such as normal phase (NP), reverse phase (RP), and polar organic (PO). This review critically discusses method development, emphasizing the additional chemoselective separation mechanisms of CSPs. It also explores possibilities for method optimization and development, concluding with future perspectives on this evolving field. Despite the inherent challenges in understanding the retention mechanisms involved in chemoselective separations, this review highlights promising trends and anticipates a growing number of simultaneous enantio- and chemoselective methods in pharmaceutical analyses, pharmacokinetic studies, and environmental sample determinations.
]]>Molecules doi: 10.3390/molecules29061345
Authors: Huijuan Ying Chenglin Jia Ganning Zeng Ning Ai
Converting Sargassum horneri (SH)—a harmful marine stranding that can cause golden tide—to highly porous bio-adsorbent material (via one-step catalytic oxidative pyrolysis with K2FeO4) can be a strategically useful method for obtaining low-cost materials suitable for CO2 capture. In this manuscript, the behavior of different mass ratios of K2FeO4/SH precursor acting on the surface physicochemical properties of carbon materials are reported. The results suggest that specific surface area and total pore volume first increased to the mass ratio of K2FeO4/carbon precursor, then decreased. Among the samples prepared, the highest specific surface area was obtained with a K2FeO4/SH precursor ratio of 1:4 (25%-ASHC), and the CO2 adsorption performance was significantly increased and faster compared with the original biochar. The fitted values of the three kinetic models showed that the double exponential model provided the best description of carbon adsorption, indicating both physical and chemical adsorption; 25%-ASHC also exhibited excellent cyclic stability. The improved CO2 adsorption performance observed after K2FeO4 activation is mainly due to the increase in material porosity, specific surface area, and the enrichment of nitrogen and oxygen functional groups.
]]>Molecules doi: 10.3390/molecules29061344
Authors: Martin Breza
The dimethylaminophenyl-substituted silver phthalocyanine [dmaphPcAg] can be used as a UV-vis photoinitiator for in situ preparation of a silver/polymer nanocomposite. To verify early steps of the supposed mechanism of radical polymerization, we performed quantum chemical calculations of m[dmaphPcAg]q complexes with charges q = +1 to −2 in the two lowest spin states m, of a free ligand and its dehydrogenated/deprotonated products m[dmaphPcHn]q, n = 2 to 0, q = 0, −1 or −2, in the lowest spin states m. The calculated electronic structures and electron transitions of all the optimized structures in CHCl3 solutions are compared with experimental EPR and UV-vis spectra, respectively. The unstable 3[dmaphPcAg]+ species deduced only from previous EPR spin trap experiments was identified. In addition to 2[dmaphPcAg]0, our results suggest the coexistence of both reaction intermediates 1[dmaphPcAg]− and 3[dmaphPcAg]− in reaction solutions. Silver nanoparticle formation is a weak point of the supposed reaction mechanism from the energetic, stereochemistry, and electronic structure points of view.
]]>Molecules doi: 10.3390/molecules29061342
Authors: Xiaohu Xu Kaiwei Guo Xinyue Yu
Recently, perovskite (ABO3) nanomaterials have been widely explored as a class of versatile electrocatalysts for oxygen evolution reactions (OER) due to their remarkable compositional flexibility and structural tunability, but their poor electrical conductivity hinders hydrogen evolution reaction (HER) activity and further limits the large-scale application of perovskite oxide in overall water splitting (OWS). In this study, hollow-nanotube-structure LaxCo0.4Fe0.6O3−δ (x = 1.0, 0.9, and 0.8) perovskites with superior HER/OER activity were synthesized on nickel-iron alloy foam (denoted LaxCoFe/NFF) using hydrothermal with a subsequent calcination strategy. Among them, La0.9CoFe/NFF not only exhibited extraordinary HER electrocatalytic performance (160.5 mV@10 mA cm−2 and 241.0 mV@100 mA cm−2) and stability (20 h@10 mA cm−2), but also displayed significant OER electrocatalytic activity (234.7 mV@10 mA cm−2 and 296.1 mV@100 mA cm−2) and durability (20 h@10 mA cm−2), outperforming many recently reported HER/OER perovskite catalysts. The increase in oxygen vacancies caused by the introduction of La deficiency leads to the expansion of the lattice, which greatly accelerates the HER/OER process of La0.9CoFe/NFF. Additionally, the naturally porous skeleton can prevent catalysts from aggregating as well as delay the corrosion and dissolution of catalysts in the electrolyte under high applied potentials. Furthermore, the assembled two-electrode configuration, utilizing La0.9CoFe/NFF (cathode and anode) electrodes, only requires a low cell voltage of 1.573 V at 10 mA cm−2 for robust alkaline OWS, accompanied by remarkable durability over 20 h. This work provides inspiration for the design and preparation of high-performance and stable bifunctional perovskite electrocatalysts for OWS.
]]>Molecules doi: 10.3390/molecules29061343
Authors: Qianqian Qian Zhihang Zhuo Yaqin Peng Danping Xu
Essential oils are secondary metabolites in plants with a variety of biological activities. The flavor and quality of Zanthoxylum armatum DC. are mainly determined by the essential oil components in the Chinese prickly ash peels. In this study, the correlation between climate change in different regions and the content of essential oils of Z. armatum was investigated using gas chromatography–mass spectrometry (GC/MS) and multivariate statistical analysis. The Z1–24 refers to 24 batches of samples from different habitats. A total of 145 essential oils were detected in 24 batches of samples, with the highest number of terpene species and the highest content of alcohol. The relative odor activity (ROAV) values identified nine main flavor compounds affecting the odor of Z. armatum. Linalool, decanal, and d-limonene were the most critical main flavor compounds, giving Z. armatum a spicy, floral, oily, and fruity odor. The results of hierarchical cluster analysis (HCA) and principal component analysis (PCA) classified Z5 into a separate group, Z2 and Z7 were clustered into one group, and the rest of the samples were classified into another group. Correlation analysis and path analysis showed that temperature and precipitation were the main climatic factors affecting essential oils. Comparisons can be made with other plants in the genus Zanthoxylum to analyze differences in essential oil type and content. This study contributes to the identification of Z. armatum quality, promotes the accumulation of theories on the effects of climatic factors on essential oils, and enriches the site selection and breeding of Z. armatum under similar climatic conditions.
]]>Molecules doi: 10.3390/molecules29061341
Authors: Jacek E. Nycz Natalia Martsinovich Jakub Wantulok Tieqiao Chen Maria Książek Joachim Kusz
Water-soluble ligands based on a 1,10-phenanthroline core are relatively poorly studied compounds. Developing efficient and convenient syntheses of them would result in new interesting applications because of the importance of 1,10-phenanthrolines. In this manuscript, we describe novel and practical ways to introduce a carboxyl and, for the first time, a phenol and dithiocarboxyl group under mild reaction conditions. This strategy enables highly efficient and practical synthesis of suitable organosulfur compounds with high added value, high chemoselectivity, and a broad substrate range. We present the selective conversion of a hydroxydialdehyde in the form of 10-hydroxybenzo[h]quinoline-7,9-dicarbaldehyde into its derivative, unique hydroxydicarboxylic acid, by an oxidation procedure, giving 10-hydroxybenzo[h]quinoline-7,9-dicarboxylic acid. A similar procedure resulted in the formation of 9-methyl-1,10-phenanthroline-2-carboxylic acid by oxidation of commercially available neocuproine. An alternative method of obtaining 1,10-phenanthroline derivatives possessing carboxylic acid group can be based on the hydrolysis of ester or nitrile groups; however, this synthesis leads to unexpected products. Moreover, we apply Perkin condensation to synthesize a vinyl (or styryl) analog of 1,10-phenanthroline derivatives with phenol function. This reaction also demonstrates a new, simple, and efficient strategy for converting methyl derivatives of 1,10-phenanthroline. We anticipate that the new way of converting methyl will find wide application in chemical synthesis.
]]>Molecules doi: 10.3390/molecules29061340
Authors: Ju Hee Gu Dongho Park Kyung-Hye Jung Byung Chul Lee Yoon Soo Han
Redox mediators comprising I−, Co3+, and Ti3C2Tx MXene were applied to dye-sensitized solar cells (DSCs). In the as-prepared DSCs (I-DSCs), wherein hole conduction occurred via the redox reaction of I−/I3− ions, the power conversion efficiency (PCE) was not altered by the addition of Ti3C2Tx MXene. The I-DSCs were exposed to light to produce Co2+/Co3+-based cells (Co-DSCs), wherein the holes were transferred via the redox reaction of Co2+/Co3+ ions. A PCE of 9.01% was achieved in a Co-DSC with Ti3C2Tx MXene (Ti3C2Tx-Co-DSC), which indicated an improvement from the PCE of a bare Co-DSC without Ti3C2Tx MXene (7.27%). It was also found that the presence of Ti3C2Tx MXene in the redox mediator increased the hole collection, dye regeneration, and electron injection efficiencies of the Ti3C2Tx-Co-DSC, leading to an improvement in both the short-circuit current and the PCE when compared with those of the bare Co-DSC without MXene.
]]>Molecules doi: 10.3390/molecules29061339
Authors: Dominik Dörfel Sascha Rohn Eckard Jantzen
Supplementing fish oil is one of the strategies to reduce the risk of cardiovascular disease, the leading cause of death around the world. Contradictorily, fish oil may also contain trimethylamine-N-oxide, a recently emerged risk factor for cardiovascular disease, as well as one of its precursors, trimethylamine. A method suitable for routine quantification of trimethylamine-N-oxide and trimethylamine in fish oil with a quick and easy liquid extraction without derivatization has been developed. Liquid chromatography with tandem mass spectrometry detection was employed along with a zwitterionic hydrophilic interaction liquid chromatography column and a gradient elution with eluents containing 50 mmol/L of ammonium formate. An internal standard (triethylamine) was used for quantification by mass spectrometry with an external calibration. The assay proved high linearity in the ranges of 10 to 100 ng/mL and 100 to 1000 ng/mL for trimethylamine-N-oxide and trimethylamine, respectively. The lowest limit of quantification was determined to be 100 µg/kg for trimethylamine and 10 µg/kg for trimethylamine-N-oxide, with the limit of detection at 5 µg/kg and 0.25 µg/kg, respectively. Accuracy ranged from 106–119%. Precision was below 7% the relative standard deviation for both analytes. The method was successfully applied for the determination of trimethylamine-N-oxide and trimethylamine contents in nine commercially available liquid fish oils and three commercially available fish oil capsules, showing that trimethylamine and trimethylamine-N-oxide are not present in highly refined fish oils.
]]>Molecules doi: 10.3390/molecules29061338
Authors: Zhi Qu Lin Zhang Yan Sun
PETase exhibits a high degradation activity for polyethylene terephthalate (PET) plastic under moderate temperatures. However, the effect of non-active site residues in the second shell of PETase on the catalytic performance remains unclear. Herein, we proposed a crystal structure- and sequence-based strategy to identify the key non-active site residue. D186 in the second shell of PETase was found to be capable of modulating the enzyme activity and stability. The most active PETaseD186N improved both the activity and thermostability with an increase in Tm by 8.89 °C. The PET degradation product concentrations were 1.86 and 3.69 times higher than those obtained with PETaseWT at 30 and 40 °C, respectively. The most stable PETaseD186V showed an increase in Tm of 12.91 °C over PETaseWT. Molecular dynamics (MD) simulations revealed that the D186 mutations could elevate the substrate binding free energy and change substrate binding mode, and/or rigidify the flexible Loop 10, and lock Loop 10 and Helix 6 by hydrogen bonding, leading to the enhanced activity and/or thermostability of PETase variants. This work unraveled the contribution of the key second-shell residue in PETase in influencing the enzyme activity and stability, which would benefit in the rational design of efficient and thermostable PETase.
]]>Molecules doi: 10.3390/molecules29061337
Authors: Jingwen Wu Shuaihui Dang Yan Zhang Sha Zhou
The meta-diamide (m-diamide) insecticide, Broflanilide, was characterized by its high efficiency, low toxicity and lack of cross-resistance with traditional GABA receptors. In accordance with the principles of drug molecular design, easily derivable sulfur with diverse bioactivities was introduced while leading with the parent Broflanilide. Twelve novel m-diamide target compounds containing sulfide derivatives were synthesized through exploration guided by the literature. Their structures were confirmed by melting points, 1H NMR, 13C NMR and HRMS. Insecticidal activity assessments revealed that most target compounds A–D exhibited 100% lethality against Plutella xylostella (P. xylostella) and Aphis craccivora Koch (A. craccivora) at 500 mg·L−1. Notably, for P. xylostella, compounds C-2, C-3, C-4 and D-2 demonstrated 60.00–100.00% insecticidal activity even at a concentration as low as 0.625 mg·L−1. As determined by structure–activity relationship (SAR) analysis, compounds with R1 = CH3 and R2 = Br (B-1, C-2 and D-2) and sulfoxide compound C-3 contained 100.00% lethality against A. craccivora at 500 mg·L−1, surpassing the lethality when leading with the parent Broflanilide in terms of efficacy. Consequently, it can be inferred that the sulfoxide compound (C-3) requires further investigation as a potential active molecule for new insecticides. These explorations provide valuable references for future research on the synthesis and insecticidal activities of sulfide-containing m-diamide compounds.
]]>Molecules doi: 10.3390/molecules29061336
Authors: Alina Florina Serb Marius Georgescu Robert Onulov Cristina Ramona Novaconi Eugen Sisu Alexandru Bolocan Raluca Elena Sandu
Cosmetic products are chemical substances or mixtures used on the skin, hair, nails, teeth, and the mucous membranes of the oral cavity, whose use is intended to clean, protect, correct body odor, perfume, keep in good condition, or change appearance. The analysis of cosmetic ingredients is often challenging because of their huge complexity and their adulteration. Among various analytical tools, mass spectrometry (MS) has been largely used for compound detection, ingredient screening, quality control, detection of product authenticity, and health risk evaluation. This work is focused on the MS applications in detecting and quantification of some common cosmetic ingredients, i.e., preservatives, dyes, heavy metals, allergens, and bioconjugates in various matrices (leave-on or rinse-off cosmetic products). As a global view, MS-based analysis of bioconjugates is a narrow field, and LC- and GC/GC×GC-MS are widely used for the investigation of preservatives, dyes, and fragrances, while inductively coupled plasma (ICP)-MS is ideal for comprehensive analysis of heavy metals. Ambient ionization approaches and advanced separation methods (i.e., convergence chromatography (UPC2)) coupled to MS have been proven to be an excellent choice for the analysis of scented allergens. At the same time, the current paper explores the challenges of MS-based analysis for cosmetic safety studies.
