Search Results (506)

The experimental IR and Raman vibrational spectra of a hydrated La(III) complex with a 1,2,3-triazole ligand were characterized by using four different Density Functional Theory (DFT) levels and two accurate scaling procedures. In the theoretical calculations, the hydration water in the experimental sample was considered under the Discrete Model (DM) with different numbers of explicit water molecules and different positions around the La(III) ion and the carboxylate groups. The predicted IR spectra at the M06-2X/Lanl2dz level appear to be the closest to the experimental ones. Based on the optimized structures, molecular properties and global chemical descriptors were also calculated, and the findings obtained are discussed in detail herein. Additionally, several photophysical properties were determined in both the free ligand and in several lanthanide complexes, and with the sample in the solid state and in DMSO solution. A blue shift in the fluorescence of the complexes was observed compared to the free ligand, as well as in the solid-state sample compared to the solution. Full article

The impact of final surface preparation immediately prior to hydrogen content measurements in aluminum alloy samples was investigated using thermal desorption analysis (TDA). Samples ground in water showed an apparent hydrogen signal. Glow-discharge optical emission spectroscopy (GDOES) confirmed that the analyzed hydrogen originated from the subsurface layer. X-ray photoelectron spectroscopy (XPS) revealed the presence of a thin aluminum oxide/hydroxide layer on the surface. Formation of these compounds indicates that hydrogen was introduced into the material by the reaction of oxide-free aluminum with water molecules during the grinding, followed by its entrapment at near-surface interstitial lattice sites. Chemical pickling in concentrated nitric acid and combined grinding, chemical pickling, and electrochemical polishing approaches are proposed as proper surface-preparation techniques for samples without and with adherent corrosion products, respectively. Full article

Natural products possess potent pharmacological activities and health benefits. However, drawbacks such as water insolubility, poor stability, and low bioavailability limit their practical applications. This research is dedicated to the development of suitable natural self-assembled nano-delivery systems to encapsulate natural molecule drugs, improving their dispersion and stability in aqueous solution. As a model drug, curcumin (Cur) was encapsulated in zinc–adenine nanoparticles (Zn–Adenine), based on the self-assembly of a coordination matrix material. Hyaluronic acid (HA) was further functionalized on the surface of Cur@(Zn–Adenine) to realize a tumor-targeted delivery system. The morphology was characterized through TEM and zeta potential analyses, while the encapsulation mechanism of the nanoparticles was researched via XRD and FTIR. The formed Cur@(Zn–Adenine)@HA nanoparticles exhibited good drug loading efficiency and drug loading rate. Moreover, compared to free Cur, Cur-loaded (Zn–Adenine)@HA showed enhanced pH stability and thermal stability. In particular, Cur@(Zn–Adenine)@HA demonstrated excellent biocompatibility and strong specificity for targeting CD44 protein on cancer cells. The above results indicate that (Zn–Adenine)@HA NPs can serve as an effective nano-delivery system for hydrophobic substances. Full article

In this study, we develop a graphene-trenched silicon Schottky junction for humidity sensing. This novel structure comprises suspended graphene bridging etched trenches on a silicon substrate, creating both free-standing and substrate-contacting regions of graphene that enhance water adsorption sensing. Suspended graphene is intrinsically insensitive to water adsorption, making it difficult for adsorbed H₂O to effectively dope the graphene. In contrast, when graphene is supported on the silicon substrate, water molecules can effectively dope the graphene by modifying the silicon’s impurity bands and their hybridization with graphene. This humidity-induced doping leads to a significant modulation of the Schottky barrier at the graphene–silicon interface, which serves as the core sensing mechanism. We investigate the current–voltage (I–V) characteristics of these devices as a function of trench width and relative humidity. Our analysis shows that humidity influences key device parameters, including the Schottky barrier height, ideality factor, series resistance, and normalized sensitivity. Specifically, larger trench widths reduce the graphene density of states, an effect that is accounted for in our analysis of these parameters. The sensor operates under both forward and reverse bias, enabling tunable sensitivity, high selectivity, and low power consumption. These features make it promising for applications in industrial and home safety, environmental monitoring, and process control. Full article

