Search Results (202)

A triphenylphosphine-functionalized silica gel material, optimized for lead adsorption, was synthesized via a one-pot sol–gel reaction and characterized using FTIR and solid-state ¹³C and ²⁹Si NMR and XPS spectroscopy. The interaction between lead cations and phosphine groups was evaluated using the ³¹P NMR chemical shift tensor as a sensor. Two distinct types of phosphine groups, exhibiting different rotational mobility behaviors, were identified, with their ratio influenced by the presence of lead cations. These results suggest that the adsorption behavior of lead on this functionalized silica gel adsorbent can be directly evaluated by its lead–phosphorus interaction. This association was corroborated by the shifting of the binding energies of phosphorus functional groups after lead uptake in the XPS analysis. Full article

Searching for new and efficient transfer hydrogenation catalysts, a series of new organometallic ruthenium(II)-arene complexes of the formulae [Ru(η⁶-p-cymene)(L)Cl][PF₆] (1–8) and [Ru(η⁶-p-cymene)(L)Cl][Ru(η⁶-p-cymene)Cl₃] (9–11) were synthesized and fully characterized. These were prepared from the reaction of pyridine–quinoline and biquinoline-based ligands (L) with [Ru(η⁶-p-cymene)(μ-Cl)Cl]₂, in 1:2 and 1:1, metal (M) to ligand (L) molar ratios. Characterization includes a combination of spectroscopic methods (FT-IR, UV-Vis, multi nuclear NMR), elemental analysis and single-crystal X-ray crystallography. The pyridine–quinoline organic entities encountered, were prepared in high yield either via the thermal decarboxylation of the carboxylic acid congeners, namely 2,2′-pyridyl-quinoline-4-carboxylic acid (pqca), 8-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8-Mepqca), 6′-methyl-2,2′-pyridyl-quinoline-4-carboxylic acid (6′-Mepqca) and 8,6′-dimethyl-2,2′-pyridyl-quinoline-4-carboxylic acid (8,6′-Me₂pqca), affording the desired ligands pq, 8-Mepq, 6′-Mepq and 8,6′-Me₂pq, or by the classical Friedländer condensation, to yield 4,6′-dimethyl-2,2′-pyridyl-quinoline (4,6′-Me₂pq) and 4-methyl-2,2′-pyridyl-quinoline (4-Mepq), respectively. The solid-state structures of complexes 1–4, 6, 8 and 9 were determined showing a distorted octahedral coordination geometry. The unit cell of 3 contains two independent molecules (Ru-3), (Ru′-3) in a 1:1 ratio, due to a slight rotation of the arene ring. All complexes catalyze the transfer hydrogenation of acetophenone, using 2-propanol as a hydrogen donor in the presence of KOiPr. Among them, complexes 1 and 5 bearing methyl groups at the 8 and 4 position of the quinoline moiety, convert acetophenone to 1-phenylethanol quantitatively, within approximately 10 min with final TOFs of 1600 h⁻¹. The catalytic performance of complexes 1–11, towards the transfer hydrogenation of p-substituted acetophenone derivatives and benzophenone, ranges from moderate to excellent. An inner-sphere mechanism has been suggested based on the detection of ruthenium(II) hydride species. Full article

The misfolding and aggregation of proteins into amyloidogenic assemblies are key features of several metabolic and neurodegenerative diseases. Human insulin has long been known to form amyloid fibrils under various conditions, which affects its bioavailability and function. Clinically, insulin aggregation at recurrent injection sites poses a challenge for diabetic patients who rely on insulin therapy. Furthermore, decreased responsiveness to insulin in type 2 diabetic (T2D) patients may lead to its overproduction and accumulation as aggregates. Earlier reports have reported that various factors such as pH, temperature, agitation, and the presence of lipids or other proteins influence insulin aggregation. Our present study aims to elucidate the effects of non–micellar anionic DMPG (1,2–dimyristoyl–sn–glycero–3–phosphoglycerol) lipids on insulin aggregation. Distinct pathways of insulin aggregation and intermediate formation were observed in the presence of DMPG using a ThT fluorescence assay. The formation of soluble intermediates alongside large insulin fibrils was observed in insulin incubated with DMPG via TEM, DLS, and NMR as opposed to insulin aggregates generated without lipids. ¹³C magic angle spinning solid–state NMR and FTIR experiments indicated that lipids do not alter the conformation of insulin fibrils but do alter the time scale of motion of aromatic and aliphatic side chains. Furthermore, the soluble intermediates were found to be more cytotoxic than fibrils generated with or without lipids. Overall, our study elucidates the importance of anionic lipids in dictating the pathways and intermediates associated with insulin aggregation. These findings could be useful in determining various approaches to avoid toxicity and enhance the effectiveness of insulin in therapeutic applications. Full article

