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The responses of the N-alkyl diamine groups to variations in pH affect their conformations and surface activities, making them relevant to applications relying on interfacial interactions, such as controlled emulsification and mineral flotation. An in-depth understanding of interfacial self-assembly is crucial. Herein, a molecular-level study was performed to investigate the adsorption and self-assembly of N-dodecylpropane-1,3-diamine (DPDA) at the air–water (A/W) interface using sum frequency generation (SFG) spectroscopy and molecular dynamics (MD) simulations. The SFG spectra of DPDA, acquired under three pH conditions, suggest that the protonation of the DPDA diamine group influences the alkyl chain arrangement at a varying degree at the A/W interface. Analysis of the di-cationic DPDA SFG spectrum at a low pH showed fewer gauche defects at low concentration, as indicated by the relatively higher intensity ratio (ICH3SS/ICH2SS) of 18.1 ± 0.6. The density profiles from MD simulations at different surface areas per molecule and pH conditions, showing varying degrees of packing, support the observation of gauche defects in SFG. With MD simulation, the radial distribution factor for di-cationic species has the highest probability of forming hydrogen bonds compared to mono-cationic and non-ionic species. These g(r) probability results conform with observations obtained from SFG spectroscopy, where we observed a strong hydrogen bond interaction at low pH conditions with di-cationic species, forming tetrahedrally arranged water molecules at the A/W interface. Overall, comprehensive insights will facilitate the visualization of alkyl diamines and their potential derivatives at the A/W interface, enabling a better understanding of their behavior across various applications. [ABSTRACT FROM AUTHOR]

Microsolvation of the carbamate moiety delivers precise information on complexation effects on the N–C=O backbone and is of relevance to the peptide bond functionality. In this context, the mono-, di-, and trihydrated complexes of methyl carbamate have been studied in molecular expansion by high-resolution microwave spectroscopy, using chirped-pulse and Fabry–Perot resonator Fourier transform microwave instruments covering the frequency range from 2 to 18 GHz. From the rotational constants of the parent and the 18Ow substituted monoisotopologues, accurate values have been derived for the geometries of the hydrogen bond interactions. The nuclear quadrupole coupling constant χcc of the nitrogen nucleus provides a direct measure of complexation changes and decreases with the degree of hydration, whereas the hindered internal rotation barrier increases slightly with microsolvation. Both tendencies could have a common origin in the π-cooperative inductive effects as the microsolvation series progresses. All transitions are split by the internal rotation of the methyl top and the nuclear quadrupole coupling, and in the largest cluster, they are additionally split by an inversion motion. [ABSTRACT FROM AUTHOR]

In the past five years, over 20 types of cyclo-N5− energetic materials (EMs) have been successfully synthesized. Metallic cyclo-N5− EMs exhibit higher density and performance compared to non-metallic cyclo-N5− EMs. However, the mechanisms for such metallic cyclo-N5− EMs remain unexplored. Herein, we performed a thorough quantum chemistry study on the mechanistic pathway for the cyclo-N5− trapped by metal cations in four cyclo-N5− EMs: [Na(H2O) (N5)] · 2H2O, [M(H2O)4(N5)2] · 4H2O (M = Mn, Fe, and Co), by density functional theory methods and transition state theory. During the synthesis process, the cyclo-N5− in the precursor hybrid aromatic compound is susceptible to electrophilic attack by metal cations. This attack disrupts the hydrogen bond interaction surrounding the cyclo-N5−, ultimately leading to the formation of either an ionic bond or a coordination bond between the metal cation and the cyclo-N5−, resulting in an electrophilic substitution reaction. In addition, solvent effects reduce the energy of the ionic bond, thereby promoting the reaction. Our findings will provide valuable insights for future route design and contribute to enhancing the synthesis yield of cyclo-N5− EMs in both theoretical and experimental aspects. [ABSTRACT FROM AUTHOR]

Eutectic systems design requires an in-depth understanding of their solid–liquid equilibria (SLE). Modeling SLE in eutectic systems has as prerequisites, the melting properties and activity coefficients of components in the liquid phase. Thus, due to the unavailable melting properties of thermally unstable substances, it is impossible to estimate their activity coefficients from experimental SLE data and model the SLE phase diagram of their eutectic systems. Here, we evaluate the activity coefficients of thermally unstable constituents in the liquid phase, which were calculated independent of their melting properties by correlating the SLE data of their cocrystals. Differential scanning calorimetry and powder x-ray diffraction were employed to obtain the SLE phase diagram of three eutectic systems, i.e., tetramethylammonium chloride/catechol, tetraethylammonium chloride/catechol, and betaine/catechol systems, and identify the formation of nine cocrystals. The non-random, two-liquid equation was used to calculate the activity coefficients of the components in the liquid phase. The substantial negative deviation from ideality in the three studied systems indicated strong hydrogen bonding interactions in the liquid solution. Furthermore, modeling ion–ion interactions in eutectic systems containing ionic constituents is of utmost importance for understanding their nonideality. [ABSTRACT FROM AUTHOR]

Pristine metal–organic frameworks (MOFs) are built through self-assembly of electron rich organic linkers and electron deficient metal nodes via coordinate bond. Due to the unique properties of MOFs like highly tunable frameworks, huge specific surface areas, flexible chemical composition, flexible structures and a large volume of pores, they are being used to design the electrode materials for electrochemical energy storage devices. As per the literature, MOFs (including manganese, nickel, copper, and cobalt-based zeolitic imidazolate frameworks (ZIFs), University of Oslo (UiO) MOFs, Hong Kong University of Science and Technology (HKUST) MOFs and isoreticular MOFs (IRMOFs)) have attracted much attention in the field of supercapacitors (SCs)/batteries. According to their dimensionality such as 1D, 2D and 3D, pristine MOFs are mainly used as SC materials. Highly porous materials and their composites are capable for intercalation of metal ions (Na+/Li+). Moreover, the supramolecular features (π⋯π, C–H⋯π, hydrogen bond interactions) of redox stable MOFs provide better insight for electrochemical stability. So, this review provides an in-depth analysis of pure MOFs and MOF derived composites (MOF composites and MOF derived porous carbon) as electrode materials and also discusses their metal ion charge storage mechanism. Finally, we provide our perspectives on the current issues and future opportunities for supercapacitor materials. [ABSTRACT FROM AUTHOR]

A key factor in optimizing organic solar cells (OSCs) is the precise control of blend film morphology to enhance exciton dissociation and charge transport. Solid additives play a vital role in this process, with 3D polyhedral or spherical molecules being ideal candidates due to their delocalized π‐orbitals and omnidirectional charge transport. However, the application of classical fullerene derivatives as spherical additives is limited by their synthetic complicacy and poor solubility. Herein, the potential of 3D globally aromatic carboranyl cages as solid additives, specifically 1‐amino‐o‐carborane (CB‐NH2) and 1‐carboxy‐o‐carborane (CB‐COOH), is explored to fine‐tune the film morphology and improve the performance of OSCs. These spherical molecules provide an extensive surface for hydrogen bonding interactions, which serve as the driving force for manipulating the vertical phase separation and active layer crystallinity. Remarkably, CB‐NH2‐processed devices with well‐tuned morphology yield a remarkable power conversion efficiency of 19.48%, highlighting the effectiveness of 3D carboranyl additives on improving OSC performance. This work challenges the reliance on fullerene derivatives as spherical additives and offers new insights into the mechanisms by which 3D globally aromatic additives can achieve high performance in OSCs, emphasizing the significance of molecular engineering in the development of next‐generation solar cell technology. [ABSTRACT FROM AUTHOR]