Measurements of the surface tension of aqueous solutions of some trisiloxane surfactants containing various polyether groups (HOL7, HOL9, and HOL12) at 293 K, 303 K, and 313 K were performed. The studied surfactants were synthesized by hydrosilylation reaction and their structural analysis was carried out by the ¹H NMR, ¹³C NMR, ²⁹Si NMR, as well as FT-IR techniques. The thermal stability of HOL7, HOL9, and HOL12, as well as their molecular weight distributions, were also studied. On the basis of the obtained experimental results of the surface tension of aqueous solutions of HOL7, HOL9, and HOL12, the activity of the studied surfactants at the water–air interface was determined and discussed in the light of intermolecular interactions. Using the measured values of the surface tension, the Gibbs surface excess concentration, the area occupied by the surfactant molecule in the adsorption layer, and the standard Gibbs free energy of adsorption of the studied surfactants at the water–air interface were also calculated. Based on the obtained thermodynamic parameters of adsorption of the studied surfactants at the water–air interface, temperature, as well as a number of polyether groups in the hydrophilic part of surfactant, impact on particular surfactant adsorption was deduced. In general, the changes in the standard Gibbs free energy of adsorption of the studied surfactants at the water–air interface indicate that their adsorption tendency decreases with decreasing temperature. In addition, that tendency also diminishes as the number of the polyether groups in the hydrophilic part of the surfactant increases. Full article

Microbial transglutaminase (mTG) is most frequently utilized in order to increase the gelling properties of soybean protein isolate (SPI), but there are still some limitations of mTG-based hydrogel fabrication technology. Therefore, we aimed to develop a dual modification technique based on enzyme plus organic acid treatment to fabricate SPI hydrogels with high gel strength and stability. Our results showed that mTG plus glucose-δ-lactone (GDL), lactobionic acid (LBA) or maltobionic acid (MBA) treatment could significantly improve the gel strength, textural properties, and water-holding capacity of SPI hydrogels. Also, the addition of these organic acids remarkably reduced the surface hydrophobicity (H₀) and intrinsic fluorescence as well as increased the storage modulus (G′), loss modulus (G″) values, average particle size, and the absolute value of zeta potential of samples. GDL, LBA, or MBA greatly increased the β-sheet level and decreased the α-helix level in hydrogels, as well as dissociated 11S subunits of SPI into 7S subunits. Notably, covalent interactions, hydrogen bonding, and hydrophobic interactions of three organic acids with SPI, as well as the effects of organic acids on the interactions among the intramolecular and intermolecular forces of SPI molecules, contributed to their promoting effects on the formation of hydrogels. The LF-NMR and SEM analyses confirmed the effects of GDL, LBA, and MBA on converting the free water into immobilized and bound water as well as forming a dense stacked aggregate structure. Therefore, GDL, LBA, and MBA are promising agents to be combined with mTG in the fabrication of SPI hydrogels with high gel strength and stability. Full article