Medicinal mushroom production utilising rural cultivation (solid state fermentation) requires approximately six months compared to culinary mushroom production (7 days). Urban cultivation (submerged liquid fermentation) can be used as a sustainable method of producing medicinal mushroom biomass. In this study, chicken patties were fortified with liquid-fermented Ganoderma lucidum flour (GLF) and Pleurotus djamor mushroom biomass flour (PDF) at concentrations of 3%, 6%, and 9%. These were compared to a negative control (0% mushroom flour chicken patty) and a commercial patty. Chicken patties fortified with 3% PDF and 9% GLF recorded the lowest cooking loss, at 5.55% and 10.3%, respectively. Mushroom chicken patties exhibited lower cooking losses and significant changes in colour and texture compared to control samples. Notably, 3% GLF chicken patty achieved the highest overall acceptability score of 6.55 followed by 9% PDF chicken patty (6.08) (p < 0.05). Biomass flour of liquid-fermented Ganoderma lucidum (ENS-GL) and Pleurotus djamor (ENS-PD) were extracted for their endopolysaccharide and analysed for their functional properties. All elemental, FT-IR, and NMR spectroscopy analyses revealed the existence of a comparable beta-glucan polymer structure, linkages, and absorptions when compared to the Laminarin standard. In addition, ENS-GL also proved to possess higher antimicrobial activities and significant antioxidant levels (DPPH-scavenging activity, ferric reduction potential and total phenolic content) compared to ENS-PD. Overall, this study revealed that sustainable liquid-fermented Ganoderma lucidum, a medicinal mushroom, outperformed Pleurotus djamor, a culinary mushroom, as a potential alternative flour for combating hunger in the future. Full article

The organic compounds 2-aminopyrimidine (AP) and 4-aminobenzoic acid (PABA) were selected for the synthesis of a compound by establishing the phase diagram and adopting the solid-state synthesis method. The phase diagram analysis suggested the formation of a novel intermolecular compound (IMC) at a 1:1 stoichiometric ratio of AP and PABA, along with two eutectics at 0.25 and 0.90 mole fractions of AP. FTIR and NMR spectroscopy were used for the structure elucidation of the intermolecular compound. The powder X-ray diffraction analysis revealed the novel nature of IMC (APPABA) and the mechanical mixture nature of eutectics. The sharp and single peak of the DSC curve suggested the melting and pure nature of the synthesized IMC. Various thermodynamic parameters of IMC and eutectics were studied. A single crystal of the IMC was grown from solution and its single-crystal X-ray diffraction analysis revealed that it crystallized in a monoclinic system with the P21/n space group. Hirshfeld surface analysis further validated the weak non-covalent interactions summarized through the single-crystal X-ray analysis. Studies on the IMC were thoroughly conducted to evaluate its antibacterial activity with reference to antibiotics, and it showed significant positive responses against various pathogenic microbial isolates (Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Klebsiella aerogenes, and Shigella boydii) and non-pathogenic microbial isolates (Enterobacter cloacae, Pseudomonas azotoformans, and Burkholderia paludis). It was also found effective against methicillin-resistant bacterial strains viz. Staphylococcus aureus MRSA. Full article

