Search Results (495)

Hydrogen sulfide (H₂S) is a toxic and biologically relevant gas, necessitating sensitive and interference-resistant detection methods for environmental monitoring. Here, we develop a donor–acceptor molecular platform incorporating a polarized conjugated double bond bridge and demonstrate its application, using YG2 as the representative probe, as a dual-peak ratiometric UV–Vis sensor for H₂S. UV–Vis spectroscopy, supported by ¹H NMR analysis, indicates HS^--induced interaction with the conjugated linkage, leading to disruption of π-conjugation, suppression the intramolecular charge-transfer (ICT) band at 409 nm, and enhancing the locally excited (LE) band at 279 nm. The ratiometric parameter log(Abs₂₇₉/Abs₄₀₉) affords a linear response over the concentration range of 1.0 × 10⁻⁶–1.0 × 10⁻⁴ M with a detection limit of 8.3 × 10⁻⁷ M, providing approximately an order-of-magnitude improvement in analytical sensitivity compared with single-wavelength methods, and the reaction reaches completion within ~10 s. YG2 exhibits excellent selectivity toward H₂S over common anions and enables accurate quantification in real water samples, with recoveries of 95.43–105.86% and relative standard deviations (RSDs) of 0.56–9.58%. These results suggest that YG2 is a rapid, self-calibrating, and spectroscopically interpretable ratiometric probe suitable for reliable H₂S detection in complex aqueous environments. Full article

The high pressure response and structural stability of crystalline racemic (RS) ibuprofen up to 7 GPa are explored by Raman spectroscopy, employing diamond anvil cells for the pressure application and glycerol as the pressure transmitting medium. Two independent high pressure experiments were performed with practically identical results. Both intermolecular vibrations (associated with weak van der Waals interactions and hydrogen bonding between ibuprofen molecules) and intramolecular vibrations (associated with strong covalent bonding within the ibuprofen molecule) are monitored as a function of pressure, with the former being far more susceptible to volume contraction. The pressure dependence of the Raman peak frequencies undergoes two distinct changes at ~2 and ~6 GPa, indicating the occurrence of pressure-induced structural modifications of ibuprofen. Based on the high pressure Raman data for the intermolecular vibrations of the RS ibuprofen below 2 GPa, a zero pressure value for the bulk modulus of ~7.5 GPa is also extracted. Full article

In this work, three 3-carboxamidecoumarin derivatives (3b, 3c, and 4) were synthesized and characterized by NMR, IR, and single-crystal X-ray. All compounds maintain an essentially planar coumarin scaffold stabilized by an intramolecular N–H⋯O hydrogen bond (S(6) motif), though compound 4 exhibits a more complex bifurcated S₃²(11)[S(6)S(6)S(5)] network that enhances its conformational rigidity. The crystal packing analysis reveals that while all derivatives form one-dimensional (1D) supramolecular tapes through C–H⋯O interactions, their 3D architectures differ significantly: 3b and 3c rely on a diverse combination of π⋯π stacking and lone pair⋯π contacts, whereas 4 is governed by highly directional stacking between the pyran and pyridine rings. Hirshfeld surface analysis and CE-B3LYP energy framework calculations quantified the balance between intermolecular forces, showing that 3b is dispersion-dominated (H⋯H, 43.5%), while 3c achieves a balanced electrostatic–dispersion regime due to the nitro group, which increases O⋯H/H⋯O contacts to 37.1% and yields the highest stabilization energy (−69.1 kJ/mol). These results demonstrate that the electronic nature of the substituents at the 3- and 6-positions drastically modulates the hierarchy of non-covalent interactions, providing key insights for the crystal engineering of coumarin-based supramolecular systems. Full article

4-Methyl- (1) and 4-ethyl-8-hydroxyquinoline (2) crystallize from a mixture of diethyl ether and chloroform in the triclinic space group P$\overline{1}$. X-ray analysis reveals that both compounds form discrete molecular dimers stabilized by intermolecular O-H∙∙∙N and C-H∙∙∙O hydrogen bonds, resulting in $R_2^2\left(5\right)$ cyclic synthons. This pattern of hydrogen bonds is further stabilized by intramolecular O-H∙∙∙N bonds so that the quinoline nitrogen atom acts as a bifurcated binding site. The dimers exhibit a planar geometry and arrange into layer-like structures held together by π∙∙∙π stacking and van der Waals forces. While the fundamental bonding motifs are similar, the increased steric demand of the ethyl group in compound 2 induces a shift in the crystallographic orientation of the layers and alters the degree of π-overlap compared to the methyl-substituted analogue 1. Full article