The stability of aqueous zinc metal batteries is significantly affected by side reactions and dendrite growth on the anode interface, which primarily originate from water and anions. Herein, we introduce a multi H‐bond site additive, 2, 2′‐Sulfonyldiethanol (SDE), into an aqueous electrolyte to construct a sieving‐type electric double layer (EDL) by hydrogen bond interlock in order to address these issues. On the one hand, SDE replaces H2O and SO42− anions that are adsorbed on the zinc anode surface, expelling H2O/SO42− from the EDL and thereby reducing the content of H2O/SO42− at the interface. On the other hand, when Zn2+ are de‐solvated at the interface during the plating, the strong hydrogen bond interaction between SDE and H2O/SO42− can trap H2O/SO42− from the EDL, further decreasing their content at the interface. This effectively sieves them out of the zinc anode interface and inhibits the side reactions. Moreover, the unique characteristics of trapped SO42− anions can restrict their diffusion, thereby enhancing the transference number of Zn2+ and promoting dendrite‐free deposition and growth of Zn. Consequently, utilizing an SDE/ZnSO4 electrolyte enables excellent cycling stability in Zn//Zn symmetrical cells and Zn//MnO2 full cells with lifespans exceeding 3500 h and 2500 cycles respectively. [ABSTRACT FROM AUTHOR]

Short peptides are versatile molecules for the construction of supramolecular materials. Most reported peptide materials are hydrophobic, stiff, and show limited response to environmental conditions in the solid‐state. Herein, we describe a design strategy for minimalistic supramolecular metallo‐peptide nanofibers that, depending on their sequence, change stiffness, or reversibly assemble in the solid‐state, in response to changes in relative humidity (RH). We tested a series of histidine (H) containing dipeptides with varying hydrophobicity, XH, where X is G, A, L, Y (glycine, alanine, leucine, and tyrosine). The one‐dimensional fiber formation is supported by metal coordination and dynamic H‐bonds. Solvent conditions were identified where GH/Zn and AH/Zn formed gels that upon air‐drying gave rise to nanofibers. Upon exposure of the nanofiber networks to increasing RH, a reduction in stiffness was observed with GH/Zn fibers reversibly (dis‐)assembled at 60–70 % RH driven by a rebalancing of hydrogen bonding interactions between peptides and water. When these metallo‐peptide nanofibers were deposited on the surface of polyimide films and exposed to varying RH, peptide/water‐vapor interactions in the solid‐state mechanically transferred to the polymer film, leading to the rapid and reversible folding‐unfolding of the films, thus demonstrating RH‐responsive actuation. [ABSTRACT FROM AUTHOR]

Curcumin (Cur) considered as a golden nutraceutical, is emerging as one of bioactive compounds demonstrating the most promising biological activities, including antioxidant, antibacterial, anti-inflammatory, anticancer. It is also used for coloring and seasoning in foods. However, Cur applications are limited due to factors like low aqueous solubility, poor colloidal stability and bioavailability. Extensive efforts were made using pure zein (Ze) to develop nanoparticles (NPs) for encapsulation of Cur to overcome the aforementioned issues. Nevertheless, zein nanoparticles (ZeNPs) have limitations related to their instability to neutral pH and rapid degradation by gastric proteases. Thus, the combination between Ze and different biopolymers to produce zein nanocomposites (ZeNCs) for improving the stability of ZeNPs were scrutinized in this study. The mass ratio of Ze/polymer played a critical in the formation and stability of ZeNCs. Electrostatic attraction, hydrogen bonding and intermolecular interaction were responsible for ZeNCs formation. High encapsulation efficiency (EE), storage stability, solubility, bioaccessibility, intestinal permeability and antioxidant activity (AA) for Cur were achieved in ZeNCs compared to ZeNPs. ZeNCs did not show toxicity towards normal NCM460 and 293 cells, but potent anticancer activity against MCF-7, HepG2, Hela, and HCT 116 cells. ZeNCs displayed potential applications in different food matrices. [ABSTRACT FROM AUTHOR]

[Display omitted] Elucidation of the micro-mechanisms of sol–gel transition of gelling glucans with different glycosidic linkages is crucial for understanding their structure–property relationship and for various applications. Glucans with distinct molecular chain structures exhibit unique gelation behaviors. The disparate gelation phenomena observed in two methylated glucans, methylated (1,3)- β - d -glucan of curdlan (MECD) and methylated (1,4)- β - d -glucan of cellulose (MC), notwithstanding their equivalent degrees of substitution, are intricately linked to their unique molecular architectures and interactions between glucan and water. Density functional theory and molecular dynamics simulations focused on the electronic property distinctions between MECD and MC, alongside conformational variations during thermal gelation. Inline attenuated total reflection Fourier transform infrared spectroscopy tracked secondary structure alterations in MECD and MC. To corroborate the simulation results, additional analyses including circular dichroism, rheology, and micro-differential scanning calorimetry were performed. Despite having similar thermally induced gel networks, MECD and MC display distinct physical gelation patterns and molecular-level conformational changes during gelation. The network of MC gel was formed via a "coil-to-ring" transition, followed by ring stacking. In contrast, the MECD gel comprised compact irregular helices accompanied by notable volume shrinkage. These variations in gelation behavior are ascribed to heightened hydrophobic interactions and diminished hydrogen bonding in both systems upon heating, resulting in gelation. These findings provide valuable insights into the microstructural changes during gelation and the thermo-gelation mechanisms of structurally similar polysaccharides. [ABSTRACT FROM AUTHOR]

PIK3CA gene encoding PI3K p110α is one of the most frequently mutated and overexpressed in majority of human cancers. Development of potent and selective novel inhibitors targeting PI3Kα was considered as the most promising approaches for cancer treatment. In this investigation, a virtual screening platform for PI3Kα inhibitors was established by employing machine learning methods, pharmacophore modeling, and molecular docking approaches. 28 potential PI3Kα inhibitors with different scaffolds were selected from the databases with 295,024 compounds. Among the 28 hits, hit15 exhibited the best inhibitory effect against PI3Kα with IC50 value less than 1.0 µM. The molecular dynamics simulation indicated that hit15 could stably bind to the active site of PI3Kα, interact with some residues by hydrophobic, electrostatic and hydrogen bonding interactions, and finally induced PI3Kα active pocket substantial conformation changes. Stable H-bond interactions were formed between hit15 and residues of Lys776, Asp810 and Asp933. The binding free energy of PI3Kα-hit15 was − 65.3 kJ/mol. The free energy decomposition indicated that key residues of Asp805, Ile848 and Ile932 contributed stronger energies to the binding free energy. The above results indicated that hit15 with novel scaffold was a potent PI3Kα inhibitor and considered as a promising candidate for further drug development to treat various cancers with PI3Kα over activated. [ABSTRACT FROM AUTHOR]

Piezoelectric nanogenerators (PENGs), the current pathway to sustainable energy harvesting, are mostly comprised of bulk oxide ceramics which are toxic, rigid, and costly to synthesize. A suitable alternative to them is flexible polar polymers like polyvinylidene fluoride (PVDF), but stabilizing its polar phase is also a daunting task. all these aforementioned issues by employing a biocompatible have been solved, above‐room‐temperature (Tc > 390 K) ferroelectric discrete molecular complex [Cu(L‐His)(bpy)]ClO4.1.5H2O (Cu‐FE) which is not only suitable for piezoelectric energy harvesting due to its large values of piezoelectric co‐efficient (d33 = 17 pm V−1) but also is capable of imparting polar β‐phase in PVDF via hydrogen bonding interactions under mild condition (60 °C). Among the PENG devices prepared with the composite films of PVDF and various weight % (w/V) compositions of Cu‐FE, the highest output voltage of 8 V (peak to peak) has been obtained, a power density of 4 µW cm−2, and an output current of 3 µA from the 1 wt.% composite film. The fabricated PENG device also exhibits swift capacitor charging in 40 s, and acts as an excellent pressure sensor, with exceptional sensitivity to low pressures (7 kPa), giving an output of 0.4 V. [ABSTRACT FROM AUTHOR]