Methylene blue (MB), a widely used industrial dye, is a persistent pollutant with documented toxicity to aquatic organisms and potential health risks to humans, even at ultra-trace levels. Conventional monitoring techniques such as UV–Vis spectroscopy and fluorescence emission suffer from limited sensitivity, typically failing to detect MB below ~10⁻⁷ M. In this study, we introduce a surface-enhanced Raman spectroscopy (SERS) platform based on silver nanowire (AgNW) substrates that enables MB detection over an unprecedented dynamic range—from 1.5 × 10⁻⁴ M down to 1.5 × 10⁻¹⁶ M. Raman mapping confirmed the presence of individual signal hot spots at the lowest concentration, consistent with the theoretical number of analyte molecules in the probed area, thereby demonstrating near-single-molecule detection capability. The calculated enhancement factors reached up to 1.90 × 10¹², among the highest reported for SERS-based detection platforms. A semi-quantitative calibration curve was established spanning twelve orders of magnitude, and this platform was successfully applied to monitor MB degradation during two advanced oxidation processes (AOPs): TiO₂ nanotube-mediated photocatalysis under UV irradiation and atmospheric-pressure dielectric barrier discharge (DBD) plasma treatment. While UV–Vis and fluorescence techniques rapidly lost sensitivity during the degradation process, the SERS platform continued to detect the characteristic MB Raman peak at ~1626 cm⁻¹ throughout the entire treatment duration. These persistent SERS signals revealed the presence of residual MB or partially degraded aromatic intermediates that remained undetectable by conventional optical methods. The results underscore the ability of AgNW-based SERS to provide ultra-sensitive, molecular-level insights into pollutant transformation pathways, enabling time-resolved tracking of degradation kinetics and validating treatment efficiency. This work highlights the importance of integrating SERS with AOPs as a powerful complementary strategy for advanced environmental monitoring and water purification technologies. By delivering an ultra-sensitive, low-cost sensor (<USD 0.16 per test) and promoting reagent-free treatment methods, this study directly advances SDG 6 (Clean Water and Sanitation) and SDG 12 (Responsible Consumption and Production). Full article

Superoxide dismutase 1 (SOD1) is a crucial enzyme that protects cells from oxidative damage by converting superoxide radicals into H₂O₂ and O₂. This detoxification process, essential for cellular homeostasis, relies on a precisely orchestrated catalytic mechanism involving the copper cation, while the zinc cation contributes to the structural integrity of the enzyme. This study presents the 2.3 Å crystal structure of human SOD1 (PDB ID: 9IYK), revealing an assembly of six homodimers and twelve distinct active sites. The water molecules form a complex hydrogen-bonding network that drives proton transfer and sustains active site dynamics. Our structure also uncovers subtle conformational changes that highlight the intrinsic flexibility of SOD1, which is essential for its function. Additionally, we observe how these dynamic structural features may be linked to pathological mutations associated with amyotrophic lateral sclerosis (ALS). By advancing our understanding of hSOD1’s mechanistic intricacies and the influence of water coordination, this study offers valuable insights for developing therapeutic strategies targeting ALS. Our structure’s unique conformations and active site interactions illuminate new facets of hSOD1 function, underscoring the critical role of structural dynamics in enzyme catalysis. Moreover, we conducted a molecular docking analysis using SOD1 for potential radical scavengers and Abelson non-receptor tyrosine kinase (c-Abl, Abl1) inhibitors targeting misfolded SOD1 aggregation along with oxidative stress and apoptosis, respectively. The results showed that CHEMBL1075867, a free radical scavenger derivative, showed the most promising docking results and interactions at the binding site of hSOD1, highlighting its promising role for further studies against SOD1-mediated ALS. Full article

The flower buds of Syzygium nervosum are traditional edible and medicinal plant materials for the treatment of inflammation and stomach disorders. With rising demand for natural products in food and cosmetics, the nutraceutical and nutricosmetic potential of the flower buds has been evaluated in this work. The antioxidant activity of ethanol and water extracts of S. nervosum flower buds were detected through free radical scavenging (DPPH, ·OH, and ABTS) assays, and their inhibitory effects on tyrosinase and elastase enzymes were also evaluated. The ethanol extract (SNEE) exhibited stronger antioxidant activity and superior inhibitory effects on both enzymes compared with the water extract (SNWE), highlighting its potential for anti-aging and skin-whitening applications. Meanwhile, the LC-QTOF-MS was employed for the identification of key chemical molecules responsible for the nutricosmetic properties. Moreover, the enzyme inhibitory mechanisms of the flower bud extracts were further elucidated using inhibition kinetics and molecular docking methods. This research underscores the promising nutraceutical and nutricosmetic potential of S. nervosum flower buds so as to offer important information for further developing the edible flower resource as skin feeding bioactive ingredients. Full article

