Search Results (544)

A novel Ag(I) coordination polymer, [Ag₂(bipy)(btca)]_n, (SCP 1) was synthesized using 4,4′-bipyridyl (bipy) and 1,2,4,5-benzene-tetracarboxylic acid (H₄BTC). Characterization by FT-IR, ¹H/¹³C NMR, and single-crystal X-ray diffraction confirmed its 3D network structure. The structure of SCP 1 consists of two chains arranged in …ABAB… fashion. Chain A is one-dimensional, containing [Ag(4,4′-bipy)]_n chain, while chain B is free, containing uncoordinated 1,2,4,5-benzene tetracarboxylate and water molecules. The stacking and argentophilic interactions extend the chain A of [Ag(4,4′-bipy)]_n into a two-dimensional layer. In contrast, chain B of uncoordinated 1,2,4,5-benzene tetracarboxylate and water molecules form a 1-D chain through extensive hydrogen bonds between water molecules and BTC ions and between water molecules themselves. Chains A and B are connected through extensive hydrogen bonds, generating a three-dimensional network structure. This Silver I supramolecular coordination polymer (SCP 1) demonstrated high catalytic activity as a recyclable heterogeneous catalyst for the synthesis of 5-substituted 1H-tetrazoles via [3+2] cycloaddition of NaN₃ and terminal nitriles under solvent-free conditions in a Q-tube pressure reactor (yields: 94–99%). A mechanistic proposal involving cooperative Lewis acidic Ag(I) sites and Brønsted acidic -COOH groups facilitates the cycloaddition and protonation steps. SCP 1 catalyst exhibits reusability up to 4 cycles without significant loss of activity. The structural stability of the SCP 1 catalyst was assessed based on PXRD and FTIR analyses of the catalyst after usage, confirming its integrity during the recycling process. Full article

This study reports on the synthesis, structural characterization and gas sorption studies of a homometallic 2D Cd²⁺ MOF and two heterometallic 3D Cd²⁺/Ca²⁺ and Cd²⁺/Sr²⁺ -MOFs based on the angular tetracarboxylic ligand 3,3′,4,4′-sulfonyltetracarboxylic acid (H₄STBA). The homometallic 2D Cd²⁺ MOF with the formula [NH₂(CH₃)₂]⁺₂[Cd(STBA)]²⁻_n·nDMF·1.5nH₂O—(1)_n·nDMF·1.5nH₂O was synthesized from the reaction of CdCl₂·H₂O and 3,3′,4,4′-diphthalic sulfonyl dianhydride (3,3′,4,4′-DPSDA) with stoichiometric ratio of 1:1.3 in DMF/H₂O (5/2 mL) at 100 °C. The two heterometallic Cd²⁺/Ca²⁺ and Cd²⁺/Sr²⁺ compounds were prepared from analogous reactions to this afforded (1)_n·nDMF·1.5nH₂O with the difference that the reaction mixture also contained AE(NO₃)₂ (AE²⁺ = Ca²⁺ or Sr²⁺) and, in particular, from the reaction of AE(NO₃)₂, CdCl₂·H₂O and 3,3′,4,4′-DPSDA with stoichiometric ratio 1:1.1:1.4 in DMF/H₂O (5/2 mL) at 100 °C. Notably, compounds [CdCa(STBA)(H₂O)₂]_n·0.5nDMF—(2)_n·0.5nDMF and [CdSr(STBA)(H₂O)₂]_n·0.5nDMF—(3)_n·0.5nDMF are the first heterometallic compounds Mⁿ⁺/AE²⁺ (M = any metal ion) reported containing ligand H₄STBA. The structure of (1)_n·nDMF·1.5nH₂O comprises a 2D network based on helical 1D chain secondary building unit (SBU) [Cd²⁺(STBA)⁴⁻)]²⁻. The 2D sheets are linked through hydrogen bonding interactions, giving rise to a pseudo-3D structure. On the other hand, compounds (2)_n·1.5nH₂O and (3)_n·1.5nH₂O display 3D microporous structures consisting of a helical 1D chain SBU [Cd²⁺AE²⁺(STBA)⁴⁻)]. All three compounds contain rhombic channels along c axes. The three MOFs exhibit an appreciable thermal stability, up to 350–400 °C. Gas sorption measurements on activated materials (2)_n and (3)_n revealed moderate BET surface areas of 370 m²/g and 343 m²/g, respectively, along with CO₂ uptake capacity of 2.58 mmol/g at 273 K. Full article