]]>Molecules doi: 10.3390/molecules29061335
Authors: Zongyi Su Wei Chen Shanshan Liang Hao Fang Minglu Zhang Meng Wang Lingna Zheng Bing Wang Yi Bi Weiyue Feng
Understanding the final fate of nanomaterials (NMs) in the liver is crucial for their safer application. As a representative two-dimensional (2D) soft nanomaterial, graphene oxide (GO) has shown to have high potential for applications in the biomedical field, including in biosensing, drug delivery, tissue engineering, therapeutics, etc. GO has been shown to accumulate in the liver after entering the body, and thus, understanding the GO–liver interaction will facilitate the development of safer bio-applications. In this study, the hepatic clearance of two types of PEGylated GOs with different lateral sizes (s-GOs: ~70 nm and l-GOs: ~300 nm) was carefully investigated. We found that GO sheets across the hepatic sinusoidal endothelium, which then may be taken up by the hepatocytes via the Disse space. The hepatocytes may degrade GO into dot-like particles, which may be excreted via the hepatobiliary route. In combination with ICP-MS, LA-ICP-MS, and synchrotron radiation FTIR techniques, we found that more s-GO sheets in the liver were prone to be cleared via hepatobiliary excretion than l-GO sheets. A Raman imaging analysis of ID/IG ratios further indicated that both s-GO and l-GO generated more defects in the liver. The liver microsomes may contribute to GO biotransformation into O-containing functional groups, which plays an important role in GO degradation and excretion. In particular, more small-sized GO sheets in the liver were more likely to be cleared via hepatobiliary excretion than l-GO sheets, and a greater clearance of s-GO will mitigate their hepatotoxicity. These results provide a better understanding of the hepatic clearance of soft NMs, which is important in the safer-by-design of GO.
]]>Molecules doi: 10.3390/molecules29061334
Authors: Kun Yu Wei He Xiaoli Ma Qi Zhang Chunxu Chen Peiyan Li Di Wu
Currently, little is known about the characteristics of polyphenol oxidase from wheat bran, which is closely linked to the browning of wheat product. The wheat PPO was purified by ammonium sulfate precipitation, DEAE-Sepharose ion-exchange column, and Superdex G-75 chromatography column. Purified wheat PPO activity was 11.05-fold higher, its specific activity was 1365.12 U/mg, and its yield was 8.46%. SDS-PAGE showed that the molecular weight of wheat PPO was approximately 21 kDa. Its optimal pH and temperature were 6.5 and 35 °C for catechol as substrate, respectively. Twelve phenolic substrates from wheat and green tea were used for analyzing the substrate specificity. Wheat PPO showed the highest affinity to catechol due to its maximum Vmax (517.55 U·mL−1·min−1) and low Km (6.36 mM) values. Docking analysis revealed strong affinities between catechol, gallic acid, EGCG, and EC with binding energies of −5.28 kcal/mol, −4.65 kcal/mol, −4.21 kcal/mol, and −5.62 kcal/mol, respectively, for PPO. Sodium sulfite, ascorbic acid, and sodium bisulfite dramatically inhibited wheat PPO activity. Cu2+ and Ca2+ at 10 mM were considered potent activators and inhibitors for wheat PPO, respectively. This report provides a theoretical basis for controlling the enzymatic browning of wheat products fortified with green tea.
]]>Molecules doi: 10.3390/molecules29061332
Authors: Wei Xu Li Du Zhengkun Du Wei He Hongxiang Li Guojuan Li Cheng Yang Pei Cheng Zhong Cao Donghong Yu
Although much promising synthetic progress in conjugated polymer-based organic solar cells (OSCs) has resulted in significant improvement in power conversion efficiencies (PCEs) of from over 15 to >19.0% in the last five years, the sophisticated and complex reactions from at least two families’ monomers with remarkably different electron push–pull effects could still pose an unavoidable material burden for the commercialization of OSCs in the coming future. Therefore, the method of preparing a homopolymer from a sole monomer would significantly reduce the synthetic steps and costs in order to pave the way for the large-scale production of OSC materials. Therefore, alkylthio-thiophenyl-substituted benzo[1,2-b;4,5-b′]dithiophene (BDTTS) as the sole and key structural moiety with dihalogen and distannyl functional groups was designed and synthesized, respectively, in this study, for facile monomer syntheses and polymerizations to achieve three wide-bandgap homopolymer donors of BDTTS-alt-BDTT-Cl (P13), BDTTS-alt-BDTT (P15), and BDTTS (P14), respectively. The structural symmetry dependency on their physical, electrochemical, and optical properties, thin-film morphologies, and photovoltaic (PV) performance was investigated in detail. As a result, OSCs based on the asymmetric polymer P15, paired with BTP-eC9 as the electron acceptor, presented the best PV performance, with a PCE of 11.5%, a fill factor (FF) of 65.87%, and a short-circuit current (JSC) of 22.04 mA·cm−2, respectively. This PCE value is among the highest ones reported for BDT-type homopolymer donor-based OPVs, providing us with knowledge for obtaining promising PV performance from devices made of P15-like materials.
]]>Molecules doi: 10.3390/molecules29061333
Authors: Sara Janowska Joanna Stefańska Dmytro Khylyuk Monika Wujec
The search for new antibacterial compounds is still a huge challenge for scientists. Each new chemotherapy drug is not 100% effective when introduced into treatment. Bacteria quickly become resistant to known structures. One promising group of new compounds is thiosemicarbazides. In the presented work, we looked for the relationship between structure and antibacterial activity within the group of thiosemicarbazide derivatives. This is a continuation of our previous work. Here, we decided to check to what extent the position of the 3-methoxyphenyl substituent affects potency. We obtained new structures that differ in the positions of the substituent in the thiosemicarbazide skeleton. Based on the obtained results of the biological tests, it can be concluded that the substituent in position 1 of thiosemicarbazide derivatives significantly determines their activity. Generally, among the substituents used, trifluoromethylphenyl turned out to be the most promising. The MIC values for compounds with this substituent are 64 µg/mL towards Staphylococci sp. Using molecular docking, we tried to explain the mechanism behind the antibacterial activity of the tested compounds.
]]>Molecules doi: 10.3390/molecules29061331
Authors: Shun Hase Kyohei Yamashita Yoshihito Kayaki
The carboxylation of unsaturated amine and alcohol compounds, including 4-benzylamino-1-phenyl-1-butyne (homopropargylamine), 2-butyne-1-ol (propargylic alcohol), and 2,3-butadiene-1-ol (allenylmethyl alcohol), using the hydroxidogold(I) complex, AuOH(IPr) [IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene], produces corresponding alkenylgold(I) complexes with a cyclic urethane or carbonate framework in high yields. The reaction takes place in aprotic THF at room temperature under the atmospheric pressure of CO2 in the absence of base additives. The products were characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The functionalized alkenyl complexes prepared from the alkynes can be protonated by treatment with an equimolar amount of acetic acid to afford five- or six-membered carboxylation products, whereas the related alkenyl complex derived from allenylmethyl alcohol decomposed to recover the starting allene via ring-opening decarboxylation.
]]>Molecules doi: 10.3390/molecules29061330
Authors: Jikang Xu Yu Zhang Lijuan Shen Lingyu Du Hongjuan Xue Bin Wu Bo OuYang
Cytotoxic T-lymphocyte antigen 4 (CTLA-4) is a pivotal immune checkpoint receptor, playing a crucial role in modulating T-cell activation. In this study, we delved into the underlying mechanism by which a common mutation, G199R, in the cytoplasmic domain of CTLA-4 impacts its inhibitory function. Utilizing nuclear magnetic resonance (NMR) spectroscopy and biochemical techniques, we mapped the conformational changes induced by this mutation and investigated its role in CTLA-4 activity. Our findings reveal that this mutation leads to a distinct conformational alteration, enhancing protein–membrane interactions. Moreover, functional assays demonstrated an improved capacity of the G199R mutant to downregulate T-cell activation, underscoring its potential role in immune-related disorders. These results not only enhance our understanding of CTLA-4 regulatory mechanisms but also provide insights for targeted therapeutic strategies addressing immune dysregulation linked to CTLA-4 mutations.
]]>Molecules doi: 10.3390/molecules29061329
Authors: Luyan Zou Shuhan Yi Yuanliang Wang
In Asian regions, areca nuts are tropical fruits that are extensively consumed. The areca nut contains a lot of polyphenols and its safety is unknown. In this research, we investigated the effects of lipopolysaccharides (LPS) and areca nut polyphenols (ANP) on normal RAW264.7 cells. The results showed that LPS stimulated adverse effects in normal cells by affecting cytokine production. The GO analysis results mainly affected DNA repair, cell division, and enzyme activities. In the KEGG analysis results, the NOD-like receptor signaling pathway, which is related to NF-κB, MAPK, and the pro-inflammatory cytokines, is the most significant. In the protein–protein interaction network (PPI) results, significant sub-networks in all three groups were shown to be related to cytokine–cytokine receptor interaction. Collectively, our findings showed a comprehensive understanding of LPS-induced toxicity and the protective effects of ANP by RNA sequencing.
]]>Molecules doi: 10.3390/molecules29061328
Authors: Yuliang Hu Jinping Bao Dongyu Tang Shushan Gao Fei Wang Zhongtao Ding Chengsen Cui
(R)-Homobenzylic amines are key structural motifs present in (R)-selegiline, a drug indicated for the treatment of early-stage Parkinson’s disease. Herein, we report a new short chemoenzymatic approach (in 2 steps) towards the synthesis of (R)-selegiline via stereoselective biocatalytic reductive amination as the key step. The imine reductase IR36-M5 mutant showed high conversion (97%) and stereoselectivity (97%) toward the phenylacetone and propargyl amine substrates, offering valuable biocatalysts for synthesizing alkylated homobenzylic amines.
]]>Molecules doi: 10.3390/molecules29061327
Authors: Mihaela Brumă (Călin) Ina Vasilean Leontina Grigore-Gurgu Iuliana Banu Iuliana Aprodu
Pepsin, trypsin and proteinase K were used in the present study to hydrolyse the proteins from whole eggs, yolks or whites, and the resulting hydrolysates were characterised in terms of antioxidant and IgE-binding properties, using a combination of in vitro and in silico methods. Based on the degree of hydrolysis (DH) results, the egg yolk proteins are better substrates for all the tested enzymes (DH of 6.2–20.1%) compared to those from egg whites (DH of 2.0–4.4%). The SDS-PAGE analysis indicated that pepsin and proteinase K were more efficient compared to trypsin in breaking the intramolecular peptide bonds of the high molecular weight egg proteins. For all the tested substrates, enzyme-assisted hydrolysis resulted in a significant increase in antioxidant activity, suggesting that many bioactive peptides are encrypted in inactive forms in the parent proteins. The hydrolysates obtained with proteinase K exhibited the highest DPPH radical scavenging activity (124–311 µM Trolox/g protein) and the lowest residual IgE-binding capacity. The bioinformatics tools revealed that proteinase K is able to break the integrity of the main linear IgE-binding epitopes from ovalbumin and ovomucoid. It can be concluded that proteinase K is a promising tool for modulating the intrinsic properties of egg proteins.
]]>Molecules doi: 10.3390/molecules29061326
Authors: Mohamed S. Mostafa Ibrahim Ali M. Radini Naglaa M. Abd El-Rahman Rizk E. Khidre
This review article examines the synthetic pathways for triazolothiadiazine derivatives, such as triazolo[3,4-b]thiadiazines, triazolo[5,1-b]thiadiazines, and triazolo[4,3-c]thiadiazines, originating from triazole derivatives, thiadiazine derivatives, or thiocarbohydrazide. The triazolothiadiazine derivatives exhibit several biological actions, including antibacterial, anticancer, antiviral, antiproliferative, analgesic, anti-inflammatory, and antioxidant properties. The review article aims to assist researchers in creating new biologically active compounds for designing target-oriented triazolothiadiazine-based medicines to treat multifunctional disorders.
]]>Molecules doi: 10.3390/molecules29061325
Authors: Boshen Du Wanyuan Li Lin Zhang Pei Chen Fengniu Lu
In recent years, high-power white light-emitting diode (wLED)/laser diode (wLD) lighting sources based on transparent phosphor ceramic (TPC) materials have attracted increasing application interest in automotive headlights, projection displays, and space navigation lighting due to their superior brightness, lighting distance, compactness, lifespan, and environmental resistance compared with the widely used phosphor-converted wLEDs. However, preparing TPC-converted wLEDs/wLDs with high color rendering index (CRI) remains a huge challenge, which limits their widespread application. In this review, we summarize the recently adopted strategies for constructing TPCs to develop high-power wLEDs/wLDs with high CRI values (>75). The construction protocols were categorized into four groups: host regulation, red-emitter doping, host regulation/red-emitter doping combination, and composite structure design. A comprehensive discussion was conducted on the design principles, photoluminescent properties, and device performances for each strategy. The challenges and future trends of high-power and high-CRI wLEDs/wLDs based on TPCs are also discussed toward the end of this review.
]]>Molecules doi: 10.3390/molecules29061324
Authors: Greg Brewer Cynthia Brewer Raymond J. Butcher Peter Zavalij
The Schiff base condensation of 5-methyl-4-imidazole carboxaldehyde, 5Me4ImCHO, and the anion of an amino acid, H2N-CH(R)CO2− (R = -CH3, -CH(CH3)2 and -CH2CH(CH3)2), gives the aldimine tautomer, Im-CH=N-CH(R)CO2−, while that of 5-methylimidazole-4-methanamine, 5MeIm-4-CH2NH2, with a 2-oxocarboxylate anion, R-C(O)-CO2−, gives the isomeric ketimine tautomer, Im-CH2-N=C(R)CO2−. All are isolated as the neutral nickel(II) complexes, NiL2, and are characterized by single crystal structure determination, IR, and positive ion ESI MS. In the cases of the 4 substituted imidazoles, either 5MeIm-4-CHO or 5MeIm-4-CH2NH2, both the aldimine and ketimine complexes are isolated cleanly with no evidence of an equilibrium between the two tautomers under the experimental conditions. The aldimines are blue while the tautomeric ketimines are green. In contrast, for the 2-substituted imidazoles, with either Im-2-CHO or Im-2-CH2NH2, the isolated product from the Schiff base condensation is the ketimine, which in the solid is green, as observed for the 4-isomer. These results suggest that for the 2-substituted imidazoles, there is a facile equilibrium between the aldimine and ketimine tautomers, and that the ketimine form is the thermodynamically favored tautomer. The aldimine tautomers of the 4-substituted imidazoles have three stereogenic centers, the nickel (Δ or Ʌ) and the two alpha carbon atoms (R or S). The observed pair of enantiomers is the ɅRR/ΔSS enantiomeric pair, suggesting that this pair is lower in energy than the others and that this is in general the preferred chiral correlation in these complexes.
]]>Molecules doi: 10.3390/molecules29061323
Authors: Yu Cao Changlong Leng Kuan Lin Youwei Li Meiling Zhou Mei Zhou Xiji Shu Wei Liu
Previous studies have revealed the microbial metabolism of dietary choline in the gut, leading to its conversion into trimethylamine (TMA). Polymethoxyflavones (PMFs), exemplified by tangeretin, have shown efficacy in mitigating choline-induced cardiovascular inflammation. However, the specific mechanism by which these compounds exert their effects, particularly in modulating the gut microbiota, remains uncertain. This investigation focused on tangeretin, a representative PMFs, to explore its influence on the gut microbiota and the choline–TMA conversion process. Experimental results showed that tangeretin treatment significantly attenuated the population of CutC–active bacteria, particularly Clostridiaceae and Lactobacillus, induced by choline chloride in rat models. This inhibition led to a decreased efficiency in choline conversion to TMA, thereby ameliorating cardiovascular inflammation resulting from prolonged choline consumption. In conclusion, tangeretin’s preventive effect against cardiovascular inflammation is intricately linked to its targeted modulation of TMA–producing bacterial activity.