The interaction between water molecules and surfaces in porous carbon‐based materials plays a significant role in various fields including but not limited to catalysis, gas sorption, or electrochemical energy storage and conversion. The incorporation of nitrogen enhances the hydrophilicity of typically rather nonpolar carbon‐based materials but the molecular understanding of water chemical configuration in such porous materials remains incomplete. Water adsorption on nitrogen‐containing nanoporous carbon surfaces is governed by a subtle balance between water–water and water–surface hydrogen bonding interactions, which together determine the water structures formed and their stability. In this work, in situ Scanning Transmission X‐ray microscopy performed on individual nanoporous carbon particles under a humid atmosphere is used to elucidate the interactions between nitrogen‐containing carbon surfaces and water molecules. The hydrogen bonding of water is found to be nonuniform within the particles and to depend on the nanopore size and the chemical bonding of nitrogen atoms. The nature of the nitrogen sites interacting with water is further characterized by resonance inelastic X‐ray Scattering and near ambient pressure X‐ray Photoelectron Spectroscopy. This study provides new perspectives on water interaction when confined in nanoporous nitrogen‐rich carbons. [ABSTRACT FROM AUTHOR]

Hydrogel‐based flexible solid‐state supercapacitors (SSCs) hold great promise for wearable electronics, yet significant challenges persist in simultaneously achieving excellent mechanical properties, high ionic conductivity, outstanding electrochemical properties, and wide operating temperature ranges. Here, this study presents a straightforward method for synthesizing dual crosslinked polyvinyl alcohol‐polyimide (PVA‐PI) organohydrogels via a simple one‐pot synthesis followed by a freezing‐thawing process. The controlled dual crosslinked networks with significanonetly different crosslinking densities and robust intermolecular hydrogen bonding interactions facilitated by the macromolecular crosslinker of PI, endow the organohydrogels with both high mechanical properties and ionic conductivity. Furthermore, SSCs based on PVA‐PI organohydrogels are fabricated, which can exhibit outstanding electrochemical performance at temperatures ranging from −40 to 80 °C. Specifically, the energy density reaches 16.7 µWh cm−2 even at −40 °C under a power density of 410.0 µW cm−2. These SSCs also show excellent performance stability under various deformations, such as bending and compression, alongside exceptional long‐term cycling stability (over 10 000 cycles) with high capacitance retention from −40 to 50 °C. The synthesis strategy, along with a robust mechanism for enhancing mechanical properties of hydrogels, demonstrated in this study offers insights for the development of strong hydrogels/organohydrogels with broad temperature adaptability for soft electronic applications. [ABSTRACT FROM AUTHOR]

Polymers derived from renewable carbon feedstock are destined to play a pivotal role in the transition to a sustainable circular economy, displacing conventional fossil‐carbon materials. Chitin (CT) and chitosan (CS) are well‐suited to develop multifunctional materials that are mechanically resilient and easy to process. Their abundance of hydroxyl and amine groups facilitates hydrogen bonding and electrostatic interactions, making them suitable for persistent pollutant removal from drinking water. Therefore, porous CS cryogels are fabricated by dissolution in acetic acid, coagulation, and subsequent freeze‐drying. To enhance durability in harsh environments, CT cryogels are obtained through acetylation. Furthermore, Fe3O4 nanoparticles are incorporated to enable removal by external magnetic fields. The rapid removal of per‐ and polyfluoroalkyl substances (PFASs) with capacities reaching 451 mg g−1 offers competitive performance against state‐of‐the‐art materials. The shear‐thinning properties of CS enable rapid additive manufacturing in predetermined free‐standing shapes, useful for accessing sites with complex geometries. Life cycle assessment (LCA) confirms the suitability of chitosan and CT cryogels for low environmental impact water remediation applications. Furthermore, the cryogels can be recycled, closing the material loops back into the economic cycle. Altogether, this work demonstrates the potential of chitosan and CT as competitive alternatives to fossil‐carbon derived systems for sustainable environmental remediation. [ABSTRACT FROM AUTHOR]

Natural polysaccharides‐based hydrogels have drawn extensive attention yet have been plagued by less desirable stretchability due to their inherent nature. Here, ultra‐stretchable starch‐based hydrogels (amylopectin/polyacrylamide, AAM) are developed by constructing reversible intramolecular physical interactions. This strategy endows the hydrogel with exceedingly ultrahigh deformation due to a continuous hydrogen bonding network. It can be stretched from less than 0.5 to >300 cm without breakage that the elongation exceeds 600 times the original length. The elongation collected by the universal testing machine reaches up to 36 000% without breakage outperforming previous reports and demonstrating extraordinary stretchability. Furthermore, an interwoven structure of hydrogen bonding interaction and trace covalent bonds make the stress of hydrogel reach 0.28 MPa, accompanied by an ultra‐high strain of 22 500% and significant toughness (47 MJ·m−3). The hydrogel displays high transparency (≈93%), low‐temperature resistance, moisturizing property, and extraordinary interfacial adhesion property. Intriguingly, the aqueous precursor can act as inks to prepare various forms of hydrogel within minutes through the facile writing or drawing method. This hydrogel verifies strong potential in both fields of human motion sensor (After long‐term or low‐temperature conditions) and energy storage. This study will facilitate the progress of ultra‐stretchable or multifunctional hydrogels. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (AZIBs) have become a promising energy storage device due to their low cost and high security. However, the severe dendrite growth and side reactions on metallic zinc (Zn) anode hamper their commercial implementation. Herein, a strongly electronegative trifluoroborate anion (─BF3−) functionalized polyacrylamide hydrogel (PAME) is well‐designed and constructed as the quasi‐solid‐state electrolyte to overcome these obstacles. The PAME chain segments terminated with strongly polar functional groups promote the conversion of water molecules from free water to bound water through the enhanced hydrogen bonding interaction to alleviate the side reactions. Furthermore, the PAME electrolyte featured with hierarchically porous structure and enhanced electrostatic interaction among the ─BF3− groups, and Zn2+ ions homogenizes the high‐flux Zn ion transport and induce the uniform deposition to restrain dendrite growth. Consequently, the assembled Zn‖PAME‖Zn batteries deliver remarkable cycling stability over 1800 h at 1 mA cm−2 and 900 h at 15 mA cm−2. Additionally, the constructed Zn‖PAME‖MnO2 full cells achieve a reversible capacity of 202 mAh g−1 at 2.0 A g−1 with a capacity retention rate of 91.4% over 500 cycles. This work sheds light on constructing the strongly polar hydrogel electrolyte to boost free‐dendrite Zn anodes for long‐lifespan AZIBs. [ABSTRACT FROM AUTHOR]

ABSTRACT Catalyst design and fabrication with safe and affordable components and methods is a high‐value‐added business. In this work, a vitamin‐based hybrid nanomaterial (PMoB1) is prepared by simple stirring of thiamine hydrochloride (vitamin B1, VB1) as an inexpensive commercially available biologically active compound with phosphomolybdic acid (PMo12) in acidic aqueous solution to catalyze selective oxidation of sulfides using aqueous H2O2. A small amount of this heterogeneous catalyst drives rapidly the sulfoxidation reaction under mild and solvent‐free conditions facilitating the product separation and reducing significantly the environmental impacts. The main factors of the catalytic reaction were optimized by the central composite design (CCD) method. The solid catalyst tolerates a wide range of pH and retained its structural integrity even at alkaline solution (pH = 11). PMoB1 composed of two VB1 and one PMo12 was found to be partially reduced based on 13P NMR and UV–Vis spectra. An amorphous structure with aggregated nanoparticles with sizes ranging between 50 and 70 nm and a specific surface area of 35 m2/g are important reasons for enhanced catalytic activity and selectivity. Nevertheless, non‐covalent interactions such as hydrogen bonding and the π–π stacking can also significantly affect the catalyst performance. Given the scavenging tests and spectral evidences, a non‐radical mechanism involving peroxo species is postulated. The catalysis is shown to be truly heterogeneous while the solid catalyst largely maintains its structural integrity during the recycling test. [ABSTRACT FROM AUTHOR]