This work studies the effect of mesostructured silica–zirconia–tungstophosphoric acid (SiO₂-ZrO₂-TPA) composites used as catalysts in the synthesis of nifedipine by the Hantzsch methodology. The selectivity for nifedipine is determined, along with that of secondary products that may form depending on the reaction conditions. The materials were synthesized via the sol–gel method and characterized by N₂ adsorption–desorption isotherms, infrared spectroscopy (FT-IR), ³¹P solid-state nuclear magnetic resonance (NMR-MAS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), and potentiometric titration. The characterization results from the XPS spectra showed that as the Si/Zr ratio drops, the Si-O-Si signal size decreases, while the Zr-O signal size increases. Characterization by titration indicated that an increase in the total acidity of the material, resulting from support modification with tungstophosphoric acid (H₃PW₁₂O₄₀, TPA), enhances the reaction yield. The catalytic activity in the solvent-free Hantzsch reaction was evaluated under thermal heating and microwave irradiation. The experiments conducted at 80 °C achieved a maximum yield of 57% after 4 h of reaction using the Si20Zr80TPA30 catalyst (50 mg), while by microwave heating, the yield significantly improved, reaching 77% in only 1 h of reaction. This catalyst exhibited stability and reusability without significant loss of activity up to the third cycle. Depending on the type of material and the reaction conditions, it is possible to modify the selectivity of the reaction, obtaining a 1,2-dihydropyridine isomeric to nifedipine. Reaction intermediates and other minor secondary products that may be formed in the process were also evaluated. Full article

The synthesis of [Cu(PteN^˄N)(P^˄P)][BF₄] complexes with pterin-fused phenanthroline (PteN^˄N) derivatives and bisphosphine (P^˄P) co-ligands was achieved through a mechanochemical approach. Due to the extremely poor solubility of PteN^˄N ligands, traditional solution methods are ineffective, whereas solid-state mechanochemistry reliably yielded the targeted heteroleptic—rather than homoleptic—complexes with considerable stability even in solution. The transformation from ligand to complex increased the solubility dramatically. The ligands and complexes were comprehensively characterised with a mixture of routine spectroscopic and spectrometric methods, the applicability of which depended to some extent on the compounds’ solubility, e.g., in the case of NMR spectroscopy. The photophysical properties of the complexes, which were not as exciting as anticipated, were assessed by absorption and emission spectroscopic methods, showing that further improvements are needed in complex design if these species are to be developed towards photocatalysis in the future. Full article

Improving the stability of drugs in the solid state, as well as improving their solubility and poor bioavailability, is highly physiologically relevant. In this study, we focused on enhancing the solubility of hypoxanthine (HYP) through salt formation resulting from the preparation of hypoxanthine–maleic acid salt (HYP-MAL). Single crystals were obtained through solvent evaporation methods, and DSC, TGA, PXRD, FT-IR, and ¹H NMR spectra were used to characterize the samples. The salt system had higher solubility properties than HYP, with an equilibrium solubility in water that was roughly 2.4 times greater than that of HYP, but the salt’s equilibrium solubility increased when the pH shifted from 7.4 to 1.2; additionally, from 0 to 10 min, the powder dissolution rate was 1.8 times that of HYP, resulting in increased bioavailability. The anti-obesity impact of HYP-MAL salt on obese mice was investigated, providing important insights for the development of future weight-loss medications. Full article