]]>Molecules doi: 10.3390/molecules29061322
Authors: Nastassja Burrini Arnaud Pâris Guillaume Collet Pierre Lafite Richard Daniellou
This study unveils an innovative method for synthesizing coumarin S-glycosides, employing original biocatalysts able to graft diverse carbohydrate structures onto 7-mercapto-4-methyl-coumarin in one-pot reactions. The fluorescence properties of the generated thio-derivatives were assessed, providing valuable insights into their potential applications in biological imaging or sensing. In addition, the synthesized compounds exhibited no cytotoxicity across various human cell lines. This research presents a promising avenue for the development of coumarin S-glycosides, paving the way for their application in diverse biomedical research areas.
]]>Molecules doi: 10.3390/molecules29061321
Authors: Guo Wang Zhao Wang Wang Yang Yang Ma
In order to evaluate the physical and chemical properties of polymer surfactants and analyze their oil displacement mechanisms, three types of poly-surfactant used in the Daqing oil field were chosen to be researched, and the oil displacement effects were studied using poly-surfactants of different viscosity, dehydrating rate, and core permeability. The main purpose is to determine the reasonable range of different characteristic indexes of polymeric surfactant flooding. The oil displacement effect of 15 cores was analyzed, and the effects of viscosity, the dehydrating rate of emulsion, and permeability on EOR (Enhanced Oil Recovery) were analyzed. The oil displacement mechanisms of polymeric surfactants were researched using a photolithographic glass core. This paper explores the mechanism underlying production enhancement as an EOR target, while simultaneously conducting laboratory tests to assess the physical and chemical properties of polymeric surfactants. The poly-surfactant agents exhibit a notable increase in viscosity, with the optimal displacement effect observed at a core effective permeability exceeding 400 mD, resulting in a potential EOR of 15% or higher. Moreover, at a viscosity ranging between 40 and 70 mPa·s, the total EOR can reach 73%, with the peak efficiency occurring at a viscosity of 60 mPa·s. The water loss rate of the emulsion, ranging between 30% and 70%, achieves optimal performance at 50%. The poly-surfactants’ higher viscosity extends the oil sweep area, enhancing recovery efficiency, and noticeably reducing residual oil compared to water flooding. During poly-surfactant flooding, a substantial amount of residual oil is extracted and transformed into droplets. The rapid emulsification of the polymeric surfactant solution with crude oil forms a stable emulsion, contributing to its significant oil recovery effect. This research provides valuable technical support for EOR in thin and low-quality reservoirs of onshore multi-layered sandstone reservoirs.
]]>Molecules doi: 10.3390/molecules29061320
Authors: Wamidh H. Talib Media Mohammed Baban Aya O. Azzam Jenan J. Issa Alaa Y. Ali Alia Kh. AlSuwais Sana Allala Lina T. AL Kury
Natural products, particularly medicinal plants, are crucial in combating cancer and aiding in the discovery and development of new therapeutic agents owing to their biologically active compounds. They offer a promising avenue for developing effective anticancer medications because of their low toxicity, diverse chemical structures, and ability to target various cancers. Allicin is one of the main ingredients in garlic (Allium sativum L.). It is a bioactive sulfur compound maintained in various plant sections in a precursor state. Numerous studies have documented the positive health benefits of this natural compound on many chronic conditions, including gastric, hepatic, breast, lung, cervical, prostate, and colon cancer. Moreover, allicin may target several cancer hallmarks or fundamental biological traits and functions that influence cancer development and spread. Cancer hallmarks include sustained proliferation, evasion of growth suppressors, metastasis, replicative immortality, angiogenesis, resistance to cell death, altered cellular energetics, and immune evasion. The findings of this review should provide researchers and medical professionals with a solid basis to support fundamental and clinical investigations of allicin as a prospective anticancer drug. This review outlines the anticancer role of allicin in each hallmark of cancer.
]]>Molecules doi: 10.3390/molecules29061319
Authors: Federica Aiello Alessandra Recchimurzo Federica Balzano Gloria Uccello Barretta Federica Cefalì
In the exploration of chiral solvating agents (CSAs) for nuclear magnetic resonance (NMR) spectroscopy designed for the chiral analysis of amino acid derivatives, notable advancements have been made with thiourea–CSAs. 1-TU, derived from 2-[(1R)-1-aminoethyl]phenol and benzoyl isothiocyanate, is effective in the enantiodifferentiation of N-3,5-dinitrobenzoyl (N-DNB) amino acids. In order to broaden the application of 1-TU for configurational assignment, enantiomerically enriched N-DNB amino acids were analyzed via NMR. A robust correlation was established between the relative position of specific 1H and 13C NMR resonances of the enantiomers in the presence of 1-TU. 1,4-Diazabicyclo[2.2.2]octane (DABCO) was selected for the complete solubilization of amino acid substrates. Notably, the para and ortho protons of the N-DNB moiety displayed higher frequency shifts for the (R)-enantiomers as opposed to the (S)-enantiomers. This trend was consistently observed in the 13C NMR spectra for quaternary carbons bonded to NO2 groups. Conversely, an inverse correlation was noted for quaternary carbon resonances of the carboxyl moiety, amide carbonyl, and methine carbon at the chiral center. This observed trend aligns with the interaction mechanism previously reported for the same chiral auxiliary. The configurational correlation can be effectively exploited under conditions of high dilution or, significantly, under sub-stoichiometric conditions.
]]>Molecules doi: 10.3390/molecules29061318
Authors: Aziadé Chemat Didier Touraud Rainer Müller Werner Kunz Anne-Sylvie Fabiano-Tixier
Coffee silverskin is a byproduct of the coffee industry, appearing in large quantities during the roasting step. In this work, a sober and simple water process is proposed, using extractions cycles, to produce valuable products including (a) an extract rich in caffeine, (b) possibly pure caffeine, and (c) insoluble fibers. The hypothetical number of necessary cycles was calculated and compared to the number of cycles used experimentally. Two types of cycles, with and without water compensation, were compared for their water consumption and the amount of caffeine extracted. The use of cycles, with the resulting product from a previous extraction as a solvent for fresh biomass, drove a significant rise in the content of caffeine determined by a UV–visible detector with a spectrophotometer and ultra-performance liquid chromatography (UPLC). After 11 extraction cycles with water compensation, we obtained an extract 4.5 times more concentrated in caffeine (4.25 mg/mL) than after a single extraction (1.03 mg/mL).
]]>Molecules doi: 10.3390/molecules29061317
Authors: George Barany Paul R. Hansen
The international peptide community rejoiced when one of its most distinguished members, Morten Meldal of Denmark, shared the 2022 Nobel Prize in Chemistry. In fact, the regiospecific solid-phase “copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes to azides” (CuACC) reaction—that formed the specific basis for Meldal’s recognition—was reported first at the 17th American Peptide Symposium held in San Diego in June 2001. The present perspective outlines intertwining conceptual and experimental threads pursued concurrently in Copenhagen and Minneapolis, sometimes by the same individuals, that provided context for Meldal’s breakthrough discovery. Major topics covered include orthogonality in chemistry; the dithiasuccinoyl (Dts) protecting group for amino groups in α-amino acids, carbohydrates, and monomers for peptide nucleic acids (PNA); and poly(ethylene glycol) (PEG)-based solid supports such as PEG–PS, PEGA, and CLEAR [and variations inspired by them] for solid-phase peptide synthesis (SPPS), solid-phase organic synthesis (SPOS), and combinatorial chemistry that can support biological assays in aqueous media.
]]>Molecules doi: 10.3390/molecules29061312
Authors: Spyridon Mourtas Georgios Kourmoulakis Stavros Kremezis Pavlos Klepetsanis Sophia G. Antimisiaris
With the aim to develop novel scaffolds for the sustained release of drugs, we initially developed an easy approach for the synthesis of α,ω-homobifunctional mercaptoacyl poly(alkyl oxide)s. This was based on the esterification of the terminal hydroxyl groups of poly(alkyl oxide)s with suitably S-4-methoxytrityl (Mmt)-protected mercapto acids, followed by the removal of the acid labile S-Mmt group. This method allowed for the efficient synthesis of the title compounds in high yield and purity, which were further used in the development of a thioether cross-linked liposome scaffold, by thia–Michael reaction of the terminal thiol groups with pre-formed nano-sized liposomes bearing maleimide groups on their surface. The reaction process was followed by 1H-NMR, using a Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion NMR experiment (1H-NMR CPMG), which allowed for real-time monitoring and optimization of the reaction process. The thioether cross-linked liposomal scaffold that was synthesized was proven to preserve the nano-sized characteristics of the initial liposomes and allowed for the sustained release of calcein (which was used as a hydrophilic dye and a hydrophilic drug model), providing evidence for the efficient synthesis of a novel drug release scaffold consisting of nanoliposome building blocks.
]]>Molecules doi: 10.3390/molecules29061316
Authors: Rui Ren Ming-yan Zhang Tengyun Shu Ya-ting Kong Li-hua Su Hai-zhou Li
The fruits of Solanum torvum Swartz, a wild relative of eggplant, are consumed as a wild vegetable in tropical regions of Africa, Asia, and South America. In traditional Chinese medicine, it is believed to have anti-inflammatory and sedative effects. In the Philippines, water decoction is used to treat hyperactivity disorder. Twenty-two steroidal saponins were isolated and purified from the fruits grown in Yunnan, China, including six new compounds: torvosides U–Z (1–6). During drying and cooking, the saponins may undergo transformation, resulting in small amounts of sapogenins. These transformations can include dehydration of hydroxyl groups at position C22, formation of double bonds at position 20, 22 or 22, 23, and even formation of peroxide products. Saponin compounds torvoside X (4), torvoside Y (5), torvoside A (7), and (25S)-3-oxo-5α-spirostan-6α-yl-O-β-d-xylopyranoside (20), which are glycosylated at C-6, showed certain anti-epileptic activity in a pentylenetetrazole-induced zebrafish seizure model. No antiproliferative activity was detected when tested on the cancer cell line HepG2, and no hepatotoxic effect was noted on normal liver cell line LO2.
]]>Molecules doi: 10.3390/molecules29061315
Authors: Na Su
Owing to their special structure and excellent physical and chemical properties, conducting polymers have attracted increasing attention in materials science. In recent years, tremendous efforts have been devoted to improving the comprehensive performance of conducting polymers by using the technique of “doping.” Spherical polyelectrolyte brushes (SPBs) bearing polyelectrolyte chains grafted densely to the surface of core particles have the potential to be novel dopant of conducting polymers not only because of their spherical structure, high grafting density and high charge density, but also due to the possibility of their being applied in printed electronics. This review first presents a summary of the general dopants of conducting polymers. Meanwhile, conducting polymers doped with spherical polyelectrolyte brushes (SPBs) is highlighted, including the preparation, characterization, performance and doping mechanism. It is demonstrated that comprehensive performance of conducting polymers has improved with the addition of SPBs, which act as template and dopant in the synthesis of composites. Furthermore, the applications and future developments of conductive composites are also briefly reviewed and proposed, which would draw more attention to this field.
]]>Molecules doi: 10.3390/molecules29061314
Authors: Xiaolan Chen Guangjie Zhang Wenjin Cui Chunbo Ge Bin Li Min Li Shuchen Liu Lin Wang
Orychophragmus violaceus (L.) O. E. Schulz (Brassicaceae) is widely distributed and plentiful in China and has been widely used for its application in ornamental, oil, ecology, foraging, and food. Recent studies have revealed that the main components of Orychophragmus violaceus include flavonoids, alkaloids, phenylpropanoids, phenolic acids, terpenoids, etc., which have pharmacological activities such as antioxidation, antiradiation, antitumor, hepatic protection, antiferroptosis, anti-inflammatory, and antibacterial. In this paper, the nutritional value, chemical compositions, pharmacological activity, and application value of Orychophragmus violaceus are summarized by referring to the relevant domestic and international literature to provide a reference for further research, development, and utilization of Orychophragmus violaceus in the future.
]]>Molecules doi: 10.3390/molecules29061313
Authors: Muhamad Jalu Purnomo Yosi Febrita Okto Dinaryanto Wojciech Gierlotka Ing-Song Yu
Boron nitride (BN) is a wide-bandgap material for various applications in modern nanotechnologies. In the technology of material science, computational calculations are prerequisites for experimental works, enabling precise property prediction and guidance. First-principles methods such as density functional theory (DFT) are capable of capturing the accurate physical properties of materials. However, they are limited to very small nanoparticle sizes (<2 nm in diameter) due to their computational costs. In this study, we present, for the first time, an important computational approach to DFT calculations for BN materials deposited on different substrates. In particular, we predict the total energy and cohesive energy of a variety of face-centered cubic (FCC) and hexagonal close-packed (HCP) boron nitrides on different substrates (Ni, MoS2, and Al2O3). Hexagonal boron nitride (h-BN) is the most stable phase according to our DFT calculation of cohesive energy. Moreover, an experimental validation equipped with a molecular beam epitaxy system for the epitaxial growth of h-BN nanodots on Ni and MoS2 substrates is proposed to confirm the results of the DFT calculations in this report.
]]>Molecules doi: 10.3390/molecules29061311
Authors: Ziming Wang Qiu Wang Yingrui Jin Kun Guo Xiaoling Wang Xueting Feng
According to ancient Chinese books, bear grease has the effects of strengthening muscles and bones, which is beneficial for weakness, but there is relatively little research on it. Thus, the extraction of it is beneficial for compensating for research in this area. In this study, a uniform experimental design method was used to optimize the extraction process of bear grease by enzymatic hydrolysis extraction, and the extraction rate can reach 81.89% under optimized extraction conditions. Furthermore, the components of bear grease obtained by this study were analyzed by GC-MS, and the results showed that ursolic oil was rich in unsaturated fatty acids (67.51%), which was higher than that of the traditional method (66.92%). The composition of bear grease extracted by the enzymatic method was also better than that extracted by the traditional method. In addition, bear grease obtained in this study had the obvious activity of promoting hair growth. The length, weight, and number of hair follicles in the depilation area of mice in the high-dose group were significantly different from those in the blank group (p < 0.01). This study optimized the extraction process of bear grease and conducted a preliminary analysis of its fatty acid composition, which is expected to provide some reference for the development of the medicinal value of bear grease.
]]>Molecules doi: 10.3390/molecules29061310
Authors: Jolanta Polak Marcin Grąz Katarzyna Szałapata Justyna Kapral-Piotrowska Kamila Wlizło Marcin Polak Anna Jarosz-Wilkołazka
Biocatalysis processes based on oxidoreductases, such as fungal laccase, are important for discovering new organic compounds with broad structures and potential applications. They include bioactive compounds, which can be obtained through laccase-mediated oxidation of organic substrates having hydroxyl and/or amino groups especially, e.g., 5-aminosalicylic acid (5-ASA) is characterised for its potential for oxidation by a fungal laccase obtained from a Cerrena unicolor strain. The biotransformation process was optimised in terms of the buffer and co-solvent concentration, buffer pH value, and laccase activity. Selected crude dyes were analysed for their bioactive properties, toxicity, and suitability for the dyeing of wool fibres. The data obtained clearly indicated that a low concentration of the reaction buffer in the pH range from 5 to 6 and in the presence of 10% acetonitrile increased the rate of substrate oxidation and the amount of the product formed. The red-brown compound obtained via laccase-mediated oxidation of 5-aminosalicylic acid showed antioxidant properties and unique antimicrobial activity against Staphylococcus aureus and Staphylococcus epidermidis strains with the MIC value of 0.125 mg/mL detected for the purest dye. In addition, it was reported to have good wool fibre dyeing properties and no irritant effect after patch tests on a selected group with increased skin sensitivity.