The selective adsorption and separation of benzene from structurally similar six-membered hydrocarbons and fluorocarbons remain a significant challenge due to their comparable physical properties. In this study, we investigated the molecular recognition and separation properties of a perfluorinated triketonate Cu(II) complex (1) as a Nonporous Adaptive Crystal (NAC). In addition to the previously reported benzene (2)-encapsulated crystal of 1•(2)₃, we report here the crystal structures of guest-free 1 and cyclohexene (3)-encapsulated 1•(O)₂•3, where (O)₂ represents two water molecules. Single-crystal analysis demonstrated that 1 selectively encapsulates 2 while excluding other hydrocarbons, including 3, cyclohexane (4), trifluorobenzene (5), and hexafluorobenzene (6). Gas adsorption experiments confirmed this high affinity for 2, as reflected in its preferential adsorption behavior in mixed solvent and vapor environments. The molecular selectivity of 1 was attributed to strong π-hole···π and metal···π interactions, which favor electron-rich aromatic guests. Additionally, crystallization experiments in competitive solvent systems consistently led to the formation of 1•(2)₃, reinforcing the high selectivity of 1 for 2. These findings highlight the unique molecular recognition capabilities of NACs, providing valuable insights into the rational design of advanced molecular separation materials for industrial applications involving aromatic hydrocarbons. Hirshfeld surface analysis revealed that the contribution of F···F interactions to crystal packing decreased upon guest recognition (48.8% in 1, 34.2% in 1•(O)₂•3, and 22.2% in 1•(2)₃), while the contribution of F···H/H···F interactions increased (8.6% in 1, 22.2% in 1•(O)₂•3, and 35.4% in 1•(2)₃). Regarding Cu interactions, the self-assembled columnar structure of 1 results in close contacts at the coordination sites, including Cu···Cu (0.1%), Cu···O (0.7%), and Cu···C (1.3%). However, in the guest-incorporated structures 1•(O)₂•3 and 1•(2)₃, the Cu···Cu contribution disappears; instead, 1•(O)₂•3 exhibits a significant increase in Cu···O interactions (1.2%), corresponding to water coordination, while 1•(2)₃ shows an increase in Cu···C interactions (1.5%), indicative of the metal···π interactions of benzene. Full article

Water molecules in the cytosol of red blood cells (RBCs) may exist in a free or bound state. The ratio between the free and bound water depends on the composition of the cytoplasm, particularly on the hemoglobin concentration. Microwave dielectric spectroscopy (MDS) provides information on the state of intracellular water in red blood cell suspension and the erythrocyte cytosol state. In the presented study, we used MDS to assess the differences in the free-to-bound water ratio in subpopulations of freshly donated human erythrocytes of different ages (young, mature, and senescent cells) obtained by fractionation in a Percoll density gradient. The obtained MDS parameters (dielectric strength ∆ε, the relaxation time τ, and the broadening parameter α) were compared with the red blood cell indices and single cell deformability measurements obtained for each subpopulation. We demonstrated that the unique hematological indices and deformability of red blood cells of different ages are well-correlated with the specific values of dielectric fitting parameters. The obtained results indicate that the dielectric properties of cytosolic water can serve as a sensitive marker of changes occurring in the cytosol of red blood cells during cell aging. Full article

Electrolytes play a vital role in the performance and safety of electrochemical energy storage devices, such as lithium-ion batteries (LIBs). While traditional LIBs rely on organic electrolytes, these flammable solutions pose safety risks and require expensive, moisture-sensitive manufacturing processes. Aqueous electrolytes offer a safer, more cost-effective alternative, but their narrow electrochemical window, corrosivity to electrodes, and enabling of dendritic growth on metal anodes limit their practical applications. Water-in-salt electrolytes (WiSEs) have emerged as a promising solution to these challenges. By significantly reducing water activity and forming a stable solid–electrolyte interphase (SEI), WiSEs can expand the electrochemical stability window, inhibit material dissolution, and suppress dendritic growth. This unique SEI formation mechanism, which is similar to that observed in organic electrolytes, contributes to the improved performance and stability of WiSE-based batteries. Additionally, the altered solvation structure of WiSEs minimizes the presence of free water molecules, further stabilizing the SEI and reducing water activity. This review comprehensively examines the composition, mechanisms, and characterization of WiSEs and their application in monovalent-metal-ion batteries. Full article