The application of biochar to traditional soil and soilless growth media in agriculture has been reported to increase plant production. However, it remains unclear which biochar component drives this process or which biogeochemical process is attributed to better plant productivity. Therefore, this study aims to determine how biochar organic carbon (C) composition and thermal stability influence nitrogen availability and tomato production. Soilless growth media composed of a mixture of 60% and 40% coconut coir (CC) (Cocos nucifera L.) and fine pine bark (PB) (Pinus genus), respectively, was amended with 0, 1, 2, 3, 4, 6, 8, 10, and 12% biochar per dry weight. The amended media were used to grow Red Bounty tomatoes (Lycopersicum esculentum) for three months. After harvesting tomatoes and determining yield, organic C composition and C thermal stability of the biochar amended soilless growth media mixtures were determined using solid-state ¹³C nuclear magnetic resonance (¹³C NMR) and multi-elemental scanning thermal analysis (MESTA), respectively. Thermal stability data were used to determine the “R400 index”, and nitrate (NO₃⁻) concentration was determined using the water extractable method. Results showed that biochar-amended media significantly increased pH (p < 0.0001) and NO₃⁻ (p = 0.0386) compared to the no-char control. Biochar amended soilless media organic C composition was dominated by O-alkyl-C as a result of a higher fraction of soilless media; however, total C, carboxyl-C, phenolic-C, and aromatic-C increased with increasing biochar content and related negatively to R400, which decreased with increasing biochar content. Nitrate retention and tomato yield increased with increasing total C, carboxyl-C, phenolic-C, and aromatic-C and decreasing R400. This indicates that the stable form of C, carboxyl-C, phenolic-C, aromatic-C, and low R400 enhanced NO₃⁻ sorption, reducing leaching and enhancing its availability for tomato growth. Full article

In this work, we studied the thermal behavior and infrared fingerprint of anhydrous and hydrated DL-tartaric acid via conventional and modulated Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA), Fourier Transform Infrared Spectroscopy (FTIR), nuclear magnetic resonance (NMR), pH measurements, and ab initio density functional theory (DFT) calculations. Six samples were examined in total (raw, recrystallized from D₂O solution, freeze-dried, and three heated samples). The results reveal that both forms (anhydrous and hydrated) do not exhibit melting prior to decomposition. It is also shown that the so-called DL-tartaric acid does not exist in the solid state in pure form, but it contains water and a tartaric acid oligomer, which is produced through esterification. Alteration of the chemical structure (reflected through decomposition) is initiated at quite low temperatures and is more pronounced for the hydrated form. Up to 75 °C, decomposition proceeds through esterification, while at higher temperatures it seems to be reversed due to the increase in water and decrease in COOH groups emerging through anhydride formation. Either upon heating or at sub-zero temperatures during freeze-drying, the hydrated form decomposes, and although some water is removed, new water is produced due to esterification. The conclusions are also supported by DFT calculations. Full article

The synthesis and characterization of the tripodal phosphines RSi(CH₂CH₂PPh₂)₃ (R = Me, OMe, OEt) (1–3) is described. The ¹H NMR spectra of all phosphines display virtual coupling patterns. The ligands form the corresponding trinuclear Pd complexes [RSi(CH₂CH₂PPh₂)₃]₂(PdCl₂)₃ (4–6) with three PdCl₂ moieties sandwiched between two tripodal ligands. The complexes 4, 5, and 7 (R = OH) have been analyzed by single crystal X-ray diffraction. The coordination at the Pd center is square planar with the phosphine groups occupying trans positions. The ³¹P{¹H} MAS NMR spectra of polycrystalline 1 are in accordance with the packing motif of the molecules in the unit cell. The tripodal ligand 3 has successfully been immobilized on silica as 3i. It coordinates PdCl₂ on the surface, as demonstrated by ³¹P{¹H} MAS NMR. Hereby, the cis coordination is prevalent when 3i has maximal surface coverage. At low surface coverage, one tripodal linker can accommodate trans coordination at the metal center. A surface-bound trinuclear Pd complex has been generated, as well as a heterobimetallic Pd/Cu complex. All surface species have been characterized by ³¹P{¹H} MAS NMR. Full article

Current research in bone tissue engineering is focused not only on basic parameters of the materials, such as biocompatibility and degradation rate but also on intrinsic osteogenic and antimicrobial properties, essential to provide a rapid tissue regeneration without negative effects due to periprosthetic infections, that may result in revision surgeries. One of the major strategies to enhance the osteogenic and antimicrobial performance of calcium phosphates is the ionic substitution, in particular, with magnesium and borates. In this study, we focused on the synthesis of boron-substituted tricalcium phosphate (B-TCP) with a target of 5 mol.% substitution via the solid-state synthesis with mechano-activation. Synthesis from raw precursors, without the preliminary brushite wet precipitation, led to the primary phase of β-TCP, which was proved by the XRD analysis. According to the IR-spectroscopy and ³¹P NMR analysis, boron substitution occurred in the synthesized sample. The developed material showed a modest antibacterial performance against E. coli, with 13.5 ± 5.0% growth inhibition, and E. faecalis, with 16.7 ± 5.5% inhibition. The biocompatibility of β-TCP and B-TCP was tested through the MTT assay and osteogenic differentiation of the mesenchymal stromal cells. The proposed synthesis approach can be useful for the fabrication of B-TCP ceramics for bone tissue engineering. Full article