Background/Objectives: The present work deals with the sol–gel synthesis of hybrid materials based on a silica–polyvinylpyrrolidone (Si-PVP) system. Methods: The nanohybrids have been prepared using an acidic catalyst at ambient temperature. Ibuprofen (IBP) was used as a model substance in the obtained model drug systems, while tetraethyl orthosilicate (TEOS) was used as a silica precursor. Poly(vinylpyrrolidone) (PVP) and IBP were introduced into the reaction mixture as solutions in ethanol using two different approaches: (i) a direct introduction of a drug solution into the reaction mixture during sol–gel synthesis, and (ii) a solvent deposition technique. Results: XRD data provide evidence that IBP entrapped in the silica–PVP network is in an amorphous state. By SEM it was revealed that in the adsorbate, the IBP particles possess an average particle size of about 20 μm. Based on the obtained IR and UV-Vis spectral results, the existence of hydrogen bonding of IBF with silica and PVP could be suggested. Solid-state NMR analysis allowed the identification of the presence of both crystalline-like and amorphous phases in the hybrid material prepared by the sol–gel method, while it was demonstrated that in the adsorbate, the rigid crystalline dimeric structure of the drug has been preserved. Conclusions: The overall analysis of the structural characteristics of the two materials indicated that in the hybrid material obtained by the sol–gel method, the interactions between the amorphous drug, PVP, and the silica matrix are more pronounced as compared to the adsorbate. An improvement of the drug’s aqueous solubility as well of in vitro drug release profile (up to 8 h) was achieved, demonstrating the potential of the developed drug–silica–organic polymer nanohybrid as a promising drug delivery system. Full article

In this study, the insufficient ability of tartary buckwheat protein (TBP) to stabilize Pickering emulsions was addressed by preparing TBP–sodium alginate (SA) composite particles via cross-linking and systematic optimization of the preparation parameters. The results showed that at a pH of 9.0 with 1.0% (w/v) TBP and 0.2% (w/v) SA, the zeta potential of the prepared TBP–SA composite particles was significantly more negative, and the particle size was significantly larger, than those of TBP, while emulsifying activity index and emulsifying stability index increased to 53.76 m²/g and 78.78%, respectively. Scanning electron microscopy confirmed the formation of a dense network structure; differential scanning calorimetry revealed a thermal denaturation temperature of 83 °C. Fourier transform infrared spectroscopy and surface hydrophobicity results indicated that the complex was formed primarily through hydrogen bonding and hydrophobic interactions between TBP and SA, which induced conformational changes in the protein. The Pickering emulsion prepared with 5% (w/v) TBP–SA composite particles and 60% (φ) oil phase was stable during 4-month storage, at a high temperature of 75 °C, high salt conditions of 600 mM, and pH of 3.0–9.0. The stabilization mechanisms may involve: (1) strong electrostatic repulsion provided by the highly negative zeta potential; (2) steric hindrance and mechanical strength imparted by the dense interfacial network; and (3) restriction of droplet mobility due to SA-induced gelation. Full article