Background: Luteolin, a flavonoid with well-documented antioxidant properties, has garnered significant attention for its potential therapeutic effects. Objectives: This study aims to investigate the antioxidant properties of luteolin under the influence of solvents, utilizing computational techniques to elucidate its interactions and its potential role as a modulator of enzymatic activities, particularly with Cytochrome 17A1. Methods: Density Functional Theory (DFT) calculations were employed to determine luteolin’s electronic and structural characteristics. Key aspects analyzed included electron density distribution and the energies of the frontier molecular orbitals (HOMO and LUMO). Free radical scavenging mechanisms were explored by comparing the dissociation enthalpy of the O–H bond in the absence and presence of water molecules. Additionally, molecular docking simulations were performed to assess the interactions of luteolin with Cytochrome 17A1, identifying preferred binding sites and interaction energies. Results: The findings indicate that luteolin possesses distinct structural and electronic features that contribute to its effectiveness in protecting against oxidative stress. However, hydrogen bonding interactions with water molecules were found to influence the dissociation enthalpy of the O–H bond. Docking simulations revealed significant interaction profiles between luteolin and Cytochrome 17A1, suggesting its potential role as a modulator of this protein. Conclusions: This study underscores the therapeutic potential of luteolin and highlights the importance of computational techniques in predicting and understanding the molecular interactions of bioactive compounds with biological targets. The results provide valuable insights that may aid in developing new therapeutic strategies for diseases associated with oxidative stress. Full article

Measuring molecular mobility (M_m) in solid food is challenging due to the rigid and heterogeneous nature of these matrices. The thermodynamic parameter Strength (S) fails to account for molecular displacement distances. This study emphasizes the role of molecular dynamic (MD) simulation in quantifying M_m on amorphous lactose at mimic water activities (a_w) at temperatures above the glass transition temperature (T_g), incorporating the S. The results show that coordinating root mean square displacement (RMSD) effectively quantifies M_m across different a_w and temperature conditions. Both increased a_w and higher temperatures facilitate M_m by expanding free volume and reducing energy barriers for molecular rearrangement, as indicated by the mobility coefficient calculations. This study also emphasizes the importance of system size in interpreting M_m, as larger systems exhibit emergent behaviors that smaller systems cannot capture. The calculated MD relaxation time for 10,000-molecule lactose/water cells at a specific S value was successfully translated to a real timescale of 1.8 × 10⁶ s, consistent with experimental data (1.2 × 10⁶ s). Moreover, water can shift from a plasticizing role to a more stabilizing one, slowing molecular motion and leading to equilibrium clustering. These findings have important implications for understanding the behavior of amorphous lactose in food and pharmaceutical formulations. Full article

The change in the surface properties of polymer materials used in an extracorporeal membrane oxygenation (ECMO) device due to nitric oxide (NO) treatment was characterized by zeta-potential and dynamic contact-angle measurements. FTIR-ATR was used to determine the stability of these effects during liquid contact. Polymethyl pentene (PMP), methyl methacrylate acrylonitrile butadiene styrene (MABS), and polyurethane (PU) were investigated. The polymer materials were treated with NO (1000 ppm) for 17 h. The samples for FTIR-ATR measurements were submerged in water or physiological sodium chloride solution for 120 and 240 h after the end of the gas treatment. PMP showed no changes at all. MABS showed decreased contact-angles and increased contact-angle hysteresis. In contrast, PU showed decreased contact-angles and a shift in its zeta-potential curve, indicating a more hydrophilic and acidic surface. The FTIR-ATR measurements showed a slight decrease in the signal intensities after liquid contact. The results indicated an improvement in the liquid contact properties of MABS and the PU due to increased surface hydrophilicity caused mainly by the adsorbed nitric acid (HNO₃) molecules formed by the NO treatment. The results presented in this paper point towards a simple and complication-free method of introducing NO into an ECMO circuit. Full article