]]>Molecules doi: 10.3390/molecules29061309
Authors: Najla A. Alshaye Mohamed K. Elgohary Mahmoud S. Elkotamy Hatem A. Abdel-Aziz
COX-2 plays a key role in converting arachidonic acid into prostaglandins. This makes it a significant target for treating inflammation. Selective COX-2 inhibitors have marked a new phase in inflammatory treatment, providing significant effectiveness while reducing negative side effects. Herein, we aimed at the design and synthesis of new anti-inflammatory agents 5a–f, 7a–b, 10a–f, and 13a–b with expected selective inhibition for COX-2. Compounds 5d–f, 7b, and 10c–f showed significant COX-2 inhibition with IC50 in the range of 0.06–0.09 μM, indicating powerful pharmacological potential. In light of this, eight compounds were selected for further testing in vivo to assess their selectivity toward COX-1/COX-2 enzymes with the ability to reduce paw thickness. Compounds 5f and 7b showed significant anti-inflammatory effects without causing stomach ulcers, as they showed significant in vivo inhibition for paw thickness at 63.35% and 46.51%, as well as paw weight at 68.26% and 64.84%. Additionally, the tested compounds lowered TNF-α by 61.04% and 64.88%, as well as PGE-2 by 60.58% and 57.07%, respectively. Furthermore, these potent compounds were thoroughly analyzed for their pain-relieving effects, histological changes, and toxicological properties. Assessing renal and stomach function, as well as measuring liver enzymes AST and ALT, together with kidney indicators creatinine and urea, offered valuable information on their safety profiles. Molecular modeling studies explain the complex ways in which the strong interacts with the COX-2 enzyme. This comprehensive strategy emphasizes the therapeutic potential and safety profiling of these new analogues for managing inflammation.
]]>Molecules doi: 10.3390/molecules29061308
Authors: Xianshu Fu Xiangliang Pan Jun Chen Mingzhou Zhang Zihong Ye Xiaoping Yu
The pollution from waste plastic express packages (WPEPs), especially microplastic (MP) fragments, caused by the blowout development of the express delivery industry has attracted widespread attention. On account of the variety of additives, strong complexity, and high diversity of plastic express packages (PEPs), the multi-class classification of WPEPs is a typical large-class-number classification (LCNC). The traceability and identification of microplastic fragments from WPEPs is very challenging. An effective chemometric method for large-class-number classification would be very beneficial for the comprehensive treatment of WPEP pollution through the recycling and reuse of waste plastic express packages, including microplastic fragments and plastic debris. Rather than using the traditional one-against-one (OAO) and one-against-all (OAA) dichotomies, an exhaustive and parallel half-against-half (EPHAH) decomposition, which overcomes the defects of the OAO’s classifier learning limitations and the OAA’s data proportion imbalance, is proposed for feature selection. EPHAH analysis, combined with partial least squares discriminant analysis (PLS-DA) for large-class-number classification, was performed on 750 microplastic fragments of polyethylene WPEPs from 10 major courier companies using near-infrared (NIR) spectroscopy. After the removal of abnormal samples through robust principal component analysis (RPCA), the root mean square error of cross-validation (RMSECV) value for the model was reduced to 0.01, which was 21.5% lower than that including the abnormal samples. The best models of PLS-DA were obtained using SNV combined with SG-17 smoothing and 2D (SNV+SG-17+2D); the latent variables (LVs), the error rates of Monte Carlo cross-validation (ERMCCVs), and the final classification accuracies were 6.35, 0.155, and 88.67% for OAO-PLSDA; 5.37, 0.103, and 87.33% for OAA-PLSDA; and 3.12, 0.054, and 96.00% for EPHAH-PLSDA. The results showed that the EPHAH strategy can completely learn the complex LCNC decision boundaries for 10 classes, effectively break the tie problem, and greatly improve the voting resolution, thereby demonstrating significant superiority to both the OAO and OAA strategies in terms of classification accuracy. Meanwhile, PLS-DA further maximized the covariance and data interpretation abilities between the potential variables and categories of microplastic debris, thereby establishing an ideal performance identification model with a recognition rate of 96.00%.
]]>Molecules doi: 10.3390/molecules29061307
Authors: Federica Cefalì Anna Iuliano Federica Balzano Gloria Uccello Barretta Valerio Zullo Carlo Baldassari
New arylamide- and arylthiourea-based chiral solvating agents (CSAs) were synthesized starting from commercially available isomannide and isosorbide. The two natural isohexides were transformed into the three amino derivatives, having isomannide, isosorbide, and isoidide stereochemistry, then the amino groups were derivatized with 3,5-dimethoxybenzoyl chloride or 3,5-bis(trifluoromethyl)phenyl isothiocyanate to obtain the CSAs. Bis-thiourea derivative containing the 3,5-bis(trifluoromethyl)phenyl moiety with exo–exo stereochemistry was remarkably efficient in the differentiation of NMR signals (NH and acetyl) of enantiomers of N-acetyl (N-Ac) amino acids in the presence of 1,4-diazabicyclo[2,2,2]octane (DABCO). Nonequivalences in the ranges of 0.104–0.343 ppm and 0.042–0.107 ppm for NH and acetyl groups, respectively, allowed for very accurate enantiomeric excess determination, and a reliable correlation was found between the relative positions of signals of enantiomers and their absolute configuration. Therefore, a complete stereochemical characterization could be performed. Dipolar interactions detected in the ternary mixture CSA/N-Ac-valine/DABCO led to the identification of a different interaction model for the two enantiomers, involving the formation of a one-to-one substrate/CSA complex for (S)-N-Ac-valine and a one-to-two complex for (R)-N-Ac-valine, as suggested by the complexation stoichiometry.
]]>Molecules doi: 10.3390/molecules29061306
Authors: Aleksandra Smejda-Krzewicka Emilia Irzmańska Konrad Mrozowski Agnieszka Adamus-Włodarczyk Natalia Litwicka Krzysztof Strzelec Małgorzata I. Szynkowska-Jóźwik
The aim of the study was to produce new elastomeric materials containing butyl rubber (IIR) filled with silica and phyllosilicates (vermiculite, montmorillonite, perlite or halloysite tubes) with enhanced hydrophobicity and barrier properties and reduced chemical degradation. It was found that the filler type had a significant impact on the degree of cross-linking of butyl rubber and the properties of its vulcanizates. The highest degree of cross-linking and the highest mechanical strength were achieved for IIR composites filled with Arsil with perlite or halloysite tubes. The highest surface hydrophobicity (119°) was confirmed for the IIR vulcanizates with Arsil and montmorillonite. All tested samples showed high barrier properties because both the gas diffusion rate coefficient and the permeability coefficient reached low values. Both unfilled and filled IIR vulcanizates retained chemical resistance in contact with methanol for 480 min. Hour-long contact of a polar solvent (methanol) with each of the vulcanizates did not cause material degradation, while the presence of a non-polar solvent (n-heptane) worsened the mechanical parameters by up to 80%. However, the presence of fillers reduced the chemical degradation of vulcanizates (in the case of cured IIR filled with Arsil and halloysite tubes by 40% compared to the composite without fillers).
]]>Molecules doi: 10.3390/molecules29061305
Authors: Valentina Venturi Elena Marchesi Daniela Perrone Valentina Costa Martina Catani Simona Aprile Lindomar Alberto Lerin Federico Zappaterra Pier Paolo Giovannini Lorenzo Preti
Ursodeoxycholic acid (UDCA) and acetoacetate are natural compounds present in the human intestine and blood, respectively. A number of studies highlighted that besides their well-known primary biological roles, both compounds possess the ability to influence a variety of cellular processes involved in the etiology of various diseases. These reasons suggested the potential of acetoacetate–UDCA hybrids as possible therapeutic agents and prompted us to develop a synthetic strategy to selectively derivatize the hydroxyl groups of the bile acid with acetoacetyl moieties. 3α-acetoacetoxy UDCA was obtained (60% isolated yield) via the regioselective transesterification of methyl acetoacetate with UDCA promoted by the Candida antarctica lipase B (CAL-B). 3α,7β-bis-acetoacetoxy UDCA was obtained instead by thermal condensation of methyl acetoacetate and UDCA (80% isolated yield). This bis-adduct was finally converted to the 7β-acetoacetoxy UDCA (82% isolated yield) via CAL-B catalyzed regioselective alcoholysis of the ester group on the 3α position. In order to demonstrate the value of the above new hybrids as UDCA-based scaffolds, 3α-acetoacetoxy UDCA was subjected to multicomponent Biginelli reaction with benzaldehyde and urea to obtain the corresponding 4-phenyl-3,4-dihydropyrimidin-2-(1H)-one derivative in 65% isolated yield.
]]>Molecules doi: 10.3390/molecules29061304
Authors: Patricia Budihartanti Liman Mulyana Yenny Ratna Djuwita
There is little data on directly measured carboxymethyl lysine (CML) content in Indonesian foods. This study aimed to generate a database of CML values in foods commonly consumed in West Java and West Sumatra. The results were to be used to update our previous estimated CML values. CML values in food samples were measured using high-pressure liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). Food protein content was analyzed by Kjeldahl’s method or inferred from the nutrition facts’ label. A total of 210 food samples were examined, with the food groups of meat and poultry (1.06 mg CML/100 g edible food), and starchy foods (0.21 mg/100 g edible food) having the highest and lowest mean CML levels, respectively. We found that the foods with the top three highest CML content were fried starch dough (cimol), fried fish crackers, and chicken gulai. The mean of the estimated values (0.80 mg CML/100 g edible food) was higher than the directly measured values (0.66 mg CML/100 g edible food), [p < 0.035]. Conclusion: This database provides information on CML values in Indonesian foods, and can be further used to make a guide policy for the selection of foods to reduce non-communicable diseases. Further measurements are needed on Indonesian dishes to complete the database.
]]>Molecules doi: 10.3390/molecules29061303
Authors: Hazuki Ito Kohei Monobe Saya Okubo Shunsuke Aoki
The emergence of multidrug-resistant and extensively drug-resistant Mycobacterium tuberculosis (M. tuberculosis) has become a major medical problem. S-adenosyl-L-homocysteine hydrolase (MtSAHH) was selected as the target protein for the identification of novel anti-TB drugs. Dual hierarchical in silico Structure-Based Drug Screening was performed using a 3D compound structure library (with over 150 thousand synthetic chemicals) to identify compounds that bind to MtSAHH’s active site. In vitro experiments were conducted to verify whether the nine compounds selected as new drug candidates exhibited growth-inhibitory effects against mycobacteria. Eight of the nine compounds that were predicted by dual hierarchical screening showed growth-inhibitory effects against Mycobacterium smegmatis (M. smegmatis), a model organism for M. tuberculosis. Compound 7 showed the strongest antibacterial activity, with an IC50 value of 30.2 µM. Compound 7 did not inhibit the growth of Gram-negative bacteria or exert toxic effects on human cells. Molecular dynamics simulations of 40 ns using the MtSAHH–Compound 7 complex structure suggested that Compound 7 interacts stably with the MtSAHH active site. These in silico and in vitro results suggested that Compound 7 is a promising lead compound for the development of new anti-TB drugs.
]]>Molecules doi: 10.3390/molecules29061302
Authors: Guido Cerri Antonio Brundu
Radioactive wastes often contain amorphous and crystalline phases, and vapor hydration can affect their durability. In this study, Cs-clinoptilolite was heated (at 1100 °C and for 2–36 h) to prepare the samples that were composed mainly of an amorphous phase (AmP) and CsAlSi5O12 (≥94%) with minor CsAlSi2O6. Six samples with an AmP/CsAlSi5O12 ratio from 26.5 to 0.1 were kept at 21 °C and 55% relative humidity, and their hydration was measured via thermogravimetry (TG) over a period of almost six years. The hydration that resulted was directly related to the AmP quantity. The increase in water content followed a logarithmic trend over time. It reached 1.95% in the AmP-richest material, while it attained only 0.07% in the most crystalline sample. The hydrolysis of the AmP led to an increase over time in the tightly bound water. Samples with an AmP of ≤19% demonstrated slightly higher durability due to the lower Cs content in the AmP.
]]>Molecules doi: 10.3390/molecules29061301
Authors: Jinhuan Li Min Wu Quan Du Gangpeng Zhai Haiyong He
With its substantial theoretical capacity, silicon (Si) is a prospective anode material for high-energy-density lithium-ion batteries (LIBs). However, the challenges of a substantial volume expansion and inferior conductivity in Si-based anodes restrict the electrochemical stability. To address this, a yolk-shell-structured Si–carbon composite, featuring adjustable void sizes, was synthesized using tin (Sn) as a template. A uniform coating of tin oxide (SnO2) on the surface of nano-Si particles was achieved through a simple annealing process. This approach enables the removal of the template with concentrated hydrochloric acid (HCl) instead of hydrofluoric acid (HF), thereby reducing toxicity and corrosiveness. The conductivity of Si@void@Carbon (Si@void@C) was further enhanced by using a high-conductivity carbon layer derived from pitch. By incorporating an internal void, this yolk-shell structure effectively enhanced the low Li+/electron conductivity and accommodated the large volume change of Si. Si@void@C demonstrated an excellent electrochemical performance, retaining a discharge capacity of 735.3 mAh g−1 after 100 cycles at 1.0 A g−1. Even at a high current density of 2.0 A g−1, Si@void@C still maintained a discharge capacity of 1238.5 mAh g−1.
]]>Molecules doi: 10.3390/molecules29061300
Authors: Tomohiro Imura Satohiro Yanagisawa Yuri Ikeda Ryodai Moriyama Kenichi Sakai Hideki Sakai Toshiaki Taira
Nanodiscs belong to a category of water-soluble lipid bilayer nanoparticles. In vivo nanodisc platforms are useful for studying isolated membrane proteins in their native lipid environment. Thus, the development of a practical method for nanodisc reconstruction has garnered consider-able research interest. This paper reports the self-assembly of a mixture of bio-derived cyclic peptide, surfactin (SF), and l-α-dimyristoylphosphatidylcholine (DMPC). We found that SF induced the solubilization of DMPC multilamellar vesicles to form their nanodiscs, which was confirmed by size-exclusion chromatography, dynamic light scattering, and transmission electron microscopy analyses. Owing to its amphiphilic nature, the self-assembled structure prevents the exposure of the hydrophobic lipid core to aqueous media, thus embedding ubiquinol (CoQ10) as a hydrophobic model compound within the inner region of the nanodiscs. These results highlight the feasibility of preparing nanodiscs without the need for laborious procedures, thereby showcasing their potential to serve as promising carriers for membrane proteins and various organic compounds. Additionally, the regulated self-assembly of the DMPC/SF mixture led to the formation of fibrous architectures. These results show the potential of this mixture to function as a nanoscale membrane surface for investigating molecular recognition events.
]]>Molecules doi: 10.3390/molecules29061299
Authors: Jiacheng Zhong Zimeng Liu Meng Zhang Feng Liu Wenjin Li Beirui Hou Wenmin Zhang Chunwang Zhao Mingxing Gong
The phase, mechanical properties, corrosion resistance, hydrophobicity, and interfacial contact resistance of Hastelloy X were investigated to evaluate its performance in proton exchange membrane fuel cells (PEMFCs). For comparison, the corresponding performance of 304 stainless steel (304SS) was also tested. Hastelloy X exhibited a single-phase face-centered cubic structure with a yield strength of 445.5 MPa and a hardness of 262.7 HV. Both Hastelloy X and 304SS exhibited poor hydrophobicity because the water contact angles were all below 80°. In a simulated PEMFC working environment (0.5 M H2SO4 + 2 ppm HF, 80 °C, H2), Hastelloy X exhibited better corrosion resistance than 304SS. At 140 N·cm−2, the interfacial contact resistance of Hastelloy X can reach as low as 7.4 mΩ·cm2. Considering its overall performance, Hastelloy X has better potential application than 304SS as bipolar plate material in PEMFCs.