Hydrogels are crosslinked polymer chains that form a three-dimensional network, widely used for wound dressing due to their ability to absorb significant amounts of fluid. This study aimed to develop a hydrogel patch for wound dressing with self-healing properties, particularly for joints and stretchable body parts, providing a physical barrier while maintaining an optimal environment for wound healing. Polyvinyl alcohol (PVA) and sodium carboxymethyl cellulose (Na CMC) were crosslinked with borax, which reacts with the active hydroxyl groups in both polymers to form a hydrogel. The patches were loaded with ciprofloxacin HCl (CIP), a broad-spectrum antibiotic used to prevent and treat various types of wound infections. Hydrogels were subjected to rheological, morphological, antimicrobial, self-healing, ex vivo release, swelling, cytotoxicity, wound healing, and stability studies. The hydrogels exhibited shear-thinning, thixotropic, and viscoelastic properties. Microscopic images of the CIP hydrogel patch showed a porous, crosslinked matrix. The antimicrobial activity of the patch revealed antibacterial effectiveness against five types of Gram-positive and Gram-negative bacteria, demonstrating a minimum inhibitory concentration of 0.05 μg/mL against E. coli. The swelling percentage was found to be 337.4 ± 12.7%. The cumulative CIP release percentage reached 103.7 ± 3.7% after 3 h, followed by zero-order release kinetics. The stability studies revealed that the crossover point shifted toward higher frequencies after 3 months of storage at room temperature, suggesting a relaxation in the hydrogel bonds. The cytotoxicity study revealed that the CIP hydrogel patch is non-cytotoxic. Additionally, the in vivo study demonstrated that the CIP hydrogel patch possesses wound-healing ability. Therefore, the CIP PVA/Na CMC/Borax patch could be used in wound dressing. Full article

The voltage-gated proton channel (H_v1) selectively transports protons (H⁺) across biological membranes in response to membrane potential changes. H_v1 is assembled as a dimer, and unlike most voltage-gated ion channels, it lacks a traditional central pore domain; instead, the voltage-sensing domain (VSD) of each monomer facilitates proton conduction via a hydrogen-bond network. H_v1 is widely expressed in various human cell types (e.g., immune cells, sperm, etc.) including tumor cells. In tumor cells, the accumulation of acidic intermediates generated by glycolysis under hypoxic conditions or ROS production leads to significant cytosolic acidification. H_v1 can remove protons from the cytosol rapidly, contributing to the adaptation of the cells to the tumor microenvironment, which may have significant consequences in tumor cell survival, proliferation, and progression. Therefore, H_v1 may be very promising not only as a tumor marker but also as a potential therapeutic target in oncology. Molecules that modulate the proton flux through H_v1 can be divided into two broad groups: inhibitors and activators. H_v1 inhibitors can be simple ions, small molecules, lipids, and peptides. In contrast, fewer H_v1 activators are known, including albumin, NH29, quercetin, and arachidonic acid. The mechanism of action of some inhibitors is well described, but not all. H_v1 modulation has profound effects on cellular physiology, especially under stress or pathological conditions, like cancer and inflammation. The therapeutic application of selective H_v1 inhibitors or activators could be a very promising strategy in the treatment of several serious diseases. Full article

This study explores the challenge of using anthocyanin-rich natural deep eutectic solvent (NADES) extracts to produce electrospun nanofibers for biodegradable freshness indicators. Red cabbage was extracted with two choline chloride-based NADESs (with citric or lactic acid), modified with 10–50% ethanol to lower viscosity, and compared with a standard 50% ethanol-water solvent. The citric acid NADES with 30% ethanol gave the highest anthocyanin yield (approx. 0.312 mg/mL, more than 20 times higher than the ethanol extract at approx. 0.014 mg/mL). For fiber fabrication, a polymer carrier blend of poly(ethylene oxide) (PEO) and sodium alginate (Alg) was employed, known to form hydrogen-bonded networks that promote chain entanglement and facilitate electrospinning. Despite this, the NADES extracts could not be electrospun into nanofibers, while the ethanol extract produced continuous, smooth fibers with diameters of approximately 100 nm. This highlights a clear trade-off; NADESs improve anthocyanin recovery, but their high viscosity and low volatility prevent fiber formation under standard electrospinning conditions. To leverage the benefits of NADES extracts, future work could focus on hybrid systems, such as multilayer films, core-shell fibers, or microcapsules, where the extracts are stabilized without relying solely on direct electrospinning. In storage tests, ethanol-extract nanofibers acted as effective pH-responsive indicators, showing visible color change from day 4 of meat storage. At the same time, alginate films with NADES extract remained unchanged after 12 days. These results highlight the importance of striking a balance between chemical stability and sensing sensitivity when designing anthocyanin-based smart packaging. Full article