This study aimed to clarify how molecular structure regulates the dissolution and transient gel-layer behavior of polyacrylamide-based dry-powder drag reducers for slickwater fracturing. In the Materials Studio 2020 software, molecular dynamics simulations were performed on five representative homopolymers, including: polyacrylamide (PAM), polyacrylic acid (PAA), poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS), poly(N-vinylpyrrolidone) (PNVP), and poly [2-(acryloyloxy)ethyl]trimethylammonium chloride (PDAC). The results show that in pure water, PAA exhibits the strongest thermodynamic driving force with an interaction energy of −1005.5 kcal/mol and the lowest solvation free energy of −373.289 kcal/mol. Quantitative correlation analysis established that solvation energy and hydrogen bond density are primary predictors of macroscopic performance, yielding a correlation coefficient of R² > 0.94. Experiments confirm that optimized AM/AA (7:3) and AM/AMPS (5:5) anionic copolymers achieve stable viscosity within 120 ± 5 s and 160 ± 8 s, respectively, representing a 60% reduction in dissolution time compared to conventional industrial PAM homopolymers. The polarity, charge density, and chain flexibility of functional groups jointly regulate polymer dissolution behavior. Anionic groups significantly improve dissolution performance by enhancing intramolecular electrostatic repulsion and hydration. Full article

Aflatoxin B1 (AFB1) is a potent mycotoxin threatening food and feed safety. Here, we report the identification and characterization of a Bacillus safensis-derived multicopper oxidase (BsaMCO) capable of efficient AFB1 detoxification. Recombinant BsaMCO exhibited robust in vitro activity, achieving >78% degradation of AFB1 under 24 h incubation at 37 °C. Optimization experiments revealed that enzyme concentration, pH, temperature, metal ions, and electron acceptors significantly influenced degradation efficiency, defining an operational window suitable for practical applications. LC–MS profiling suggested the presence of transformation products tentatively consistent with oxidative demethylation to aflatoxin P1 (AFP1) and with the formation of AFG2a-like products through subsequent hydration- and oxidation-related transformations. Molecular docking and 100 ns all-atom molecular dynamics (MD) simulations demonstrated stable binding of AFB1 in the T1 copper pocket. Van der Waals and electrostatic interactions, together with a persistent hydrogen bond at Gly323, facilitated single-electron transfer through the intramolecular T2/T3 copper cluster. Principal component and Gibbs free energy analyses confirmed a low-energy, stable conformational ensemble. HepG2 cell assays indicated that BsaMCO-degraded products substantially reduced cytotoxicity and apoptosis compared with native AFB1. Simulated feed experiments further validated enzymatic AFB1 degradation, with approximately 53% reduction after 24 h. Collectively, these findings establish BsaMCO as a safe and effective biocatalyst for AFB1 detoxification, providing mechanistic, structural, and cellular evidence supporting its application in food and feed safety. Full article

Background: Amorphous drug formulations are commonly used to improve the solubility and bioavailability of poorly soluble molecular pharmaceuticals, yet less is known about their molecular conformations and local bonding interactions than their crystalline phases. Methods: High-energy X-ray diffraction structure factor measurements have been made on liquid and glassy nifedipine (NIF), felodipine (FEL), NIF 1:3 polyvinylpyrrolidone (PVP), and FEL 1:3 PVP wt.% mixtures. The corresponding X-ray pair distribution functions have been interpreted using empirical potential structure refinement using different models and density functional theory conformer calculations. Results: In both NIF and FEL, the NH···O inter-molecular hydrogen bonds between the pyridyl nitrogen and ester carbonyls are found to be considerably weaker than those observed in the crystalline polymorphs. For nifedipine, it is proposed that either inter-molecular NH…ON nitro bonds are present and/or a fraction (<20%) of conformational changes, with the aryl ring flipped, occur in the liquid state. For felodipine, the models indicate significant disorder associated with the methyl and ethyl side chains in the liquid state, with the main peak intensity at 3.0 Å arising from intra-molecular Cl-Cl atom pairs. When nifedipine molecules are incorporated into PVP, our models show they possess stronger NH···O bonds to the PVP polymer than felodipine molecules, which have stronger affinity for bonding to the polymer than to other felodipine molecules. Conclusions: The amorphous forms of both NIF and FEL show much weaker hydrogen bonding than found in their crystalline phases. Liquid NIF also exhibits configurations which are not observed in the crystal phases. Full article