]]>Molecules doi: 10.3390/molecules29061298
Authors: Beata Pająk Rafał Zieliński Waldemar Priebe
Glucose metabolism is a crucial biological pathway maintaining the activation of extra- and intracellular signaling pathways involved in the immune response. Immune cell stimulation via various environmental factors results in their activation and metabolic reprogramming to aerobic glycolysis. Different immune cells exhibit cell-type-specific metabolic patterns when performing their biological functions. Numerous published studies have shed more light on the importance of metabolic reprogramming in the immune system. Moreover, this knowledge is crucial for revealing new ways to target inflammatory pathologic states, such as autoimmunity and hyperinflammation. Here, we discuss the role of glycolysis in immune cell activity in physiological and pathological conditions, and the potential use of inhibitors of glycolysis for disease treatment.
]]>Molecules doi: 10.3390/molecules29061297
Authors: Mpho Mamphoka Nchabeleng Thierry Youmbi Fonkui Green Ezekiel
The efficacy of 23 bacterial isolates obtained from surface-sterilized stems and leaves of three medicinal plants (Aloe barbadensis Miller, Artemisia afra, and Moringa oleifera) was investigated in an endeavour to prevent the growth of Mycobacterium bovis using the cross-streak method. Endophytes were isolated by incubating sterile plant materials on nutrient agar at 30 °C for 5 days. Two isolates showing activity were subsequently utilized to produce the extracts. Whole-genome sequencing (WGC) was used to identify the isolates. Secondary metabolites produced after 7 days of growth in nutrient broth were harvested through extraction with ethyl acetate. The extracts were chemically profiled using gas chromatography–high resolution time-of-flight mass spectrometry (GC–HRTOF-MS). NCBI BLAST search results revealed that the isolated endophytes belonged to the Pseudomonas and Enterobacter genera, based on WGC. Two endophytes, Aloe I4 and Aloe I3–I5 from Aloe barbadensis, exhibited potency based on the cross-streak method. The metabolite profiling of the selected endophytes identified 34 metabolites from Aloe I4, including ergotamine, octadecane, L-proline and 143 other metabolites including quinoline and valeramide, which inhibit microbial quorum sensing. These findings suggest that bacterial endophytes from medicinal plants, particularly Aloe barbadensis, hold promise as sources of antimycobacterial agents for human health applications.
]]>Molecules doi: 10.3390/molecules29061296
Authors: Dina Ashraf Rana Morsi Muhammad Usman Mohammed A. Meetani
Emerging pollutants (EPs) encompass natural or synthetic substances found in the environment that pose potential risks, but which have only recently been recognized or monitored. EPs consist of various categories, including pesticides, pharmaceuticals, hormones, mycotoxins, and endocrine-disrupting chemicals (EDCs). Through several pathways, EPs can access food, potentially leading to health impacts when safe concentrations are exceeded. Milk, being a highly nutritious food product that is heavily consumed by many consumers of different ages, is a crucial food matrix where EPs should be regularly monitored. In the literature, a large number of studies have been dedicated to the determination of different EPs in dairy milk, employing different analytical techniques to do so. Chromatography-based techniques are the most prevalent means used for the analysis of EPs in milk, demonstrating significant efficiency, sensitivity, and accuracy for this specific purpose. The extraction of EPs from a complex matrix like milk is essential prior to performing chromatographic analysis. This review comprehensively covers relevant research papers on the extraction and subsequent detection and determination of EPs in milk using chromatographic methods from 2018 to 2023.
]]>Molecules doi: 10.3390/molecules29061293
Authors: Vincenzo Villani
The gelation kinetics of agar aqueous solutions were studied by means of the viscosity flow curves using a coaxial Couette cylinder viscometer. The viscosity curves show an unusual sigmoidal trend or an exponential decay to a viscous steady state. An original theory of gelation kinetics was developed considering the coarsening of increasingly larger and more stable clusters due to Ostwald ripening and the breakup of clusters that were too large due to the instability of rotating large particles induced by the shear rate. The developed Bounded Ripening Growth model takes into account the trend of the viscosity curves by means of an autocatalytic process with negative feedback on aggregation according to the logistic kinetic equation, in which the constants k1(γ) and k−(ν) are governed by the surface tension and shear rate, respectively. A dimensionless equation based on the difference between the Weber number and the ratio of the inverse kinetic constant to forward constant, accounts for the behavior of the dispersed phase in equilibrium conditions or far from the hydrostatic equilibrium.
]]>Molecules doi: 10.3390/molecules29061295
Authors: Subinuer Yasen Chengrui Li Siyuan Wang Yixin Dong Hang Li Jie Chen Yifan Meng Ping Yu Haiyan Zou
Rhizoma Panacis Japonici (RPJ) is an ancient herbal medicine from China that has long been employed for its medicinal benefits in relieving arthritis physical debility and diverse afflictions. The primary bioactive constituents found in RPJ are triterpene saponins, which exhibit numerous pharmacological actions, including anti-inflammatory, antioxidant, and immunomodulating effects. The present study established a straightforward and effective approach for characterizing triterpene saponins in RPJ. An offline HILIC × RP LC/QTOF-MS method was developed, along with a self-constructed in-house database containing 612 saponins reported in the Panax genus and 228 predicted metabolites. The approach achieved good chromatographic performance in isolating triterpene saponins of RPJ, with the HILIC column as the first dimension (1D) and the BEH C18 column as the second dimension (2D). The developed two-dimensional liquid chromatography system exhibited an orthogonality of 0.61 and a peak capacity of 1249. Detection was performed using a QTOF mass spectrometer in a data-independent manner (MSE) in a negative ion mode. Using the in-house database, the collected MS data were processed by an automatic workflow on UNIFI 1.8.2 software, which included data correction, matching of precursor and product ions, and peak annotation. In this study, 307 saponins were characterized from RPJ and 76 saponins were identified for the first time in Panax japonicus. This research not only enhances our understanding of the chemical characteristics of RPJ but also offers a simple and efficient method for analyzing the complex composition of herbal medicine.
]]>Molecules doi: 10.3390/molecules29061291
Authors: Wen Zhang Xinping Zhang Xinyi Lv Ao Qu Wenjing Liang Limin Wang Pei Zhao Zijian Wu
The oral delivery strategy of natural anti-oxidant and anti-inflammatory agents has attracted great attention to improve the effectiveness of ulcerative colitis (UC) treatment. Herein, we developed a novel orally deliverable nanoparticle, carboxymethyl chitosan (CMC)-modified astaxanthin (AXT)-loaded nanoparticles (CMC-AXT-NPs), for UC treatment. The CMC-AXT-NPs were evaluated by appearance, morphology, particle size, ζ-potential, and encapsulation efficiency (EE). The results showed that CMC-AXT-NPs were nearly spherical in shape with a particle size of 34.5 nm and ζ-potential of −30.8 mV, and the EE of CMC-AXT-NPs was as high as 95.03%. The CMC-AXT-NPs exhibited preferable storage stability over time and well-controlled drug-release properties in simulated intestinal fluid. Additionally, in vitro studies revealed that CMC-AXT-NPs remarkably inhibited cytotoxicity induced by LPS and demonstrated superior antioxidant and anti-inflammatory abilities in Raw264.7 cells. Furthermore, CMC-AXT-NPs effectively alleviated clinical symptoms of colitis induced by dextran sulfate sodium salt (DSS), including maintaining body weight, inhibiting colon shortening, and reducing fecal bleeding. Importantly, CMC-AXT-NPs suppressed the expression of pro-inflammatory cytokines like TNF-α, IL-6, and IL-1β and ameliorated DSS-induced oxidative damage. Our results demonstrated the potential of CMC-modified nanoparticles as an oral delivery system and suggested these novel AXT nanoparticles could be a promising strategy for UC treatment.
]]>Molecules doi: 10.3390/molecules29061294
Authors: Fahrul Nurkolis Rudy Kurniawan Elvan Wiyarta Rony Abdi Syahputra Reggie Surya Nurpudji Astuti Taslim Trina Ekawati Tallei Raymond Rubianto Tjandrawinata Eli Y. Adashi Bonglee Kim
Diabetes, particularly type 2 diabetes (T2D), is the main component of metabolic syndrome. It is highly prevalent and has drastically increased with sedentary lifestyles, notably behaviors linked to ease of access and minimal physical activity. Central to this condition is insulin, which plays a pivotal role in regulating glucose levels in the body by aiding glucose uptake and storage in cells, and what happens to diabetes? In diabetes, there is a disruption and malfunction in insulin regulation. Despite numerous efforts, effectively addressing diabetes remains a challenge. This article explores the potential of photoactivatable drugs in diabetes treatment, with a focus on light-activated insulin. We discuss its advantages and significant implications. This article is expected to enrich the existing literature substantially, offering a comprehensive analysis of potential strategies for improving diabetes management. With its minimal physical intrusion, light-activated insulin promises to improve patient comfort and treatment adherence. It offers precise regulation and localized impact, potentially mitigating the risks associated with conventional diabetes treatments. Additionally, light-activated insulin is capable of explicitly targeting RNA and epigenetic factors. This innovative approach may pave the way for more personalized and effective diabetes treatments, addressing not only the symptoms but also the underlying biological causes of the disease. The advancement of light-activated insulin could revolutionize diabetes management. This study represents a pioneering introduction to this novel modality for diabetes management.
]]>Molecules doi: 10.3390/molecules29061290
Authors: Xianjiang Li Wen Ma
Biomedical and food analysis has always been an important topic that closely relates to health [...]
]]>Molecules doi: 10.3390/molecules29061292
Authors: Siyue Guan Yue Wang Ting Hu Lingling Che Xiaoqiao Wang Yike Huang Zhining Xia
Molecular imprinting technology is widely used for the specific identification of compounds, but the selective recognition mechanisms of the same compounds still need to be further studied. Based on differences in hydrogen bond size and orientation, molecularly imprinted polymers (MIPs) were designed to adsorb flavonols with the same parent core and different hydroxyl groups. A surface-imprinted material was designed with silicon dioxide as the carrier, myricetin as the template molecule, and methacrylic acid (MAA) as the functional monomer. Scanning electron microscopy (SEM), Brunauer–Emmett–Teller surface area (BET) analyses, Fourier-transform infrared spectroscopy (FT-IR), and other characterization experiments were carried out. The intrinsic mechanism of the MIPs was also explored. The MIPs showed good adsorption of myricetin and other flavonoids through hydrogen bonding and steric hindrance. The adsorption capacity was 3.12–9.04 mg/g, and the imprinting factor was 1.78–3.37. Flavonoids with different hydroxyl groups in different numbers and directions had different hydrogen bond strengths with functional monomers. R2, R4, and R1 on 2-phenylchromogenone had stronger electronegativity, and the hydroxyl group was also more likely to form and have stronger hydrogen bonds. The hydroxyl negativity and the degree of steric hindrance of flavonoids played a major role in the recognition of molecularly imprinted materials. This study is of great significance for the synthesis of and selection of templates for analogous molecular imprinting materials.
]]>Molecules doi: 10.3390/molecules29061289
Authors: Tomasz Jóźwiak Artur Mielcarek Urszula Filipkowska
The study investigated the possibility of using chitin flakes as an unconventional sorbent for the removal of orthophosphates and nitrates from greenhouse wastewater (GW). The effluent parameters were as follows: 66.2 mg P-PO4/L, 566.0 mg N-NO3/L, 456.0 mg S-SO4/L, 13.7 mg Cl−/L, 721 mg Ca2+/L, 230 mg Mg2+/L, hardness 11.3 °dH, and pH 5.4. The scope of the research included determinations of the influence of pH on GW composition and the efficiency of nutrient sorption, the kinetics of nutrient sorption, the influence of the dose of chitin flakes on the effectiveness of nutrient binding and the maximum sorption capacity of the sorbent. The sorption of P-PO4 on the tested sorbent was most effective at pH 4, and the sorption of N-NO3 at pH 2. The equilibrium time of sorption of both nutrients from GW to chitin depended on the sorbent dose and ranged from 150 to 180 min. The sorbent dose of 40 g/L enabled removing 90% of orthophosphates and 5.7% of nitrates from the wastewater. The maximum sorption capacity of CH towards P-PO4 and N-NO3 contained in the GW was 3.20 mg/g and 3.04 mg/g, respectively. In turn, the sorption of calcium and magnesium ions on chitin flakes was completely ineffective.
]]>Molecules doi: 10.3390/molecules29061288
Authors: Fei Yu Siyuan Liu Bo Liu
Catalytic dehydroaromatization of n-alkanes into high-value aromatics has garnered extensive interest from both academia and industry. Our group has previously reported that phosphorus-doped carbon materials exhibit high selectivity for C-H bond activation in the dehydroaromatization of n-hexane. In this study, using n-heptane as a probe, we synthesized biomass-based phosphorus-doped carbon catalysts to investigate the impact of hydrogen heat treatment and carbon deposition on catalyst structure. Despite achieving an initial conversion of n-heptane at approximately 99.6%, with a toluene selectivity of 87.9%, the catalyst activity fell quickly. Moreover, longer hydrogen treatment time and higher hydrogen concentrations were found to accelerate catalyst deactivation. Thermogravimetric analysis (TGA) and N2 adsorption measurements (BET) indicated that a small amount of coke deposition was not the primary cause of catalyst deactivation. Temperature-programmed desorption of ammonia gas (NH3-TPD) revealed a significant decrease in acid-active functional groups. X-ray photoelectron spectroscopy (XPS) and solid-state 31P NMR spectroscopy confirmed the reduction of active central phosphorus species. These results suggest that catalyst deactivation primarily arises from the decrease in acidity and the partial reduction of phosphorus-containing groups, leading to a substantial loss of active sites. This work contributes new perspectives to understanding the properties and design improvements of metal-free carbon catalysts.
]]>Molecules doi: 10.3390/molecules29061287
Authors: Natalia Rosiak Ewa Tykarska Judyta Cielecka-Piontek
Our research aimed to develop an amorphous solid dispersion (ASD) of myricetin (MYR) with Polyvinylpyrrolidone K30 (PVP30) to enhance its solubility, dissolution rate, antioxidant, and neuroprotective properties. Employing a combination of solvent evaporation and freeze drying, we successfully formed MYR ASDs. XRPD analysis confirmed complete amorphization in 1:8 and 1:9 MYR-PVP weight ratios. DSC thermograms exhibited a single glass transition (Tg), indicating full miscibility. FT-IR results and molecular modeling confirmed hydrogen bonds stabilizing MYR’s amorphous state. HPLC analysis indicated the absence of degradation products, ensuring safe MYR delivery systems. Solubility, dissolution rate (pH 1.2 and 6.8), antioxidant (ABTS, DPPH, CUPRAC, and FRAP assays), and in vitro neuroprotective activities (inhibition of cholinesterases: AChE and BChE) were significantly improved compared to the pure compound. Molecular docking studies revealed that MYR had made several hydrogen, hydrophobic, and π-π stacking interactions, which could explain the compound’s potency to inhibit AChE and BChE. MYR-PVP 1:9 w/w ASD has the best solubility, antioxidant, and neuroprotective activity. Stability studies confirmed the physical stability of MYR-PVP 1:9 w/w ASD immediately after dissolution and for two months under ambient conditions. Our study showed that the obtained ASDs are promising systems for the delivery of MYR with the potential for use in alleviating the symptoms of neurodegenerative diseases.