Cyclodextrin-based nanosponges (CDNSs) are novel polymers composed of cross-linked cyclodextrin (CD) macrocyclic units, whose characteristics make them great candidates for drug delivery systems with adjustable properties for the drug release process. Examination of the molecular structure and dynamics of CDNSs is a necessary starting point in the first step toward their broad application. Spectroscopic methods are effective analytical tools for probing the structure–property relationships of polymer structures. Infrared (IR) and Raman spectroscopies provide insight into the behavior of hydrogen bond (H-bond) networks influencing the properties of CDNS polymeric networks. Scattering techniques such as inelastic neutron scattering (INS) and Brillouin light scattering (BLS) probe elastic properties, while small-angle neutron scattering (SANS) examines the structural inhomogeneities and water sorption abilities of CDNS materials. Complete evaluation is possible using nuclear magnetic resonance (NMR), which can provide data on CDNS network dynamics. This article summarizes the results of a wide examination of CDNSs with the use of spectroscopic methods and reveals the links between the microscopic behavior and macroscopic properties of CDNSs, enabling the customization of their properties for various biomedical purposes. Full article

The growing demand for efficient thermal management in power electronics and high-density optoelectronic systems necessitates thermal interface materials (TIMs) with high through-plane thermal conductivity and minimal anisotropy. However, conventional polymer composites filled with platelet-type fillers such as hexagonal boron nitride (h-BN) suffer from strong directional thermal transport and interfacial resistance, limiting their practical effectiveness. To address this limitation, we present a hybrid filler strategy wherein h-BN and silicon carbide (SiC) nanoparticles interact via hydroxylated surfaces, forming a three-dimensional thermally conductive network. The resulting BN–SiC composite exhibits enhanced through-plane thermal conductivity (1.61 W/mK at 70 vol%) and lower anisotropy ratios (<2.0 at 30 vol%), all while maintaining mechanical integrity and processability. These results demonstrate that chemical bonding at the filler interface can reduce interfacial thermal resistance and extend thermal conduction paths three-dimensionally, providing insights into interface-based heat transfer mechanisms. This strategy presents a scalable and practical approach for next-generation thermal management solutions in electronic packaging and high-power device platforms. Full article

This study aimed to evaluate the physical properties and biodegradability of sulfur-vulcanized polyhydroxyalkanoates (PHAs) with unsaturated side chains. As a vulcanizable PHA, poly(3-hydroxybutyrate-co-3-hydroxy-5-hexenoate) [P(3HB-co-3H5HE)] was biosynthesized with a 3H5HE fraction of 3–47 mol% using recombinant Escherichia coli and subsequently vulcanized with varying sulfur contents (2–20 per hundred resin, phr) in the presence of zinc oxide, stearic acid, and 2-mercaptobenzothiazole as curing agents. The vulcanized PHA copolymers were insoluble in chloroform, indicating the formation of a cross-linked network. Raman spectroscopy revealed the functional loss of the double bonds in the polymers. After the vulcanization with 5 phr sulfur, the tensile strength and elongation at break of P(3HB-co-47 mol% 3H5HE) increased from 0.6 MPa to 6.3 MPa and from 430% to 813%, respectively. This sample exhibited low tensile set (8%) after 200% elongation, indicating rubber-like properties. Although biodegradability decreased with increasing crosslink density, vulcanized P(3HB-co-3H5HE) exhibited a greater degradation potential than vulcanized rubber but was lower than that of non-vulcanized P(3HB-co-3H5HE). These findings demonstrate that sulfur vulcanization can enhance the resilience of unsaturated PHAs, making them suitable for elastomeric and environmental applications. Full article