Simultaneous enhancement of free excitons (FEs) emission and self‐trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI‐type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5‐fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb−I−Pb angles between two halide octahedra under high pressure indeed determines the pressure‐tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure‐optical relationships of ACI‐type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure‐suppressed nonradiative recombination. [ABSTRACT FROM AUTHOR]

Cellulose-based hydrogels have attracted considerable attention in biomedical engineering. However, existing cellulose-based adhesive hydrogels have several limitations, including poor wet adhesion, average antimicrobial activity and a lack of benign on-demand detachment. Using a dual-crosslinked design strategy, we created a cellulose-based hydrogel (ACCPFM) by combining polymerisable allyl cellulose, carboxymethyl chitosan and the aldehyde-cation copolymer P(FPMA-co-META). Covalent (Schiff base) and non-covalent (electrostatic interaction and hydrogen bonding) crosslinking enhance the mechanical performance of the prepared hydrogel. The introduction of P(FPMA-co-META) into the cellulose network architecture endowed the ACCPFM hydrogel with an impressive antibacterial capacity (bacterial reduction: > 95%). The ACCPFM hydrogel used the hygroscopicity of the hydroxy, carboxyl and cationic moieties to remove interfacial water on the tissue surface and then formed physical and dynamic covalent cross-links with the tissue (shear strength: > 50 kPa, tensile strength: > 70 kPa and interfacial toughness: > 110 J m−2). Notably, due to the dominance of physical and dynamic covalent crosslinking, which transforms timescale-dependent, on-demand detachment was achieved by applying a tailored benign solution (sodium bicarbonate/glycine) at different stages, providing a wider time window and fault-tolerance for the adhesion process. Given the ACCPFM hydrogel's strong wet adhesion, excellent antimicrobial capability and cytocompatibility, and benign on-demand detachment from tissues, cellulose-based hydrogels are expected to have potential applications in the biomedical field. [ABSTRACT FROM AUTHOR]

Adoption of multitarget, cost‐effective fixed‐dose medication combinations can help lower the pill load without increasing the risk of adverse events. In this study, three new 1:1 drug‐drug binary solid forms of panobinostat (PNB) and nonsteroidal anti‐inflammatory drugs (NSAIDs) were effectively synthesized by liquid‐assisted grinding and slow evaporation crystallization techniques. The obtained solid forms were extensively characterized by various analytical techniques. The structural investigation revealed that all molecular adducts formed salt with a comparable R42${\mathrm{R}}_4^2$(10) graph set pattern created by heteromeric interactions formed between PNB and corresponding salt formers. To determine the dissolving behavior of the newly developed adducts, solubility tests were performed at various pH levels (pH 1.2 and pH 7), and the results indicated that the solubility of all forms is increased at pH 7.0, particularly PNB.NIF has a solubility of 0.195 mg/mL, which is seven times higher than the parent drug. Furthermore, PXRD was used to assess the stability of the synthesized adduct at varied temperature and humidity levels and it was found that all the adducts are stable. Based on the findings, we hope that the newly found PNB drug‐drug binary adducts have possible potential to broaden the use of drug combinations without changing the chemical structures. [ABSTRACT FROM AUTHOR]

In order to obtain food packaging film with better performance, whey protein concentrate (WPC) and egg white protein (EWP) were used as film‐forming substrates, and its film properties were modified by transglutaminase (TG). Then the effect of TG on the mechanical, physical, barrier, and microstructural properties of the WPC/EWP composite biodegradable film was investigated, and its preliminary application potential was explored. Compared to WPC and EWP films, WPC/EWP composite film had higher transmittance, tensile strength (TS), and thermal stability. Fluorescence results showed that the film experienced fluorescence quenching after TG treatment. Fourier transform infrared and x‐ray diffraction results showed that WPC and EWP had good compatibility in the biodegradable film, the hydrogen bond interaction of film was increased due to TG, resulting in an increase in TS. Meanwhile, the water vapor permeability and contact angle of WPC/EWP film treated with TG at 5 U/g protein increased by 28% and 76.1%, respectively. Besides, the WPC/EWP biodegradable film modified by TG (TG‐W/E) was applied as a coating film on cherry tomatoes, effectively reducing the weight loss rate during storage from 14.2% to 10.8%. Furthermore, indexes, such as solid content, spoilage rate, hardness, pH, and lycopene, showed that the film had a good preservation effect on cherry tomatoes. To conclude, the appropriate addition of TG has a positive effect on the film properties of the WPC/EWP biodegradable film, which is beneficial to the development and utilization of protein‐based film. WPC/EWP biodegradable film modified by TG has a great application prospect in extending the shelf life of fruit and vegetable. [ABSTRACT FROM AUTHOR]

Lightweight, flexible, and thermostable thermally conductive materials are essential for enhancing heat dissipation efficiency in advanced electronics. The development of intrinsic thermally conductive polymers is the key to expanding the space for improving the thermal conductivity of polymer‐based thermal management materials. In order to balance the thermal conductivity and mechanical performance of bulk polymers, thermally conductive aramid nanofiber (ANF) films are assembled by manipulating the proton‐donating ability of solvents. Compared to water as a conventional proton donor, ethanol‐induced multi‐scale structures composed of dense hydrogen bonding interaction, large grain size, and uniform fiber topology endow the resulting ANF films with enhanced intrinsic thermal conductivity up to 5.05 W m−1 K−1 with a 34% increase, salient mechanical performance with the tensile strength of 181.4 MPa, and exceptional thermal stability higher than 500 °C. These outstanding properties of ANF films provide many possibilities for the preparation of polymer‐based thermally conductive materials. [ABSTRACT FROM AUTHOR]

In this work, five new peptides derived from natural resources and two peptide bolaamphiphiles were designed. The self-assembling ability of the peptides and the bolaamphiphiles, as well as their predicted antioxidant activity was examined computationally. In particular, replica modeling molecular dynamics studies were carried out at three different temperatures. Results showed that the bolaamphiphiles as well as three of the peptides efficiently formed spherical or fibrous assemblies, particularly at physiological temperatures. In addition, stacking interactions and hydrogen bonds played a critical role in assembly formation. Furthermore, molecular docking studies with extracellular matrix proteins such as the triple helix motif of collagen and the fibronectin (III) motif of tenascin-X displayed binding interactions with the peptides and the bolaamphiphiles. The most optimal peptide bolaamphiphile WMYGGGWMY-CO-NH-(CH2)4-YMWGGGYMW was then synthesized in the laboratory and its ability to form functional scaffolds upon binding to collagen and tenascin-X was examined. The scaffolds were bioprinted with co-cultures of fibroblasts and keratinocytes. The cells not only proliferated over time but also showed strong adherence and spreading within the matrix. Thus, the peptides and the bolaamphiphiles studied in this work, may be potentially developed as scaffold components for tissue regeneration applications. [ABSTRACT FROM AUTHOR]