]]>Molecules doi: 10.3390/molecules29061286
Authors: Zhengxiang Sun Rui Wang Vitaly Edwardovich Matulis Korchak Vladimir
As traditional fossil fuel energy development faces significant challenges, two-dimensional layered materials have become increasingly popular in various fields and have generated widespread research interest. MXene is an exceptional catalytic material that is typically integrated into functional composite materials with other substances to enhance its catalytic-reaction performance. Improving the thermal stability, electrical conductivity, and electrochemical activity, as well as enhancing the specific surface structure, can make the material an excellent catalyst for photoelectrocatalysis and energy-regeneration reactions. The article mainly outlines the structural characteristics, preparation methods, and applications of MXene in the field of catalysis. This text highlights the latest progress and performance comparison of MXene-based catalytic functional materials in various fields such as electrochemical conversion, photocatalysis, renewable energy, energy storage, and carbon capture and conversion. It also proposes future prospects and discusses the current bottlenecks and challenges in the development of MXene-based catalytic materials.
]]>Molecules doi: 10.3390/molecules29061285
Authors: Miryam Chiara Malacarne Marzia Bruna Gariboldi Emanuela Marras Enrico Caruso
Photodynamic therapy (PDT) is a minimally invasive treatment that uses the combination of a photosensitizing agent (PS) and light to selectively target solid tumors, as well as several non-neoplastic proliferating cell diseases. After systemic administration, PSs are activated by localized irradiation with visible light; in the presence of adequate concentrations of molecular oxygen, this causes the formation of reactive oxygen species (ROS) and subsequent tissue damage. In this study, two series of tetrakis(N-alkylpyridinium-4-yl)porphyrins were synthesized, differing in the presence or absence of a zinc ion in the tetrapyrrole nucleus, as well as in the N-alkyl chain length (from one to twelve carbon atoms). The compounds were chemically characterized, and their effect on cell viability was evaluated using a panel of three tumor cell lines to determine a possible relationship between photodynamic activity and Zn presence/alkyl chain length. The types of cell death mechanisms involved in the effect of the various PSs were also evaluated. The obtained results indicate that the most effective porphyrin is the Zn-porphyrin, with a pendant made up of eight carbon atoms (Zn-C8).
]]>Molecules doi: 10.3390/molecules29061284
Authors: Hyeonjin Kim Yun-Ho Ahn
Gas hydrates, a type of inclusion compound capable of trapping gas molecules within a lattice structure composed of water molecules, are gaining attention as an environmentally benign gas storage or separation platform. In general, the formation of gas hydrates from water requires high-pressure and low-temperature conditions, resulting in significant energy consumption. In this study, tetrabutylammonium fluoride (TBAF) was utilized as a thermodynamic promoter forming a semi-clathrate-type hydrate, enabling gas capture or separation at room temperature. Those TBAF hydrate systems were explored to check their capability of CO2 separation from flue gas, the mixture of CO2 and N2 gases. The formation rates and gas storage capacities of TBAF hydrates were systematically investigated under various concentrations of CO2, and they presented selective CO2 capture behavior during the hydrate formation process. The maximum gas storage capacities were achieved at 2.36 and 2.38 mmol/mol for TBAF·29.7 H2O and TBAF·32.8 H2O hydrate, respectively, after the complete enclathration of the feed gas of CO2 (80%) + N2 (20%). This study provides sufficient data to support the feasibility of TBAF hydrate systems to be applied to CO2 separation from CO2/N2 gas mixtures based on their CO2 selectivity.
]]>Molecules doi: 10.3390/molecules29061283
Authors: Hua-Ping Ren Zhi-Xia Xie Shao-Peng Tian Si-Yi Ding Qiang Ma Yu-Zhen Zhao Zhe Zhang Jiao-Jiao Fu Qing-Qing Hao
To improve the mess-specific activity of Co supported on zeolite catalysts in Fischer–Tropsch (FT) synthesis, the Co-MCM-22 catalyst was prepared by simply grinding the MCM-22 with nanosized Co3O4 prefabricated by the thermal decomposition of the Co(II)-glycine complex. It is found that this novel strategy is effective for improving the mess-specific activity of Co catalysts in FT synthesis compared to the impregnation method. Moreover, the ion exchange and calcination sequence of MCM-22 has a significant influence on the dispersion, particle size distribution, and reduction degree of Co. The Co-MCM-22 prepared by the physical grinding of prefabricated Co3O4 and H+-type MCM-22 without a further calcination process exhibits a moderate interaction between Co3O4 and MCM-22, which results in the higher reduction degree, higher dispersion, and higher mess-specific activity of Co. Thus, the newly developed method is more controllable and promising for the synthesis of metal-supported catalysts.
]]>Molecules doi: 10.3390/molecules29061282
Authors: Shekhar Gupta Priyanka Sai Kiran Mavileti Shyam S. Pandey Tamaki Kato
Chymotrypsin, a crucial enzyme in human digestion, catalyzes the breakdown of milk proteins, underscoring its significance in both health diagnostics and dairy quality assurance. Addressing the critical need for rapid, cost-effective detection methods, we introduce a groundbreaking approach utilizing far-red technology and HOMO-Förster resonance energy transfer (FRET). Our novel probe, SQ-122 PC, features a unique molecular design that includes a squaraine dye (SQ), a peptide linker, and SQ moieties synthesized through solid-phase peptide synthesis. Demonstrating a remarkable quenching efficiency of 93.75% in a tailored H2O:DMSO (7:3) solvent system, our probe exhibits absorption and emission properties within the far-red spectrum, with an unprecedented detection limit of 0.130 nM. Importantly, our method offers unparalleled selectivity towards chymotrypsin, ensuring robust and accurate enzyme detection. This pioneering work underscores the immense potential of far-red-based homo-FRET systems in enabling the sensitive and specific detection of chymotrypsin enzyme activity. By bridging the gap between cutting-edge technology and biomedical diagnostics, our findings herald a new era of enzyme sensing, promising transformative advancements in disease diagnosis and dairy quality control.
]]>Molecules doi: 10.3390/molecules29061281
Authors: Wenxin Sun Xuening Jian Jie Zhang Xiaoni Meng Haotian Wang Deqiang Zheng Lijuan Wu Youxin Wang
Background: Immunoglobulin G (IgG) N-glycosylation is considered a potential biomarker for aging and various pathological conditions. However, whether these changes in IgG N-glycosylation are a consequence or a contributor to the aging process remains unclear. This study aims to investigate the causality between IgG N-glycosylation and aging using Mendelian randomization (MR) analysis. Methods: We utilized genetic variants associated with IgG N-glycosylation traits, the frailty index (FI), and leukocyte telomere length (LTL) from a previous genome-wide association study (GWAS) on individuals of European ancestry. Two-sample and multivariable MR analyses were conducted, employing the inverse-variance weighted (IVW) method. Sensitivity analyses were performed to assess potential confounding factors. Results: Using the IVW method, we found suggestive evidence of a causal association between GP14 and FI (β 0.026, 95% CI 0.003 to 0.050, p = 0.027) and LTL (β −0.020, 95% CI −0.037 to −0.002, p = 0.029) in the two-sample MR analysis. In the multivariable MR analysis, suggestive evidence was found for GP23 and FI (β −0.119, 95% CI −0.219 to −0.019, p = 0.019) and GP2 and LTL (β 0.140, 95% CI 0.020 to 0.260, p = 0.023). Conclusions: In conclusion, our results supported a potentially causal effect of lower GP23 levels on an advanced aging state. Additional verification is required to further substantiate the causal relationship between glycosylation and aging.
]]>Molecules doi: 10.3390/molecules29061280
Authors: Ahsan Ali Muhammad Adnan Khan Hoimyung Choi
Dibenzyltoluene (H0-DBT), a Liquid Organic Hydrogen Carrier (LOHC), presents an attractive solution for hydrogen storage due to its enhanced safety and ability to store hydrogen in a concentrated liquid form. The utilization of machine learning proves essential for accurately predicting hydrogen storage classes in H0-DBT across diverse experimental conditions. This study focuses on the classification of hydrogen storage data into three classes, low-class, medium-class and high-class, based on the hydrogen storage capacity values. We introduce Hydrogen Storage Prediction with the Support Vector Machine (HSP-SVM) model to predict the hydrogen storage classes accurately. The performance of the proposed HSP-SVM model was investigated using various techniques, which included 5-Fold Cross Validation (5-FCV), Resubstitution Validation (RV), and Holdout Validation (HV). The accuracy of the HV approach for the low, medium, and high class was 98.5%, 97%, and 98.5%, respectively. The overall accuracy of HV approach reached 97% with a miss clarification rate of 3%, whereas 5-FCV and RV possessed an overall accuracy of 93.9% with a miss clarification rate of 6.1%. The results reveal that the HV approach is optimal for predicting the hydrogen storage classes accurately.
]]>Molecules doi: 10.3390/molecules29061279
Authors: Lanyue Zhang Zeting Huang Jie Xuan Lu Yang Tiantian Zhao Weihua Peng
Psoriasis is a common chronic inflammatory disease, but most of its current treatments come with a high risk of side effects. As one of the world’s top three beverages, tea has a traditional history of being used as a treatment for skin conditions due to its high safety profile, anti-inflammatory and other properties. In this study, we investigated the anti-psoriasis effects of ethanol extracts of black tea, green tea and white tea from southeastern China. The compositions of the tea extracts (TEs) were first determined by UPLC-Q-Exactive-Orbitrap MS and then genetic analysis, antibacterial, anti-inflammatory, and immunocompetence assays were performed. Imiquimod was used to establish a mouse model of psoriasis-like dermatitis and treating with the extracts to examine their efficacy. A total of 88 chemical components, mainly phenols and organic acids, were identified from the TEs. These TEs ameliorated skin damage and they all reduced the expression of cytokines IL-17 and TNF-α. By analyzing the genes, TEs may affect the inflammatory signaling pathway by regulating the metabolic changes. In addition, TEs can significantly scavenge ROS, NO, and inhibit cellular inflammation. In conclusion, this study examined the inhibitory effects of three TEs on psoriasis and their potential as nutritional supplements for the treatment of skin inflammation.
]]>Molecules doi: 10.3390/molecules29061275
Authors: Zunhua Li Zicheng Gong Bowen Zhang Asad Nawaz
Amorphous solids exhibit enhanced solubility and dissolution rates relative to their crystalline counterparts. However, attaining optimal bioavailability presents a challenge, primarily due to the need to maintain the physical stability of amorphous solids. Moreover, the precise manner in which precipitation parameters, including the feeding rate of the anti-solvent, agitation speed, and aging time, influence the physical stability of amorphous solids remains incompletely understood. Consequently, this study aimed to investigate these three parameters during the precipitation process of the anticancer drug, nilotinib free base. The physical stability of the resultant samples was evaluated by employing characterization techniques including powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), focused beam reflectance measurement (FBRM), and data analysis methods such as pair distribution function (PDF), reduced crystallization temperature (Rc), and principal component analysis (PCA). This study’s findings indicated that amorphous solids exhibited the greatest physical stability under particular conditions, namely a feeding rate of 5 mL/min, an agitation speed of 500 rpm, and an aging time of 10 min. Furthermore, the physical stability of the amorphous solids was primarily influenced by particle size and distribution, molecular interactions, microstructure, surface area, and interfacial energy. Notably, the parameters involved in the anti-solvent precipitation process, including the feeding rate of the anti-solvent, agitation speed, and aging time, exerted a significant impact on these factors. Consequently, they directly affected the physical stability of amorphous solids. Hence, this study comprehensively elucidated the mechanistic influence of these operational parameters on the physical stability of amorphous solids during the anti-solvent precipitation process.
]]>Molecules doi: 10.3390/molecules29061277
Authors: Tamami Haraguchi Saki Hayashi Seira Nakasaka Yoshiro Hatanaka Toshihiro Nagao Shigemitsu Tanaka Miki Yoshii Fumiko Hara Masayori Hagimori Miyako Yoshida
There is an urgent need to discover and develop novel antibacterial agents. Accordingly, we synthesised 2-(piperazin-1-yl)naphtho[2,3-d]thiazole-4,9-dione (PNT), which exhibits antimicrobial activity. The aim of this study was to characterise PNT as an effective antimicrobial agent. Fluorescence microscopy was used to measure PNT’s uptake into microbial cells (strains of Staphylococcus epidermidis, Staphylococcus aureus, and methicillin-resistant S. aureus (MRSA)), transmission electron microscopy (TEM) was used to investigate the influence of PNT on the configuration of microbial cells, and a DNA gyrase supercoiling assay was used to investigate whether PNT inhibits DNA gyrase. PNT was taken up by more than 50% of microbial cells within 30 min. Using TEM, hollowed-out bacterial cytoplasms were observed in the specimen treated with PNT, although there was no disintegration of the bacterial membrane. In the DNA gyrase supercoiling assay, a dose-dependent reduction in fluorescence intensity was observed as the concentration of PNT increased. This suggests that PNT is taken up by microbial cells, resulting in cell disruption, and it reveals that one of the mechanisms underlying the antimicrobial activity of PNT is the inhibition of DNA gyrase.
]]>Molecules doi: 10.3390/molecules29061278
Authors: Yuanyuan Wang Daigang Wang Chao Ding Jing Li Shengdong Jiang
During the development of a sand-conglomerate reservoir, there is a huge variation in rock grain size and different åmineral compositions of different-sized sand grains. The mineral composition and microstructure of the rock both have an impact on the characteristics of the remaining oil in the reservoir. The stripping mechanism of a surfactant system on sand-conglomerate surface crude oil with varied grain size minerals was explored in this paper. Sand-conglomerate was classified and analyzed to determine their wettability and stripping oil effects. The optimization of the surfactant solution system and molecular dynamics simulation revealed the surfactant stripping mechanism on crude oil on distinct sandstone minerals. The results of the study showed that montmorillonite minerals are more readily adsorbed by surfactants. The crude oil within them is more likely to compete for adsorption and to be stripped off, and then extracted with the recovery fluid. The surfactant solution system can increase the hydrophilicity of the rock surface, make the crude oil on the rock surface shrink and gather, and enhance the transportation ability of the displacement fluid. And the emulsification seals part of the pore in the reservoir, increases the displacement pressure, and improves the overall wave volume. The results of this paper are of great significance for the efficient development of sand-conglomerate reservoirs.