In this article, the 1,3-dipolar cycloaddition (1,3-DC) reactions between 4-acyl-1H-pyrrole-2,3-diones fused at the [e]-side with a heterocyclic moiety (FPDs) and diphenylnitrone are studied using Molecular Electron Density Theory (MEDT) at different computational levels. An analysis of the global reactivity descriptors has determined the role of the reagents. FPDs will act as electrophiles, while diphenylnitrone will be a nucleophile. It was found that the reactions proceed according to a one-step but asynchronous mechanism. Additionally, based on the Bonding Evolution Theory (BET) analysis of the model 1,3-DC reaction between FPDs 1b and diphenylnitrone 2, we can distinguish eight different phases. The formation of the first C1-O5 single bond takes place in phase VII through the disappearance of the V(C1) monosynaptic basin and the depopulation of the V″(O5) monosynaptic basin, while the formation of the second C2-C3 single bond begins at the last phase of the reaction through the connection of two V(C2) and V(C3) monosynaptic basins. Based on this, we can classify this reaction as a “one-step two-stage” process. Furthermore, molecular dynamics (MD) simulation analysis up to 100 ns demonstrated the stability of both the 2P3B–Ligand1 and 2P3B–Zidovudine complexes. An enhancer of shape compression was generated for ligand1, whereas Zidovudine generated a more packed and stable hydrogen bond network that would allow a better occupancy of the active site. Full article

Background: Skin injuries, such as chronic wounds and inflammatory skin diseases, often face limitations in treatment efficacy due to the low efficiency of transdermal drug delivery and insufficient local concentrations. Curcumin (CUR), a natural compound with anti-inflammatory and antioxidant properties, has demonstrated potential in the repair of skin damage; however, its clinical application is hindered by its physicochemical characteristics. This study constructs a novel nanocomposite drug delivery system: CUR-loaded micellar nanocomposite gel (CUR-M-DMNs-Gel). A composite system is used to achieve the efficient solubilization and enhanced transdermal permeation of CUR, thereby providing a novel formulation approach for the treatment of skin diseases. Methods: CUR-loaded micellar (CUR-M) utilizes CUR as the core active ingredient, which possesses multiple pharmacological effects including anti-inflammatory and antioxidant properties. TPGS serves as a micellar carrier that not only enhances the solubility and stability of CUR through its amphiphilic structure but also facilitates drug absorption and transport within the body. In dissolvable microneedles (DMNs), PVP K30 forms a stable three-dimensional network structure through entanglement of polymer chains, ensuring sufficient mechanical strength for effective penetration of the skin barrier. Meanwhile, PVP K90, with its higher molecular weight, enhances the backing’s support and toughness to prevent needle breakage during application. The incorporation of hyaluronic acid (HA) improves both the moisture retention and adhesion properties at the needle tips, ensuring gradual dissolution and release of loaded CUR-M within the skin. In CUR-loaded micellar gel (CUR-M-Gel), PVP K30 increases both adhesive and cohesive forces in the gel through chain entanglement and hydrogen-bonding interactions. Tartaric acid precisely regulates pH levels to adjust crosslinking density; glycerol provides a long-lasting moisturizing environment for the gel; aluminum chloride enhances mechanical stability and controlled drug-release capabilities; NP-700 optimizes dispersion characteristics and compatibility within the system. Results: In vitro experiments demonstrated that the CUR-M-DMNs-Gel composite system exhibited enhanced transdermal penetration, with a cumulative transdermal efficiency significantly surpassing that of single-component formulations. In the mouse skin defect model, CUR-M-DMNs-Gel facilitated collagen deposition and effectively inhibited the expression of inflammatory cytokines (TNF-α, IL-6, and IL-1β). In the mouse skin photoaging model, CUR-M-DMNs-Gel markedly reduced dermal thickness, alleviated damage to elastic fibers, and suppressed inflammatory responses. Conclusions: The CUR-M-DMNs-Gel system can enhance wound healing through subcutaneous localization, achieving long-term sustained efficacy. This innovative approach offers new insights into the treatment of skin injuries. Full article