One of the most popular topics in sustainable chemistry is the creation of new eco-friendly solvents. Deep eutectic solvents (DESs) have been established as accessible and affordable substitutes for ionic liquids. Herein, we studied the formation of a novel amino acid-based DES (AADES) considering L -threonine as a hydrogen bond acceptor and glycerol as a hydrogen bond donor. Owing to their complexity, a comprehensive understanding of DESs requires combined efforts that integrate experimental observations with computational approaches. The validation of the synthesized DES was initially performed through FTIR spectroscopy, where significant changes in bond-bending vibrations indicated strong non-covalent bond formation. In differential scanning calorimetry (DSC) analysis, the 1 : 3 Thr/Gly deep eutectic system displayed phase transitions marked by a pronounced peak at −22 °C, which was lower than the melting points of threonine (Thr) and glycerol (Gly). 1H-NMR studies also revealed hydrogen bonding intermolecular interactions between glycerol and threonine. Deshielded chemical shifts of proton signals of both glycerol and threonine are due to the local changes in electron density induced by the closeness of electronegative oxygens via the inductive effect, which supports the formation of the conformer (3 : 1 glycerol/threonine DES). Molecular dynamics (MD) simulation was employed to acquire a comprehensive understanding of how these solvents form and function at both the molecular and macroscopic levels. RDF and CDF analyses revealed the non-bonding sites (C–O⋯H and C＝O⋯H), interaction intensity (2–4.7), and predominant angles (135–180 and 0–30 degrees) governing the process by which hydrogen bonds originate in the DES. SDF uncovered the conformations of the liquid DES and highlighted its variability, particularly in terms of clusters. The bulk properties of DESs are of paramount significance because they are intricately linked to their diverse applications. Transport property values were obtained through specialized MD simulations, providing crucial insights into the behavior of the systems. Non-equilibrium molecular dynamics (NEMD) simulations were performed to assess the rheological properties of viscosity at three distinct temperatures (298 K, 313 K, and 328 K). The obtained viscosity, surface tension, and self-diffusion coefficient values appear practical and fall within a reasonable range when compared to those of other well-known DESs. [ABSTRACT FROM AUTHOR]

Fluorescence sensors for complicated molecules such as pesticides were paid much attention lately due to the merits of simple operation, high sensitivity and selectivity, and in‐situ detection. In this work, a novel fluorescent sensor for pesticide starane was prepared based on imidazolium‐decorated bis‐cyanostilbene macrocycle (IBM). IBM exhibited the obvious "turn‐on" fluorescence change from dark blue‐green to bright blue after sensing starane with the high sensing selectivity among 28 kinds of guests. The detecting limitation was as low as 0.011 μM, which was the lowest one in literatures. The sensing mechanism was confirmed as that starane was located in cavity of IBM based on the molecular interaction of multiple hydrogen bonds, π‐π stacking and hydrophobic interaction. The application experiments suggested that starane was examined well on test paper with good selectivity and was quantitatively detected in water samples, implying the good real‐time and in‐situ application potential for IBM on sensing starane in real environment and daily life. [ABSTRACT FROM AUTHOR]

The pyrrolidine ring is a 5‐membered ring that holds significant importance in biological chemistry. The introduction of fluorine at position 3 of pyrrolidine results in pseudo‐axial and pseudo‐equatorial C−F bonds. However, both quantum‐chemical calculations and infrared spectroscopy reveal that the 3‐fluoropyrrolidinium cation only adopts one conformation, with the C−F bond in the pseudo‐axial orientation. Upon deprotonation of 3‐fluoropyrrolidinium, leading to the formation of 3‐fluoropyrrolidine, four conformations are predicted based on CCSD/DGTZVP quantum‐chemical calculations. Among these, the conformation favoring an N−H⋅⋅⋅F−C interaction emerges as the most stable, both in the gas phase and within an implicit DMSO medium. The heightened ring puckering observed in 3‐fluoropyrrolidinium compared to the most stable conformation of 3‐fluoropyrrolidine suggests that the singular conformation of the cation arises from a robust attractive electrostatic interaction resembling hydrogen bonding, rather than a charge‐dipole gauche effect as previously assumed. [ABSTRACT FROM AUTHOR]

In this work, we synthesized a series of new 1,3‐oxazole derivatives comprising the sulfonylamide group and tested their activity against the human tumor cell line panel. This study further explores the stereoelectronic characteristics of 1,3‐oxazol‐5‐sulfonylamides and new 1‐(1,3‐oxazol‐5‐yl)piperidine‐4‐sulfonylamides to connect their anticancer activity to the molecular structure. Combining in vitro and in silico methods, we analyzed how the proximity of the sulfonylamide group to the heterocyclic ring affects the structure–activity interplay. Herein, our assessment is based on the purported complexation of 1,3‐oxazoles with targeted biomolecular fragments involving the π‐stacking interaction and hydrogen bonding within the prospective complexes. Defining the probability of the prospective drug–target interactions, we detail conformational properties, donor/acceptor capabilities, electronic characteristics, and thermodynamic preference of produced sulfanylamide group containing 1,3‐oxazoles toward biomolecular fragments, identifying the nature of variations in anticancer activity. [ABSTRACT FROM AUTHOR]

This study examined the efficacy of Inula Racemosa leaves in the adsorption of Brilliant Cresyl Blue (BCB) from aqueous solutions. The study uses both experimental and theoretical research, including Density Functional Theory (DFT), to gain a better understanding of how the adsorbent and Brilliant Cresyl Blue molecules interact with each other. We determined the point zero value of the charged powder of Inula Racemosa and characterized the functional groups using FTIR spectroscopy. The experimental results indicate a significant ability of our adsorbent to adsorb the cationic dye Brilliant Cresyl Blue, and we have identified optimal conditions for its effective removal. The results suggest that the most effective amount of our biosorbent was 0.1 g. The equilibrium period for biosorption was 10 min, and the biosorbent capacity for biosorption improved with increasing pH. The Pseudo‐second‐order model accurately predicts the retention of Brilliant Cresyl Blue using Inula Racemosa. The Freundlich model was found to be better suitable for analyzing the isotherm data, revealing a maximum adsorption capacity of 3.49 mg g−1, achieving an efficiency removal of 89.95 %. We compared Density Functional Theory (DFT) calculations with experimental observations to validate the theoretical predictions and improve our understanding of the adsorption mechanism. Docking simulations show how the molecules of Inula Racemosa and Brilliant Cresyl Blue interact with each other, including the interactions of hydrogen bonds and electrostatic forces. [ABSTRACT FROM AUTHOR]

This study investigates the development of a biopolymer blend electrolyte composed of alginate and poly (vinyl alcohol) (PVA), doped with glycolic acid (GA) to enhance H+ conductivity. The addition of GA significantly impacts the biopolymer blend's physicochemical properties and ionic conduction performance. Fourier transform infrared (FTIR) spectroscopy verified the intricate interactions and hydrogen bonding between the alginate-PVA matrix and GA. The addition of GA was shown to increase the amorphous phase, as observed through X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. This increase in the amorphous phase was found to enhance the thermal stability. Impedance analysis demonstrated a significant increase in ionic conductivity from approximately ∼10⁻⁸ S cm⁻1 for the undoped blend to 3.45 × 10⁻⁵ S cm⁻1 with 30 wt% GA (sample GA-30). The enhanced H+ conduction behaviour was consistent across various temperatures, adhering to the Arrhenius rule. These findings suggest that the alginate-PVA-GA system is a promising candidate for efficient proton transport applications. • A bio-based polymer blend electrolyte composed of alginate-PVA containing H + carriers has been successfully prepared. • Amorphous Structure : GA doping transforms alginate-PVA into a highly amorphous, ion-conductive structure. • Strong Hydrogen Bonding : FTIR shows enhanced hydrogen bonding, aiding proton conduction via Grotthuss mechanism. • Thermal Stability : TGA confirms GA-doped alginate-PVA maintains thermal stability and boosts proton conductivity. • Enhanced Proton Conductivity : Glycolic acid-doped alginate-PVA boosts conductivity to 3.45 × 10⁻⁵ S cm⁻1. [ABSTRACT FROM AUTHOR]