Tegoprazan is a potassium ion-competitive acid blocker (P-CAB) and a novel inhibitor of gastric acid secretion. The compound exists in two crystalline polymorphs, A and B, whose structures had not previously been reported. In this study, both polymorphs were analyzed by liquid- and solid-state NMR, revealing identical tautomeric states. Using this information, the crystal structures were determined from laboratory powder X-ray diffraction data by simulated annealing and Rietveld refinement. Both forms were found to crystallize in the monoclinic space group P2₁, with Z = 4 and two independent molecules in the asymmetric unit (Z′ = 2). To assess the stability and reliability of the refined structures, we attempted geometry optimization and vibrational analysis using DFT-D methods. However, due to the high conformational complexity of Z′ = 2 systems, these calculations failed to converge or produced imaginary frequencies. Instead, single-point energy calculations were performed on the refined models. The resulting relative energy differences, together with solubility data, van’t Hoff enthalpies, and DSC profiles, consistently indicated that Polymorph A is more stable than Polymorph B. These results highlight the challenges of structure validation via DFT-D for complex molecular crystals and demonstrate the value of integrating experimental and computational approaches for polymorph characterization. Full article

Enzymatic modification of Kraft lignin under alkaline conditions was investigated using bilirubin oxidase (BOD) in borate buffer (pH 10). Control solubilization without enzyme addition revealed a notable increase in molar mass (up to 1.7-fold) and potential borate complexation with lignin hydroxyl groups, as evidenced by thermogravimetric and ¹¹B NMR analyses. BOD treatments induced substantial polymerization, with molar mass increases of up to 4-fold for insoluble fractions after 24 h, while soluble fractions exhibited progressive increases over 5 days. Quantitative ³¹P NMR showed reductions in aliphatic and phenolic hydroxyl groups by 20%, suggesting oxidative coupling reactions, particularly through 4-O-5′ and 5-5′ linkages. Solid-state ¹³C NMR confirmed structural changes associated with polymerization. Dynamic light scattering (DLS) indicated the presence of colloidal aggregates, potentially explaining challenges in HSQC NMR signal acquisition. These findings highlight the efficacy of bilirubin oxidase in catalyzing lignin polymerization and underscore the structural impact of borate–lignin interactions in alkaline media, paving the way for advanced lignin valorization strategies. Full article

ATP analogues are essential tools in enzymology and structural biology, but the structural and functional implications of their chemical modifications on nucleotide-binding proteins are often underappreciated. To address this, we evaluated a panel of ATP analogues, focusing on thiosubstituted and fluorinated molecules, using the AAA+ ATPase p97 as a benchmark system. Hydrolysis stability and impact on protein conformation, binding modes, and kinetics of enzymatic catalysis were assessed by protein-detected methyl NMR and ligand-detected ¹⁹F NMR in solution, as well as ³¹P solid-state NMR of nucleotides within protein sediments. ATPγS and AMP-PNP emerged as the most suitable analogues for preserving pre-hydrolysis states over extended periods, despite undergoing gradual hydrolysis. In contrast, both AMP-PCP and α/β-thiosubstituted analogues failed to induce native protein conformations in p97. Notably, we demonstrate a novel real-time NMR setup to explore the effect of nucleotide mixtures on cooperativity and the regulation of enzymes. Additionally, aromatic fluorine TROSY-based ¹⁹F NMR shows promise for direct ligand detection in solution, even in the context of large macromolecular complexes. These findings provide critical guidance for selecting ATP analogues in functional and structural studies of nucleotide-binding proteins. Full article