]]>Molecules doi: 10.3390/molecules29061276
Authors: Xue Zhang Qi Chen Linzhen Chen Xiaolu Chen Zhiqiang Ma
Polygonatum cyrtonema Hua, the dried rhizome of Polygonum multiflorum from the Liliaceae family, is a widely used medicinal herb with a long history of application. Its main active ingredients are polysaccharides, which have been demonstrated in contemporary studies to effectively delay the aging process. In the present study, homogeneous polysaccharide (PCP-1) was obtained after the purification and isolation of polysaccharides from Polygonatum cyrtonema Hua (PCP). The anti-aging activities of both were compared, and the possible mechanism of action for exerting anti-aging activity was explored using Caenorhabditis elegans (C. elegans). Research has indicated that PCP and PCP-1 exhibit potent anti-oxidant and anti-aging properties. Of particular note is that PCP-1 acts better than PCP. The two were able to prolong the lifespan of nematodes, improve the stress resistance of nematodes, reduce the accumulation of lipofuscin in the intestine, decrease the content of ROS and MDA in the body, increase the activity of the antioxidant enzymes SOD and CAT, promote the nuclear translocation of DAF-16, down-regulate the mRNA levels of the age-1 and daf-2 genes of the IIS pathway in nematodes, and up-regulate the expression of the daf-16, skn-1, sod-3, and hsp-16.2 genes. Based on the aforementioned findings, it is possible that the mechanism by which PCP and PCP-1 exert anti-aging effects may be through negative regulation of the IIS pathway, activation of the transcription factor DAF-16/FOXO, and enhancement of oxidative defenses and stress resistance in nematodes. Overall, the present study illustrated the great potential of polysaccharides from Polygonatum cyrtonema Hua in anti-aging and antioxidant activities. Specifically, PCP-1 demonstrated superior characteristics, which provides a reference for the future development of Polygonatum cyrtonema Hua polysaccharides.
]]>Molecules doi: 10.3390/molecules29061274
Authors: Ralfs Vevers Akshay Kulkarni Alissa Seifert Kathrin Pöschel Kornelia Schlenstedt Jochen Meier-Haack Linda Mezule
Global water scarcity is a threat that can be alleviated through membrane filtration technologies. However, the widespread adoption of membranes faces significant challenges, primarily due to membrane biofouling. This is the reason why membrane modifications have been under increasing investigation to address the fouling issues. Antibacterial membranes, designed to combat biofouling by eliminating microorganisms, offer a promising solution. Within this study, flat sheet ultrafiltration (UF) membranes with integrated photocatalytic zinc oxide (ZnO) nanoparticles were developed, characterized, and assessed through filtration and fouling tests. The antibacterial properties of the membranes were conducted in static tests using Gram-negative bacteria—Escherichia coli—and natural tap water biofilm. The results demonstrated a notable enhancement in membrane surface wettability and fouling resistance. Furthermore, the incorporation of ZnO resulted in substantial photocatalytic antibacterial activity, inactivating over 99.9% of cultivable E. coli. The antibacterial activity persisted even in the absence of light. At the same time, the persistence of natural tap water organisms in biofilms of modified membranes necessitates further in-depth research on complex biofilm interactions with such membranes.
]]>Molecules doi: 10.3390/molecules29061273
Authors: Yuxi Guo Honglin Ren Han Wang Yiran Xiao Cong Wang Mengdi Liu Fuchun Duan Haosong Li Pan Hu Yansong Li Zengshan Liu Shiying Lu
N-glycolylneuraminic acid (Neu5Gc), a sialic acid predominantly found in the non-neurohumoral fluids of hind-mouthed animals, is incapable of synthesizing Neu5Gc due to a deletion in the CMAH exon of the gene encoding human CMP-Neu5Gc hydroxylase. But consumption of animal-derived foods that contain Neu5Gc, such as red meat, can instigate an immune response in humans, as Neu5Gc is recognized as a foreign substance by the human immune system. This recognition leads to the production of anti-Neu5Gc antibodies, subsequently resulting in chronic inflammation. When Neu5Gc is consumed excessively or frequently, it may contribute to the development of heart disease and cancer. This makes Neu5Gc, an endogenous pathogenic factor derived from red meat, a new hot topic in red meat safety research. In this study, aptamers obtained by the magnetic bead SELEX technique were subjected to homology and secondary structure prediction analysis as well as affinity determination. The result indicated that the aptamer 2B.N2A9 exhibited a robust binding affinity, with an affinity constant (Ka) of 1.87 × 108 L/mol. This aptamer demonstrated optimal binding specificity within a pH range of 5.4 to 7.4. Molecular docking analysis further revealed that aptamer 2B.N2A9 formed stable binding interactions with the target Neu5Gc at specific sites, namely G-14, C-15, G-13, G-58, G-60, and C-59. An Enzyme-Linked Oligonucleotide Sorbent Assay (ELOSA) methodology was established to detect the endogenous pathogenic factor Neu5Gc present in red meat. This method demonstrated a limit of detection (LOD) of 0.71 ng/mL, along with an average recovery rate of 92.23%. The aptamer obtained in this study exhibited favorable binding properties to Neu5Gc. The assay was relatively convenient and demonstrated good sensitivity. Further investigation into the distribution of Neu5Gc in various red meats is of public health significance and scientific potential. A practical detection method should be provided to guide red meat diets and ensure the nutrition and safety of meat products.
]]>Molecules doi: 10.3390/molecules29061272
Authors: Guangling Yin Chunxing Pan Hong Liu Changzhi Dong Xia Chang Wei Zhou Shanshan Wang Zhiyun Du
Oxyresveratrol is one of the active ingredients derived from mulberry branch with strong anti-inflammatory bioactivity. In this research, we want to explore if oxyresveratrol can improve cognitive impairments and episodic-like memory and its mechanism. In LPS-induced BV-2 cells, 25 μM OXY can significantly inhibit the expression of NO and alter the M1/M2 polarization by regulating M1/M2 phenotype makers. In vivo, OXY (50, 100 mg/kg) significantly reversed cognitive impairments and alleviated neuronal injuries caused by neuroinflammation. According to network pharmacology analysis, OXY alleviated neuroinflammation via the PI3K-Akt pathway. In general, the research revealed that OXY can improve cognitive impairments and episodic-like memory through alleviating LPS-induced neuroinflammation and regulating the PI3K-Akt signaling pathway.
]]>Molecules doi: 10.3390/molecules29061271
Authors: Jingjing Wang Fulai Liu Yunfei Li Long Chen Yong Chen Hailong Zhang Zheng Xie
Although laser technology brings convenience to production and daily life, it also causes high-energy damage. Therefore, there is an urgent need to develop optical limiting materials for laser protection. In this study, a novel nonlinear optical material, red/black phosphorus lateral heterojunction, is successfully prepared through solvothermal and ultrasonic treatment. Using the Z−scan method, the nonlinear optical properties of the red/black phosphorus heterojunction are determined at wavelengths of 532 and 1064 nm. These results indicate that the red/black phosphorus heterojunction exhibits reverse saturable absorption properties in 1.2.3-glycerol. Interestingly, the red/black phosphorus heterojunction shows an enhanced performance over red phosphorus by introducing the black phosphorus phase. Moreover, the red/black phosphorus heterojunction is doped into organically modified silicate gel glass with excellent broadband optical limiting performance. This study highlights the promising prospect of the red/black phosphorus heterojunction in the nonlinear optical and optical limiting fields.
]]>Molecules doi: 10.3390/molecules29061270
Authors: Boxin Dou Mingyu Li Lirui Sun Jiaying Xin Chungu Xia
(1) Background: Particulate methane monooxygenase (pMMO) has a strong dependence on the natural electron transfer path and is prone to denaturation, which results in its redox activity centers being unable to transfer electrons with bare electrodes directly and making it challenging to observe an electrochemical response; (2) Methods: Using methanobactin (Mb) as the electron transporter between gold electrodes and pMMO, a bionic interface with high biocompatibility and stability was created. The Mb-AuNPs-modified functionalized gold net electrode as a working electrode, the kinetic behaviors of pMMO bioelectrocatalysis, and the effect of Mb on pMMO were analyzed. The CV tests were performed at different scanning rates to obtain electrochemical kinetics parameters. (3) Results: The values of the electron transfer coefficient (α) and electron transfer rate constant (ks) are relatively large in test environments containing only CH4 or O2. In contrast, in the test environment containing both CH4 and O2, the bioelectrocatalysis of pMMO is a two-electron transfer process with a relatively small α and ks; (4) Conclusions: It was inferred that Mb formed the complex with pMMO. More importantly, Mb not only played a role in electron transfer but also in stabilizing the enzyme structure of pMMO and maintaining a specific redox state. Furthermore, the continuous catalytic oxidation of natural substrate methane was realized.
]]>Molecules doi: 10.3390/molecules29061269
Authors: Fei Liu Yongfei Li Xuewu Wang Zhizeng Xia
Reversible emulsion drilling fluids can concentrate the advantages of water-based drilling fluids and oil-based drilling fluids. Most of the existing reversible emulsion drilling fluid systems are surfactant-based emulsifier systems, which have the disadvantage of poor stability. However, the use of modified nanoparticles as emulsifiers can significantly enhance the stability of reversible emulsion drilling fluids, but ordinary nanoparticles have the disadvantages of high cost and easily causing environmental pollution. In order to solve the shortcomings of the existing reversible emulsion drilling fluid system, the modified nanocrystalline cellulose was considered to be used as an emulsifier to prepare reversible emulsion drilling fluid. After research, the modified nanocrystalline cellulose NWX-3 can be used to prepare reversible emulsions, and on this basis, reversible emulsion drilling fluids can be constructed. Compared with the reversible emulsion drilling fluid stabilized by HRW-DMOB (1.3 vol.% emulsifier), the reversible emulsion drilling fluid stabilized by the emulsifier NWX-3 maintained a good reversible phase performance, filter cake removal, and oily drill cuttings treatment performance with less reuse of emulsifier (0.8 vol.%). In terms of temperature resistance (150 °C) and stability (1000 V < W/O emulsion demulsification voltage), it is significantly better than that of the surfactant system (temperature resistance 120 °C, 600 V < W/O emulsion demulsification voltage < 650 V). The damage of reservoir permeability of different types of drilling fluids was compared by physical simulation, and the damage order of core gas permeability was clarified: water-based drilling fluid > reversible emulsion drilling fluid > oil-based drilling fluid. Furthermore, the NMR states of different types of drilling fluids were compared as working fluids, and the main cause of core permeability damage was the retention of intrusive fluids in the core.
]]>Molecules doi: 10.3390/molecules29061268
Authors: Zhuang Dong Mengting Liu Xiaohong Zhong Xiaoyong Ou Xuan Yun Mingcan Wang Shurui Ren Zhixing Qing Jianguo Zeng
The article in question [...]
]]>Molecules doi: 10.3390/molecules29061265
Authors: Shuiqing Lin Yuxiao Wu Qian Huang Zhiting Liu Juan Xu Ruifeng Ji Natalia V. Slovesnova Xin He Lin Zhou
Ginseng holds high medicinal and cosmetic value, with stem and leaf extracts garnering attention for their abundant bioactive ingredients. Meanwhile, fermentation can enhance the effectiveness of cosmetics. The aim of this study was to optimize ginseng fermentation to produce functional cosmetics. Ginseng stem and leaf extracts were fermented with five different strains of lactic acid bacteria. Using 2,2-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl radical (·OH), and superoxide anion (O2·−) scavenging activities as indicators, the fermentation process was optimized via response surface methodology. Finally, validation of the antioxidant activity of the optimized fermentation broth was performed using human skin cells (HaCaT and BJ cells). Based on the antioxidant potency composite comprehensive index, Lactiplantibacillus plantarum 1.140 was selected, and the optimized parameters were a fermentation time of 35.50 h, an inoculum size of 2.45%, and a temperature of 28.20 °C. Optimized fermentation boosted antioxidant activity: DPPH scavenging activity increased by 25.00%, ·OH by 94.00%, and O2·− by 73.00%. Only the rare ginsenoside Rg5 showed a substantial rise in content among the 11 ginsenosides examined after fermentation. Furthermore, the flavonoid content and ·OH scavenging activity were significantly negatively correlated (r = −1.00, p < 0.05), while the Rh1 content and O2·− scavenging activity were significantly positively correlated (r = 0.998, p < 0.05). Both the 0.06% (v/v) and 0.25% (v/v) concentrations of the optimized broth significantly promoted cell proliferation, and notable protective effects against oxidative damage were observed in HaCaT cells when the broth was at 0.06%. Collectively, we demonstrated that ginseng fermentation extract effectively eliminates free radicals, preventing and repairing cellular oxidative damage. This study has identified new options for the use of fermented ginseng in functional cosmetics.
]]>Molecules doi: 10.3390/molecules29061267
Authors: Huma Jamil Muhammad Faizan Muhammad Adeel Teofil Jesionowski Grzegorz Boczkaj Aldona Balčiūnaitė
Shape memory and self-healing polymer nanocomposites have attracted considerable attention due to their modifiable properties and promising applications. The incorporation of nanomaterials (polypyrrole, carboxyl methyl cellulose, carbon nanotubes, titania nanotubes, graphene, graphene oxide, mesoporous silica) into these polymers has significantly enhanced their performance, opening up new avenues for diverse applications. The self-healing capability in polymer nanocomposites depends on several factors, including heat, quadruple hydrogen bonding, π–π stacking, Diels–Alder reactions, and metal–ligand coordination, which collectively govern the interactions within the composite materials. Among possible interactions, only quadruple hydrogen bonding between composite constituents has been shown to be effective in facilitating self-healing at approximately room temperature. Conversely, thermo-responsive self-healing and shape memory polymer nanocomposites require elevated temperatures to initiate the healing and recovery processes. Thermo-responsive (TRSMPs), light-actuated, magnetically actuated, and Electrically actuated Shape Memory Polymer Nanocomposite are discussed. This paper provides a comprehensive overview of the different types of interactions involved in SMP and SHP nanocomposites and examines their behavior at both room temperature and elevated temperature conditions, along with their biomedical applications. Among many applications of SMPs, special attention has been given to biomedical (drug delivery, orthodontics, tissue engineering, orthopedics, endovascular surgery), aerospace (hinges, space deployable structures, morphing aircrafts), textile (breathable fabrics, reinforced fabrics, self-healing electromagnetic interference shielding fabrics), sensor, electrical (triboelectric nanogenerators, information energy storage devices), electronic, paint and self-healing coating, and construction material (polymer cement composites) applications.
]]>Molecules doi: 10.3390/molecules29061266
Authors: Jiangang Zhang Xinyue Zhang Xiangdong Su Haijun Du Yongzhong Lu Qinglian Zhang
The extraction of rare earth elements (REEs) from phosphogypsum (PG) is of great significance for the effective utilization of rare earth resources and enhancing the resource value of PG waste residues. This study used Aspergillus niger (A. niger) fungal culture filtrate as a leaching agent to investigate the behavior of extracting REEs from PG through direct and indirect contact methods. According to the ICP-MS results, direct leaching at a temperature of 30 °C, shaking speed of 150 rpm, and a solid–liquid ratio of 2:1, achieved an extraction rate of 74% for REEs, with the main elements being yttrium (Y), lanthanum (La), cerium (Ce), and neodymium (Nd). Under the same conditions, the extraction rate of REEs from phosphogypsum using an A. niger culture filtrate was 63.3% higher than that using the simulated organic acid-mixed solution prepared with the main organic acid components in the A. niger leachate. Moreover, the morphological changes observed in A. niger before and after leaching further suggest the direct involvement of A. niger’s metabolic process in the extraction of REEs. When compared to using organic acids, A. niger culture filtrate exhibits higher leaching efficiency for extracting REEs from PG. Additionally, using A. niger culture filtrate is a more environmentally friendly method with the potential for industrial-scale applications than using inorganic acids for the leaching of REEs from PG.