Comprehensive comprehension of the interaction between proteins and polyphenols is crucial for advancing their utilization in food processing. This study investigated no‐covalent interaction between pea protein isolate (PPI) and quercetin (Que) through spectroscopic analysis and molecular simulation. Fourier transform infrared spectroscopy and circular dichroism spectrum showed that the interaction between PPI and Que changed the secondary structure of the protein due to a decrease in α‐helix content and an increase in the random coil. Thermodynamic parameters indicated that the Quebound PPI via hydrogen bonds and hydrophobic interactions (ΔH > 0, ΔS > 0, and ΔG < 0), which was also confirmed by molecular docking. Particle size and ζ‐potential showed that PPI and Que demonstrated effective interaction and binding capabilities, enhancing the stability. In addition, the antioxidant and bioaccessibility of complexes have also been enhanced. This study shed a light on the application of protein–polyphenol complexes for developing functional foods. Practical Application: Interaction between pea protein isolate and quercetin can change the protein conformation to maintain the stability of quercetin and is helpful to expand the market value and application value of plant protein. The research has important implications for using leguminous protein as embedded support to improve the stability of polyphenols compounds. [ABSTRACT FROM AUTHOR]

Recent studies have discovered that aryl-substituted pyrido[2,1-a]isoquinolines have the potential to be highly active DPP IV inhibitors. In previous studies, we reported a novel synthetic approach for the construction of their sulfur-containing bioisosteric [1,4]thiazino[3,4-a]isoquinolines analogues, incorporating an additional aryl substituent. The present study aims to investigate the DPP IV inhibitory activity and cytotoxicity of the synthesized molecules by in vitro assay. The geometry optimization and molecular docking of the synthesized compounds were used to determine their binding modes to the active site of DPP IV. The docking analysis revealed that the energy-minimized poses of the studied compounds are close to the most important selectivity cliffs for DPP IV inhibition, forming hydrogen bonds and hydrophobic interactions with them. These results can be considered as a preliminary step towards further structural activity modifications. [ABSTRACT FROM AUTHOR]

In this study, a flexible sensor is successfully fabricated using self‐healing nanocomposite hydrogels for monitoring human movement. The eco‐friendly cellulose nanocrystals (CNCs) are used as nano‐reinforcing materials, and the mechanical properties and self‐healing efficiency of the materials are improved. The self‐healing efficiency of hydrogels are realized by introducing a variety of reversible non‐covalent interactions such as hydrogen bonding, borax chelation, and metal coordination. Notably, the mechanical strength and self‐healing efficiency of these nanocomposite hydrogels can reach 2.8 MPa and 89.9%, respectively. Importantly, these self‐healing nanocomposite hydrogels have been widely used in wearable flexible sensors to achieve high sensitivity to large‐scale human movement. It is of great significance to design functional materials with good biocompatibility, sensitivity, and mechanical strength for wearable sensors. [ABSTRACT FROM AUTHOR]

The onset of SARS-CoV-2 infection in 2019 sparked a global COVID-19 pandemic. This infection is marked by a significant rise in both viral and host kinase activity. Our primary objective was to identify a pivotal host kinase essential for COVID-19 infection and the associated phenomenon of the cytokine storm, which may lead to long-term COVID-19 complications irrespective of viral genetic variations. To achieve this, our study tracked kinase phosphorylation dynamics in RAW264.7 macrophages following SPIKE transfection over time. Among the kinases surveyed, p70S6K (RPS6KB1) exhibited a 3.5-fold increase in phosphorylation at S418. This significant change prompted the selection of p70S6K for in silico investigation, utilizing its structure bound to M2698 (PDB: 7N93). M2698, an oral dual Akt/p70S6K inhibitor with an IC50 of 1.1 nM, exhibited psychosis side effects in phase I clinical trials, potentially linked to its interaction with Akt2. Our secondary objective was to discover a small-molecule analogue of M2698 that exhibits a distinct binding preference for p70S6K over Akt2 through computational modeling and analysis. The in silico part of our project began with validating the prediction accuracy of the docking algorithm, followed by an OCA analysis pinpointing specific atoms on M2698 that could be modified to enhance selectivity. Subsequently, our investigation led to the identification of an analog of M2698, designated as S34, that showed a superior docking score towards p70S6K compared to Akt2. To further assess the stability of S34 in its protein–ligand (PL) complexes with p70S6K and Akt2, MD simulations were conducted. These simulations suggest that S34, on average, forms two hydrogen bond interactions with p70S6K, whereas it only forms one hydrogen bond interaction with Akt2. This difference in hydrogen bond interactions likely contributed to the observed larger root mean square deviation (RMSD) of 0.3 nm in the S34-Akt2 complex, compared to 0.1 nm in the S34-p70S6K complex. Additionally, we calculated free binding energy to predict the strength of the binding interactions of S34 to p70S6K and Akt2, which showed ~2-fold favorable binding affinity of S34 in the p70S6K binding pocket compared to that in the Akt2 binding pocket. These observations may suggest that the S34-p70S6K complex is more stable than the S34-Akt2 complex. Our work focused on identifying a host kinase target and predicting the binding affinity of a novel small molecule to accelerate the development of effective treatments. The wet bench results specifically highlight p70S6K as a compelling anti-COVID-19 target. Meanwhile, our in silico investigations address the known off-target effects associated with M2698 by identifying a close analog called S34. In conclusion, this study presents novel and intriguing findings that could potentially lead to clinical applications with further investigations. [ABSTRACT FROM AUTHOR]

Perovskite light‐emitting diodes (PeLEDs) present potential applications for next‐generation displays due to their excellent luminescent properties and solution processing. The formamidinium‐caesium lead bromide (FAxCs1−xPbBr3) mixed cation strategy is one of the primary methods to achieve high‐performance of Cs‐dominate PeLEDs system. However, the inhomogeneous distribution of cations is detrimental to the photoelectronic performance of Cs‐dominated PeLEDs. Here, in mixed FA/Cs perovskite films, it is observed that Cs, Br and trace Pb elements precipitated on the surface of the perovskite films. It is found that the segregation of cations is induced by the uncontrollable crystallization process of Cs/FA cations. By introducing biuret additive, the hydrogen bonding interaction of biuret and FA cation balances crystallization rate, which therefore significantly improves the crystal quality and cations distribution of perovskite films. As a result, green PeLEDs with a high external quantum efficiency of 28.8% are obtained, and represent five times enhancement in half‐life time (T50) of 2.48 h at an initial luminance of 100 cd m−2 relative to the control device. The results help to understand the relationship between cationic distribution and PeLEDs properties, offering significant insights for modulating the performance of PeLEDs. [ABSTRACT FROM AUTHOR]

The conformational possibilities of the casoxin D (Tyr1-Val2-Pro3-Phe4-Pro5-Pro6-Phe7) molecule were studied by theoretical conformational analysis. The potential function of the system is chosen as the sum of non-valence, electrostatic and torsion interactions and the energy of hydrogen bonds. The low-energy conformations of the casoxin D molecule, the dihedral angles of the main and side chains of the amino acid residues that make up the molecule were found, and the energy of intra- and interresidual interactions was estimated. It has been shown that the spatial structure of the casoxin D molecule is represented by conformations of eight shapes of the peptide skeleton. The results obtained can be used to elucidate the structural and structural-functional organisation of casoxin molecules. [ABSTRACT FROM AUTHOR]