Approximately half of the world population is infected with the human pathogen Helicobacter pylori, which causes gastric inflammation, chronic gastritis, or peptide ulceration. A significant factor in the colonization of the upper digestive system is the helical shape of H. pylori. This helical form is maintained by a complex network of peptidoglycan (PG)-modifying enzymes and cytoskeletal proteins. Among these, the D,D-endopeptidase Csd2 plays a central role, working in conjunction with other cell shape-determining (Csd) proteins. Csd1 and Csd2 have been categorized as members of the M23B metallopeptidase family. These enzymes are classified as D,D-endopeptidases, and their function involves the cleavage of the D-Ala4-mDAP3 bond, which is present in the cross-linked di-mer muropeptides. Despite the fact that the structure of the Csd1:Csd2 complex has been examined via biochemical methods, information on the in vivo localization and dynamics of D,D-endopeptidases is still missing. Here, we use an approach that employs sophisticated different microscopy methods to visualize the spatial temporal localization and dynamics of Csd2, involving both structured illumination microscopy and single-molecule tracking. Our findings thus contribute to refining the existing model for this cellular complex by revealing curvature-dependent spatial organization and temporal dynamics underlying peptidoglycan remodeling processes essential for helical cell shape formation and maintenance. Understanding the dynamics provides insight into the mechanisms that maintain bacterial morphology and potential targets for therapeutic intervention. Full article

The thioether-functionalized 2-azabutadiene (ⁱPrS)₂C=C(H)-N=CPh₂ L1 ligates to Mn(CO)₅Br to form the five-membered chelate compound fac-MnBr(CO)₃[(ⁱPrS)₂C=C(H)-N=CPh₂] MnPropBr, whose crystal structure has been determined from X-ray diffraction data. In the crystal, different secondary intermolecular interactions, such as Br^…HC and π^…π, give rise to a supramolecular network. The electronic properties of the metal–ligand bonds in MnPropBr are similar to those of complex MnPhBr (with R = SPh instead of ⁱPrS); this also applies to a series of structurally analogous fac-ReX(CO)₃[(RS)₂C=C(H)-N=CPh₂] (X = Cl, Br and I; R = SⁱPr, SPh and S^tBu) rhenium complexes and are discussed on the basis of QT-AIM (Quantum Theory of Atoms in Molecules) calculations. New bond length/electron density relationships are proposed for the metal–halide bonds, including, for the first time, complexes of one given metal and all three corresponding halides. In order to obtain a set of coherent data, three manganese complexes that belong to the family fac-MnX(CO)₃[N∩N] (X = Cl, Br and I; N∩N is a chelating ligand with two coordinating N atoms) were included in this study. Full article

Polymorphism critically influences the solid-state properties of organic molecules, affecting stability, solubility, and functionality. We investigated the polymorphic behavior of enantiomerically pure (+)-(6aS,11aS)-medicarpin through combined experimental and computational analyses. Single-crystal X-ray diffraction revealed two distinct chiral polymorphs: the previously reported monoclinic P2₁ form and a newly identified orthorhombic P2₁2₁2₁ form with a fully chiral packing arrangement. The discovery of this previously unreported polymorph underscores the subtle yet decisive effects of solvent and conformational flexibility in directing crystallization. Detailed structural analysis reveals that, whereas the P2₁ form is only stabilized by a single dominant electrostatic interaction, the P2₁2₁2₁ form features a more complex network comprising C-H···π contacts, bifurcated C-H···O hydrogen bonds, and aromatic edge-to-face interactions. Further investigation of a functionalized p-nitrobenzoate derivative corroborates the critical influence of molecular substituents and crystallization conditions on packing motifs. Lattice energy DFT calculations confirm that each polymorph is stabilized by distinct electrostatic and dispersive interaction patterns, illustrating the complex energetic landscape of polymorph selection. Altogether, this work provides a framework for understanding and anticipating which polymorph is likely to form under specific solvent and crystallization conditions, offering insights for future strategies in materials design and guiding the pursuit of patentable crystalline forms in pharmaceutical applications. Full article