]]>Molecules doi: 10.3390/molecules29061264
Authors: Mayuri Gupta Jun Feng Govinda Bhisetti
In CNS drug discovery, the estimation of brain exposure to lead compounds is critical for their optimization. Compounds need to cross the blood–brain barrier (BBB) to reach the pharmacological targets in the CNS. The BBB is a complex system involving passive and active mechanisms of transport and efflux transporters such as P-glycoproteins (P-gp) and breast cancer resistance protein (BCRP), which play an essential role in CNS penetration of small molecules. Several in vivo, in vitro, and in silico methods are available to estimate human brain penetration. Preclinical species are used as in vivo models to understand unbound brain exposure by deriving the Kp,uu parameter and the brain/plasma ratio of exposure corrected with the plasma and brain free fraction. The MDCK-mdr1 (Madin Darby canine kidney cells transfected with the MDR1 gene encoding for the human P-gp) assay is the commonly used in vitro assay to estimate compound permeability and human efflux. The in silico methods to predict brain exposure, such as CNS MPO, CNS BBB scores, and various machine learning models, help save costs and speed up compound discovery and optimization at all stages. These methods enable the screening of virtual compounds, building of a CNS penetrable compounds library, and optimization of lead molecules for CNS penetration. Therefore, it is crucial to understand the reliability and ability of these methods to predict CNS penetration. We review the in silico, in vitro, and in vivo data and their correlation with each other, as well as assess published experimental and computational approaches to predict the BBB penetrability of compounds.
]]>Molecules doi: 10.3390/molecules29061263
Authors: Hongtai Xu Zijiang Yang
The dynamic mechanisms and intramolecular isotope effects of the Be(1S) + HD (v0 = 2, j0 = 0) → BeH/BeD + H/D reaction are studied at the state-to-state level using the time-dependent wave packet method on a high-quality potential energy surface. This reaction can proceed along the indirect pathway that features a barrier and a deep well or the smooth direct pathway. The reaction probabilities, total and state-resolved integral cross sections, and differential cross sections are analyzed in detail. The calculated dynamics results show that both of the products are mainly formed by the dissociation of a collinear HBeD intermediate when the collision energy is slightly larger than the threshold. As the collision energy increases, the BeH + D channel is dominated by the direct abstraction process, whereas the BeD + H channel mainly follows the complex-forming mechanism.
]]>Molecules doi: 10.3390/molecules29061262
Authors: Gangqiang Zhou Guo Liang Wei Xiao Liangliang Tian Yanhua Zhang Rong Hu Yi Wang
Porous α-Fe2O3 hollow rods/reduced graphene oxide (α-Fe2O3 HR/RGO) composites with unique morphological characteristics and a high surface area are prepared through a template strategy, which was systematically studied and found to have outstanding supercapacitive properties. When served as active material in a three-electrode setup, the optimized α-Fe2O3 HR/RGO-30, comprised 76.5 wt% α-Fe2O3 and 23.2 wt% RGO, was able to offer the largest specific capacitance of 426.3 F g−1, an excellent rate capability as well as satisfactory cycle life with capacitance retention of 87.7% and Coulombic efficiency of 98.9% after continuously charging/discharging at 10 A g−1 for beyond 10,000 cycles. Such electrochemical behaviors of the α-Fe2O3 HR/RGO-30 electrode can rival or even surpass those of many Fe2O3-based electrodes documented in the previous literature. Later, a symmetric supercapacitor cell of α-Fe2O3 HR/RGO-30//α-Fe2O3 HR/RGO-30 was fabricated. The assembled device offers the maximum energy density of 18.7 Wh kg−1, and also exhibits commendable rate capability, and features stable cycling durability (with capacitance retention of 83.2% together with a Coulombic efficiency of 99.3% after 10,000-cycle charge/discharge at 5 A g−1). These notable electrochemical performances enable the α-Fe2O3 HR/RGO-30 composite to be a high-potential material for advanced energy storage systems.
]]>Molecules doi: 10.3390/molecules29061261
Authors: Tomasz Jeliński Maciej Przybyłek Magdalena Mianowana Kinga Misiak Piotr Cysewski
In this study, both practical and theoretical aspects of the solubility of edaravone (EDA) in Deep Eutectic Solvents (DESs) were considered. The solubility of edaravone in some media, including water, can be limited, which creates the need for new efficient and environmentally safe solvents. The solubility of EDA was measured spectrophotometrically and the complex intermolecular interactions within the systems were studied with the COSMO-RS framework. Of the four studied DES systems, three outperformed the most efficient classical organic solvent, namely dichloromethane, with the DES comprising choline chloride and triethylene glycol, acting as hydrogen bond donor (HBD), in a 1:2 molar proportion yielding the highest solubility of EDA. Interestingly, the addition of a specific amount of water further increased EDA solubility. Theoretical analysis revealed that in pure water or solutions with high water content, EDA stacking is responsible for self-aggregation and lower solubility. On the other hand, the presence of HBDs leads to the formation of intermolecular clusters with EDA, reducing self-aggregation. However, in the presence of a stoichiometric amount of water, a three-molecular EDA–HBD–water complex is formed, which explains why water can also act as a co-solvent. The high probability of formation of this type of complexes is related to the high affinity of the components, which exceeds all other possible complexes.
]]>Molecules doi: 10.3390/molecules29061260
Authors: Fuyun Su Tingshu He Zhongmao He Qihao Yu Haiyan Wang
Polymer-modified cement-based materials have been widely used in building materials. Polymers play a crucial role in improving the performance of cement-based materials. At the same time, different polymers are added according to specific special requirements to meet the needs of the industry. Therefore, this paper reviewed the research on the performance and mechanism of acrylic lotion in modifying cement-based materials. Firstly, the role of acrylate lotion in the improvement of the volume stability, mechanical properties, and durability of cement-based materials was discussed to explore the advantages and disadvantages further, optimize the application of polymer in cement-based materials according to the performance improvement, and amplify the advantages of polymer modification. Secondly, the physicochemical mechanism of acrylate-lotion-modified cement-based materials was discussed, and the products and reactants of acrylate lotion in the reaction process of cement-based materials, as well as the interaction mechanism of acrylic lotion and cement hydrates, were clarified. Cement hydration is a crucial step in exploring the mechanism of polymer-modified cement-based materials. Due to the acrylate lotion filled on the cement surface and the physical and chemical interaction between them, the cement hydration is delayed, resulting in the cement retarding phenomenon. This paper describes its mechanism. Finally, the improvement effect of acrylate lotion on the performance of cement-based materials was reviewed, the research methods of mechanism research on acrylate-lotion-modified cement-based materials were evaluated, and suggestions for future research methods were provided.
]]>Molecules doi: 10.3390/molecules29061259
Authors: Melisa Donda Zbinden Mario Schmidt Charito Ivana Vignatti María Élida Pirovani Volker Böhm
The effects of high-pressure processing (HPP) (450 MPa/600 MPa/3 min) on the carotenoid and vitamin E contents of smoothies made from strawberry, orange juice, banana and apple, and the same smoothies enriched with dietary fiber from discarded carrots were compared. The contents and bioaccessibilities of these compounds were also evaluated over the course of 28 days at 4 °C. The application of HPP in the formulations significantly increased the contents of β-cryptoxanthin, α-carotene and β-carotene and retained the contents of lutein, zeaxanthin and vitamin E compared to untreated samples. A decreasing trend in the content of each compound was observed with an increase in storage time. The application of HPP initially led to reductions in the bioaccessibility of individual compounds. However, overall, during storage, there was an increase in bioaccessibility. This suggests that HPP influences cell structure, favoring compound release and micelle formation. HPP is a sustainable method that preserves or enhances carotenoid extractability in ready-to-drink fruit beverages. Furthermore, the incorporation of dietary fiber from carrot processing discards supports circular economy practices and enhances the health potential of the product.
]]>Molecules doi: 10.3390/molecules29061258
Authors: Ewelina Honkisz-Orzechowska Dorota Łażewska Grzegorz Baran Katarzyna Kieć-Kononowicz
The resolution of inflammation is the primary domain of specialised pro-resolving mediators (SPMs), which include resolvins, protectins, and their forms synthesised under the influence of aspirin and the maresins. The role of these SPMs has been discussed by many authors in the literature, with particular reference to neuroinflammation and significant neurological disorders. This review discusses the role of G protein-coupled receptor 18 (GPR18), resolvin D2 (RvD2) activity, and the GPR18-RvD2 signalling axis, as well as the role of small molecule ligands of GPR18 in inflammation in various health disorders (brain injuries, neuropathic pain, neurodegenerative/cardiometabolic/cardiovascular/gastrointestinal diseases, peritonitis, periodontitis, asthma and lung inflammation, Duchenne muscular dystrophy, SARS-CoV-2-induced inflammation, and placenta disorders. The idea of biological intervention through modulating GPR18 signalling is attracting growing attention because of its great therapeutic potential. With this paper, we aimed to present a comprehensive review of the most recent literature, perform a constructive view of data, and point out research gaps.
]]>Molecules doi: 10.3390/molecules29061257
Authors: Xiaoxin Zhao Yuanyuan Ge Xuejian Yu Chong Liu Haizhi Li Xi Wang Su Yao
The lactic acid bacteria Streptococcus thermophilus and Lactobacillus helveticus are commonly used as starter cultures in dairy product production. This study aimed to investigate the characteristics of fermented milk using different ratios of these strains and analyze the changes in volatile compounds during fermentation and storage. A 10:1 ratio of Streptococcus thermophilus CICC 6063 to Lactobacillus helveticus CICC 6064 showed optimal fermentation time (4.2 h), viable cell count (9.64 log10 colony-forming units/mL), and sensory evaluation score (79.1 points). In total, 56 volatile compounds were identified and quantified by solid-phase microextraction and gas chromatography–mass spectrometry (SPME-GC-MS), including aldehydes, ketones, acids, alcohols, esters, and others. Among these, according to VIP analysis, 2,3-butanedione, acetoin, 2,3-pentanedione, hexanoic acid, acetic acid, acetaldehyde, and butanoic acid were identified as discriminatory volatile metabolites for distinguishing between different time points. Throughout the fermentation and storage process, the levels of 2,3-pentanedione and acetoin exhibited synergistic dynamics. These findings enhance our understanding of the chemical and molecular characteristics of milk fermented with Streptococcus thermophilus and Lactobacillus helveticus, providing a basis for improving the flavor and odor of dairy products during fermentation and storage.
]]>Molecules doi: 10.3390/molecules29061256
Authors: Yuanxi Deng Ningning Yang
A disposable electrochemical sensor based on silver nanoparticle-embedded cellulose hydrogel composites was developed for sensitive detection of sulfamethoxazole residues in meat samples. Scanning electron microscopy confirmed the porous structure of the cellulose matrix anchored with 20–50 nm silver nanoparticles (AgNPs). Fourier transform infrared spectroscopy and X-ray diffraction verified that the metallic AgNPs coordinated with the amorphous cellulose chains. At an optimum 0.5% loading, the nanocomposite sensor showed a peak-to-peak separation of 150 mV, diffusion-controlled charge transfer kinetics, and an electron transfer coefficient of 0.6 using a ferro/ferricyanide redox probe. Square-wave voltammetry was applied for sensing sulfamethoxazole based on its two-electron oxidation peak at 0.72 V vs. Ag/AgCl in Britton–Robinson buffer of pH 7.0. A linear detection range of 0.1–100 μM sulfamethoxazole was obtained with a sensitivity of 0.752 μA/μM and limit of detection of 0.04 μM. Successful recovery between 86 and 92% and less than 6% RSD was achieved from spiked meat samples. The key benefits of the proposed disposable sensor include facile fabrication, an antifouling surface, and a reliable quantification ability, meeting regulatory limits. This research demonstrates the potential of novel cellulose–silver nanocomposite materials towards developing rapid, low-cost electroanalytical devices for decentralized on-site screening of veterinary drug residues to ensure food safety.
]]>Molecules doi: 10.3390/molecules29061255
Authors: Silvia Pezzola Mariano Venanzi Pierluca Galloni Valeria Conte Federica Sabuzi
The selection of a “perfect tool” for the theoretical determination of acid-base dissociation constants (Ka) is still puzzling. Recently, we developed a user-friendly model exploiting CAM-B3LYP for determining pKa with impressive reliability. Herein, a new challenge is faced, examining a panel of functionals belonging to different rungs of the “Jacob’s ladder” organization, which classifies functionals according to their level of theory. Specifically, meta-generalized gradient approximations (GGAs), hybrid-GGAs, and the more complex range-separated hybrid (RSH)-GGAs were investigated in predicting the pKa of differently substituted carboxylic acids. Therefore, CAM-B3LYP, WB97XD, B3PW91, PBE1PBE, PBEPBE and TPSSTPSS were used, with 6-311G+(d,p) as the basis set and the solvation model based on density (SMD). CAM-B3LYP showed the lowest mean absolute error value (MAE = 0.23) with relatively high processing time. PBE1PBE and B3PW91 provided satisfactory predictions (MAE = 0.34 and 0.38, respectively) with moderate computational time cost, while PBEPBE, TPSSTPSS and WB97XD led to unreliable results (MAE > 1). These findings validate the reliability of our model in predicting carboxylic acids pKa, with MAE well below 0.5 units, using a simplistic theoretical level and a low-cost computational approach.
]]>Molecules doi: 10.3390/molecules29061254
Authors: Gulzhan Ye. Yerlan Michael Shen Bakyt B. Tyussyupova Sagdat M. Tazhibayeva Kuanyshbek Musabekov Paul Takhistov
There is a strong need to develop an insulin delivery system suitable for oral administration and preserving natural (α-helix) insulin conformation. In this work, we fabricated alginate–gelatin hydrogel beads for insulin encapsulation. Altering matrix composition and crosslinking agents has resulted in various surface morphologies and internal spatial organization. The structures of the insulin-loaded matrices were studied using optical and field emission electronic microscopy. We use FTIR spectroscopy to identify insulin conformation changes as affected by the hydrogel matrices. It was found that blended alginate–gelatin matrices demonstrate better encapsulation efficiency and stronger swelling resistance to a simulated gastric environment than sodium alginate beads crosslinked with the CaCl2. FTIR measurements reveal conformation changes in insulin. It is also confirmed that in the presence of gelatin, the process of insulin fibrinogenesis ceases due to intermolecular interaction with the gelatin. Performed molecular modeling shows that dipole–dipole interactions are the dominating mechanism that determines insulin behavior within the fabricated matrix.
]]>Molecules doi: 10.3390/molecules29061253
Authors: Mei Sun Nong-Qi Mao Sheng-Long Wang Xin-Ming Han Gang Yao Ping Xue Chong-Yang Zeng Yu-Ting Liu Kai Chen Xiao-Qing Gao Jun Xiong
An unparalleled copper(I)-catalyzed synthesis of 1,3,4-oxadiazoles from tertiary amines in one step has been described. The one-pot reactions involving (N-isocyanimine)triphenylphosphorane, tertiary amines, and carboxylic acids resulted in the formation of 1,3,4-oxadiazoles in moderate to good yields through a consecutive oxidative Ugi/aza-Wittig reaction, enabling the direct functionalization of sp3 C-H bonds adjacent to the nitrogen atom. This method offered several notable advantages, including ligands-free, exceptional productivity and a high functional group tolerance. The preliminary biological evaluation demonstrated that compound 4f inhibited hepatoma cells efficiently, suggesting potentially broad applications of the approach for synthesis and medicinal chemistry.
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