The activation of the Neuraminidase 3 (NEU3) enzyme has been associated with the hyperphosphoryla-tion of Epidermal Growth Factor Receptor (EGFR) in Nonsmall Cell Lung Carcinoma (NSCLC). Existing EGFR inhibitors (such as gefitinib, erlotinib, lapatinib, icotinib, afatinib and osimertinib) reduce the hyperactivation of downstream signaling pathways (Akt, Mapk, Jak-Stat, Plc) but fail to completely abolish EGFR hyperphosphorylation. Therefore, co-targeting NEU3 and EGFR presents a greater potential to be used as a combinatorial therapy for NSCLC. This study employs structure guided approaches to elucidate the binding hypothesis of NEU3 and EGFR inhibitors. Toward this, important 3D features associated with high inhibitory potency of NEU3, and EGFR modulators were identified through SAR. The triazole substitution in acetamide dihydropyran carboxylic acid derivatives is mainly responsible for improved inhibitory potency against NEU3. Therefore, the hydrophobic (ϕ -H) interaction with the benzene ring and hydrogen bonding with the hydroxyl group of triazole are critical for designing new NEU3 modulators. Molecular Dynamics (MD) simulation studies demonstrate the stability of hydrogen bonding interactions of highly active NEU3 inhibitors with Pro66, Gly199 and Glu410 residues. Similarly, pyrimidine ring of EGFR inhibitors forms stable hydrogen bonds with Lys721 and Asp831 residues, contributing to their inhibitory potency. Our findings suggest that incorporating these identified 3D features associated with triazole and pyrimidine substitutions into a suitable scaffold could be a valuable strategy for developing a new generation of NEU3 and EGFR modulators. This approach offers a potential multi-targeted therapy for NSCLC patients. This study explores co-targeting NEU3 and EGFR for treating NSCLC by identifying key 3D features that enhance inhibitor potency. The research highlights that triazole substitutions improve NEU3 inhibition, while pyrimidine rings contribute to EGFR inhibition through stable hydrogen bonding and hydrophobic interactions. By integrating the identified interactions associated with the potent triazole and pyrimidine substitutions into a new scaffold may provide a promising approach for developing multi-targeted therapies for NSCLC. [ABSTRACT FROM AUTHOR]

Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation of viscous flow for binary mixtures of Hexylene glycol (2-methyl-pentanediol-2,4 or MPD) with aliphatic ketones (4-hydroxy-4-methyl-pentan-2-one (J1), 4-methyl-pentan-2-one (J2), and pentan-2-one (J3)) components selected compositions were determined from the measured values of densities (ρ), viscosities (η), and speeds of sound (u) of pure components and their mixtures from 303.15 K to 313.15 K. The results were analysed in terms of intermolecular interactions or hydrogen bonding or hetero-association interactions in the binary mixtures. Finally, the Prigogine-Flory-Patterson (PFP) theory is applied to identify the most predominant molecular interaction. The results of the Jouyban-Acree model are discussed in terms of mean relative deviation (MRDs) and individual relative deviation (IRD) between calculated and experimental densities, speeds of sound, and viscosities as an accuracy criterion. [ABSTRACT FROM AUTHOR]

Proteins and peptides have been increasingly developed as pharmaceuticals owing to their high potency and low side effects. However, their administration routes are confined to injections, such as intra-muscular and intra-venous injections, making patient compliance a challenge. Hence, non-injectable delivery systems are crucial to expanding the clinical use of proteins and peptides. In this context, two choline-based ionic liquids (ILs), namely, choline geranic acid ([Ch][Ger]) and choline citric acid ([Ch][Cit]), have been identified as promising agents for enhancing the permeation and prolonging the retention time of glucagon (GC) after intra-nasal administration. Notably, intra-nasal delivery of GC via ILs (GC/ILs) elicited rapid and smooth reversal of acute hypoglycaemia without leading to rebound hyperglycaemia in type 1 diabetic rats subjected to insulin induction. In addition, ILs could improve the transcellular transport of GC through electrostatic interaction. ILs could also transiently open inter-cellular tight junctions transiently to facilitate the paracellular transport of GC. Safety tests indicated that continuous intra-nasal delivery of ILs led to reversible changes, such as epithelial cell inflammation, goblet cell overgrowth, and impacts on the distribution of nasal cilia. However, these changes could be alleviated by the innate self-repair ability of mucosal epithelial cells. This study highlights the considerable potential of ILs for long-term nasal delivery of biomacromolecules. [Display omitted] • Intra-nasal delivery of glucagon in ionic liquids (GC/ILs) for acute hypoglycaemia rescue • ILs improved the stability and solubility of GC through hydrogen bonding interactions. • ILs enhanced the paracellular transport of GC as a novel transient permeation enhancer. • The water content of ILs significantly affected the nasal retention and efficacy of GC/ILs. • The long-term regimen of nasal delivery of GC/ILs showed a favourable safety profile. [ABSTRACT FROM AUTHOR]

BACKGROUND: Folic acid (FA), a synthetically produced compound analogous to vitamin B9, also referred to as vitamin folate, is an essential compound in human health and faces challenges in stability during food processing. This study explores the incorporation of FA into carboxymethylcellulose (CMC) nanofibers using electrospinning to enhance its stability. RESULTS: In this study, optimization of both electrospinning and solution parameters facilitated the fabrication of nanofibers. Furthermore, incorporating FA into CMC/polyethylene oxide (PEO) nanofibers resulted in thinner fibers, with an average diameter of 88 nm, characterized by a flat shape and smooth surface. Fourier transform infrared spectroscopic analysis demonstrated substantial hydrogen bonding interactions between FA and the polar groups present in CMC. This interaction contributed to an encapsulation efficiency of 94.5%, with a yield exceeding 87%. Thermal analysis highlighted mutual interference between CMC and PEO, with FA enhancing the thermal stability and reducing the melting temperatures and enthalpies of PEO, while also increasing the reaction heats of CMC. The encapsulated FA remained stable in acidic conditions, with only 6% degradation over 30 days, demonstrating the efficacy of CMC/PEO nanofibers in safeguarding FA against acidic environments. Moreover, the nanofibers provided a protective barrier against UV radiation, thereby preserving the stability of FA. CONCLUSION: This study emphasizes the efficacy of CMC/PEO nanofibers as a protective matrix against FA degradation. The findings indicate that this innovative approach could significantly diversify the applications of FA in food fortification, addressing concerns regarding its vulnerability to temperature and hydrolysis reactions during food processing. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

BACKGROUND: Sturgeon cartilage type II collagen peptides (SHCPs) can self‐assemble and be used to prepare collagen peptide assemblies. Self‐assembled peptides have great potential for applications in the food industry. In the present study, self‐assembled peptides were prepared from sturgeon cartilage and then characterized. RESULTS: The SHCPs self‐assembled and formed collagen peptide assemblies. After response surface experiment optimization, the optimal enzyme digestion process comprised 43.1 °C, 3.37 h and 0.96% enzyme addition, and the peptide yield was 78.46%. Physicochemical analysis showed that the SHCPs were amphiphilic, with an average molecular weight of 1081 Da, and were rich in hydrophobic amino acids. Peptide sequence identification showed that the peptides of SHCPs with polar amino acids followed by hydrophobic amino acids could be self‐assembled through hydrogen bonding and hydrophobic interaction. Through turbidity experiments, Fourier transform infrared spectroscopy and scanning electron microscopy, we demonstrated that SHCPs can self‐assemble into reticular and tubular structures under specific conditions. Furthermore, both the SHCPs‐Ca and SHCPs‐Mg assemblies were stabilized within a pH range consistent with that of the human gastrointestinal tract. CONCLUSION: The present study provides a simple and safe method for preparing novel self‐assembled peptide materials from sturgeon by‐products, providing a scientific basis for the exploitation of sturgeon cartilage and potentially reducing resource wastage. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

In the current study, three different carboxylic acids were incorporated as a cross-linker into the blend films of polyvinyl alcohol (PVA) and basmati rice starch (BRS) at a 70/30 ratio and plasticized with glycerol. The cross-linking succeeds through the creation of ester bonds between the free hydroxyl groups of PVA/BRS and the C = O groups. The effect of this cross-linking on physicochemical properties (film thickness, retraction ratio, moisture content, water absorption, and water vapor permeability) and optical (transmittance and color analysis), antimicrobial, and antioxidant properties was assessed. The current findings showed that COA incorporation into the PVA/BRS blend films demonstrated better hydrophobicity and excellent UV light-blocking properties. The incorporation of COA has no impact on radical scavenging activity; however, the cinnamic acid- and benzoic acid-containing films at higher percentages possess antimicrobial properties. FTIR studies confirm the existence of hydrogen bonding interactions among the PVA/BRS blend film and COA. The study encompasses the swelling properties of the blend film in water, brine, and seawater. The cast blend films can be utilized for the packaging purposes of foodstuffs. [ABSTRACT FROM AUTHOR]