To investigate the potential of halogen-containing building blocks in the development of artificial carbohydrate receptors, the 1,3,5-trisubstituted 2,4,6-triethylbenzene scaffold with halogenated subunits and classical hydrogen bonding sites was used as a model system. In the first studies, the influence of the presence of halogens on the binding properties of compounds bearing benzamidomethyl units was investigated, whereby the type of halogen and its ring position were varied. The question was whether the presence of halogens could lead to an increase in binding effectivity and whether this increase can be attributed to the formation of halogen bonds (especially for X = Br and I in ortho position) with the sugar substrate or to other effects. The binding studies revealed some interesting relationships between structure and binding affinity for the tested compounds 1–9. For those bearing the halogen substituent in the ortho position to the amide functionality, the binding affinity increases in the expected order 4 (o-F) < 3 (o-Cl) < 2 (o-Br) < 1 (o-I). In the presence of small amounts of water in CDCl₃, an increase in binding strength was observed in comparison to experiments conducted in dry CDCl₃. The present studies aim to provide impulses for the use of halogenated building blocks in the design of artificial carbohydrate receptors. Optimizing the type of halogenated units and the receptor architecture should result in more effective carbohydrate receptors capable of functioning effectively in aqueous media through a combination of different noncovalent interactions. Full article

Three multicomponent crystals of metformin were investigated to elucidate factors governing crystal architecture. Structures were determined by X-ray diffraction and analyzed using the Atoms-in-Molecules (AIM) approach, focusing on critical points and electron density topology. Three types of crystals were obtained: salt, cocrystal salt solvate and mixed salt with both organic and inorganic anions. Protonation of nitrogen atoms in metformin alters bond lengths and electron density, while strong intramolecular hydrogen bonds in hydrogenmaleate anions stabilize the structures and define the preferred anion geometry. Comparison with monoprotonated metformin revealed similar topological features despite differing protonation states. Mechanochemical synthesis via liquid-assisted grinding (LAG) enabled selective formation of specific crystalline forms, with the solvent type and acid polymorph influencing product distribution. These results highlight the critical roles of protonation, hydrogen bonding, and synthetic methodology in designing and controlling multicomponent metformin crystal structures. Full article

The optimization of membrane permeability is a pivotal approach for mitigating late-stage failures in peptide drug development. By leveraging linker chemical diversity, stapled peptides utilize linker engineering to precisely modulate key physicochemical parameters—such as lipophilicity and conformational constraints—to overcome the desolvation energy penalty. This review systematically evaluates linker-based strategies for enhancing the permeability of stapled peptides, categorized into two primary dimensions: (1) high-throughput screening (HTS) compatibility, focusing on the integration of functionalized linkers into mRNA display, phage display, and DNA-encoded libraries (DELs) to identify lead scaffolds with inherent permeability potential during early discovery; and (2) post-screening structural refinement, covering rational design strategies including intramolecular hydrogen-bond (IMHB) shielding, “chameleonic” adaptations, and stimuli-responsive reversible stapling. Furthermore, we analyze the paradigm shift in assessment methodologies from qualitative imaging to quantitative cytosolic delivery assays, which have deepened our understanding of mechanisms such as the charge/lipophilicity threshold balance and metabolism-driven trapping. Overall, linker engineering provides a robust technical roadmap for developing the next generation of cell-permeable stapled peptide therapeutics. Full article

The utilization and chemical transformation of carbon dioxide remains a pressing problem in modern chemistry. Numerous experimental and theoretical studies have focused on the interaction of CO₂ with amines. In this work, quantum chemical density functional theory (DFT) calculations of equilibrium geometries, energies, electronic and vibrational characteristics of CO₂-sensitive mono-, di-, tris-hydroxyamidines and their associates were carried out by the B3LYP/6-31G(d, p) method. The harmonic vibrational frequencies were scaled and compared with the experimental FTIR spectra for supporting wavenumber assignments. Natural bond orbital (NBO) analysis of the atomic charges and charge delocalization was employed to investigate the nature of hydrogen bonding in hydroxyamidine associates. We also used the intrinsically polarizable continuum model (IEFPCM), and the DFT-D3 method was applied to account for dispersion effects during associate formation. Using the 6-311+G(2d, p) basis set for tris-hydroxyamidine, and its adducts, a comparative analysis of the experimental and calculated ¹H NMR spectra was performed. Here, we considered non-trivial sites of carbon dioxide absorption and hydroxyamidine protonation, which, to our knowledge, have hardly been considered by other authors. Present DFT results agree rather well with the experimental data and support new insight into the formation of the PIL structure. Full article

In our previous study, a taste sensor employing a lipid/polymer membrane modified with 2,6-dihydroxyterephthalic acid (2,6-DHTPA) enabled the detection of the umami substances monosodium glutamate (MSG) and inosinate monophosphate (IMP). The taste sensor was also able to evaluate the synergistic effect, an umami enhancement phenomenon that occurs between MSG and IMP. However, the structural requirements for modifiers capable of detecting IMP have not yet been clarified. In the present study, to elucidate these requirements, nine different modifiers were prepared, and taste sensor measurements for IMP were conducted in combination with ¹H-NMR analysis. As a result, three distinct patterns were observed: (1) modifiers that exhibited chemical shift changes and generated a potential response in the positive direction (i.e., a positive potential response); (2) modifiers that showed chemical shift changes but produced either an almost zero or a negative potential response; and (3) modifiers that exhibited neither chemical shift changes nor any potential response. For receptor membranes that did not exhibit a positive response, the corresponding modifiers either lacked two carboxyl groups or did not possess intramolecular hydrogen bonding involving hydroxyl groups. From these results, it was clarified that the essential conditions for obtaining a positive potential response to IMP are that the modifier (1) contains two carboxyl groups and (2) possesses intramolecular hydrogen bonding. Full article

The exceptional mechanical strength and toughness of collagen arise from its well-defined hierarchical architecture. Conventional methods for obtaining collagen aggregates (CAs), such as direct extraction from native tissues or acid swelling followed by mechanical processing, offer limited control over dimensional uniformity and provide little insight into the underlying exfoliation mechanisms. To overcome these challenges, this study introduces a novel strategy that leverages insights into the hierarchical interactions within collagen. We employ the ionic liquid 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) as an exfoliating agent to successfully isolate fibrous CAs from native bovine tendon. By precisely modulating temperature and processing time, we achieve CAs with tunable mesoscale dimensions (diameter 0.9–1.1 μm, length > 160 μm). Molecular dynamics simulations reveal that [AMIM]Cl disrupts the intramolecular hydrogen-bonding network within collagen, thereby facilitating controlled exfoliation. These exfoliated aggregates serve as fundamental building blocks for fabricating collagen films. The resulting materials exhibit robust mechanical integrity, high transparency, reversible pH-responsive behavior, and excellent biocompatibility as verified by cytotoxicity assays, which together underscore their potential as versatile biomaterial platforms. Furthermore, the integration of single-walled carbon nanotubes yields conductive composites with confirmed electrical functionality. This study thus presents an innovative pathway for the precision processing of collagen and advances the design of high-performance collagen-based biomaterials. Full article

The metallogelation process has been successfully achieved by utilizing a crystal engineering approach to generate a new metallogel. While the coordination of metal ions to ligands plays a very important role for building the primary structure, the stabilization and morphology of metallogels are heavily dependent on various intra-molecular interactions and non-covalent interactions, with hydrogen bonding (HB) often playing a dominant and structurally organizing role. In the present study, gelation experiments were achieved successfully by reacting vanadium acetylacetonate with a hydrazone ligand using different solvents. The metallogel shows excellent gelation ability with 1.7 wt% minimum gelator concentrations and the gel–sol dissociation temperature, T_gel is 55 °C (water/methanol). The structural properties of the metallogel were studied using single-crystal X-ray crystallography. The crystal structure analysis of the metallogel shows the presence of various interactions such as hydrogen bonding, pi–pi interactions, pnictogen bonding, and other weak non-covalent interactions. These molecular interactions play a very important role in the gelation process and also affect the gel’s properties like swelling behavior, viscosity, and elasticity. Full article

This study aims to investigate the relative stability of the diaminodinitroethylene isomers (cis, trans, and gem). To achieve this goal, calculations at several levels of theory were carried out. The B3LYP, PBE0, and CAM-B3LYP functionals, based on density functional theory (DFT), were used. G4 and MP2 calculations were also executed. All calculation methods predicted that the gem isomer is the most stable, while the cis isomer is the least stable. The energy order obtained for the isomers studied was rationalized by analysis of the detected intramolecular hydrogen bonding, electron delocalization, charge distribution, and changes in atomic energies in the structures studied. The origins of the superior stability of the gem isomer are demonstrated and justified. Full article