A delivery system was developed according to maillard reaction using mung bean protein and maltodextrin for encapsulation and sustain release of curcumin. The ultrasound assisted (150 W, 80 °C, 10 min) and classic wet heating (80 °C, 60 min), were used to prepare conjugates at three different ratios of Mung bean protein isolate to maltodextrin. Degree of conjugation was measured using OPA method Uv-visible spectroscopy was used to estimate the final products of maillard reaction. Different amounts of curcumin (0, 0.2, 0.4 and 0.6 mg. mL-1 was loaded using ethanol and change in pH. Primary analysis showed that the optimized samples were obtained when 0. 4 mg. mL-1 of curcumin was encapsulated using pH change method. FTIR spectra confirmed the conjugation of the MPI and MD and showed the electrostatic and hydrophobic interactions as well as hydrogen bonding are the main reasons of conjugates stability and curcumin encapsulation. The prepared curcumin containing conjugates under optimized method showed the higher DPPH radical scavenging activity. Our results showed that the release rate of encapsulated curcumin under simulated condition of gastrointestinal tract (GIT) was controlled and lower than that which encapsulated in mung bean protein. [ABSTRACT FROM AUTHOR]

Collagen (Col) composite fibers containing various functionalized multiwalled carbon nanotubes (MWNTs) were prepared via microfluidic spinning, and the influences of MWNT content and type on the performances of the composite fibers were investigated by transmission electron microscope, UV–vis, SEM, Fourier Transform Infrared Spectrometer, differential scanning calorimetry, X‐ray diffraction, and tensile testing. The Col composite fibers showed tightly packed bundle structures on surfaces originated from the high shear rates in the microfluidic channels, and MWNT facilitates the self‐assembly of Col molecules, leading to the ordered arrangement of Col fibrils along the fiber axis. When the loading of carboxylated MWNT (cMWNT) was 0.5 wt%, the tensile strength of Col/cMWNT achieved the maximum of 1.94 cN/dtex owing to the excellent hydrogen bond and electrostatic interactions between the carboxyl groups in cMWNT and amino groups in Col molecules, which is significantly higher than those composite fibers made from unfunctionalized and hydroxylated MWNT. Moreover, with the incorporation of MWNT the thermal stability and water resistance of Col fibers were improved due to the enhanced interfacial interactions between Col and MWNT. The fabrication method in this work enables the controlled formation of Col fibers and demonstrates huge potential for use in Col‐based biomaterials. Highlights: Novel collagen (Col)/multiwalled carbon nanotube (MWNT) composite fibers were prepared via microfluidic spinning.The Col composite fibers showed tightly packed bundle surface structures.Col/carboxylated MWNT achieved the maximum tensile strength of 1.94 cN/dtex.MWNT enhanced thermal stability and water resistance of Col fibers. [ABSTRACT FROM AUTHOR]

Organophosphates are a type of emerging environmental contaminant, which can be removed effectively by adsorption. Here, modified steel slag was examined for its adsorptive performance in the removal of hydroxyethylidene diphosphonic acid (HEDP) from water. Compared to acid (55.3%, maximum removal rate) and base (85.5%) modification, high-temperature modification (90.6%) significantly enhanced steel slag's adsorption capacity for HEDP, surpassing that of unmodified slag (71.2%). Kinetic analyses elucidated a two-phase adsorption process—initial rapid adsorption followed by a slower equilibrium phase. The results of adsorption energy analysis showed that modified steel slag preferentially occupied the sites with higher energy, which promoted the adsorption. After five regeneration cycles, the adsorption properties of the material were not significantly reduced, which indicates that the material has good application potential. Microscopic and spectroscopic techniques, including SEM-EDS, FTIR, and XPS, were employed to uncover the surface chemistry and structural changes responsible for the enhanced adsorption efficiency. The adsorption mechanism of HEDP on steel slag is a complete process guided by hydrogen bonding interactions, strengthened surface complexation, and optimized ligand exchange. This study advances the sustainable utilization of industrial waste materials and contributes significantly to the development of innovative water treatment technologies. [ABSTRACT FROM AUTHOR]

The combination of proteins with polysaccharides and polyphenols is expected to improve their physicochemical and functional properties. In this study, a novel plant-based antioxidant emulsifier was formed by soybean protein isolate (SPI), inulin (INU), and dihydromyricetin (DMY). Based on the binary system of SPI/INU, we focused on exploring the effect of the DMY concentration (0.5 mg/mL~2.5 mg/mL) on the formation and properties of the ternary complex. The structure, interaction mechanism, and interfacial and functional properties of the ternary complex were investigated. The results indicate that compared to the SPI/INU binary complex, the SPI/INU/DMY ternary complex had a significant decrease in particle size (~100 nm) and a slight decrease in absolute zeta potential. The SPI/INU binary complex with DMY mainly interacted by hydrogen bonding and hydrophobic interactions. Due to the incorporation of DMY, the structure of SI was denser and more flexible. The ternary complex exhibited an ideal three-phase contact angle and demonstrated better foaming and antioxidant ability. Additionally, compared to SPI/INU, the ternary complex had a significant improvement in EAI. These results provide a strategy for polyphenols to modify the structure, interfacial properties, and functions of protein/polysaccharide complexes. This provides a potential reference for the preparation of more ternary complexes with excellent emulsifying and antioxidant properties for application in emulsions. [ABSTRACT FROM AUTHOR]

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Organic nonlinear optical (NLO) 2-amino-4,6-dimethoxypyrimidine-4-aminobenzoic acid (2AD4AB) single crystal was grown by slow evaporation method and characterized via single crystal X-ray diffraction (SXRD), FTIR, FT-Raman and UV–visible spectroscopy. The synthesized crystal is monoclinic with centrosymmetric space group P21/c. Using density functional theory (DFT), the quantum chemical computations were performed with a B3LYP/6-31G (d, p) basis set. Natural bond orbital analysis (NBO) was executed to analyze the hydrogen bonding interaction, stability and charge delocalization of 2AD4AB. The charge distribution of the 2AD4AB molecule can be graphically depicted by frontier molecular orbital analysis (FMO) and molecular electrostatic potential (MEP). The energy gap of 2AD4AB was estimated to be 4.96 eV. MEP analysis shows that the electrophilic attack was extended over oxygen atoms of the carboxylic group. Atoms in molecule (AIM) and reduced density gradient (RDG) analysis were carried out to investigate the O–H...N and N–H...O interactions within the 2AD4AB molecule. The presence of different functional groups and vibrational modes were validated by FT-IR and FT-Raman spectral analysis. The optical property and band gap energy of 2AD4AB were determined using the UV–Vis optical transmittance spectrum. Thermal stability of the 2AD4AB crystal was estimated to be up to 155 °C using TG–DTA analysis. The intermolecular O–H···N, N–H···O, and C–H···N interactions of the 2AD4AB molecule were revealed by Hirshfeld and 2D fingerprint plots. The potential energy scan (PES) was performed to identify the most stable conformer. To demonstrate charge transfer in the molecule, hole electron analysis was implemented. Light harvesting efficiency (LHE) of the grown crystal was 78.88%, which shows that the 2AD4AB crystal was highly efficient in fabricating organic solar cell devices. The green emission at 544 nm of the 2AD4AB single crystal was scrutinized via fluorescence spectral analysis. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDAX) analyses provide information about the surface morphology and chemical composition of 2AD4AB single crystal. In SEM analysis, it was observed that the grown crystal has a smooth surface and free from cracks. EDAX analysis confirms the presence of elemental composition like carbon, oxygen and nitrogen. Using DFT and Z-scan technique the NLO activity of the 2AD4AB molecule was examined computationally and experimentally. The first-order hyperpolarizability (β) and the third-order susceptibility (χ(3)) of the 2AD4AB was estimated to be 182.46 × 10–30 esu and 4.42 × 10–6 esu. The results of HOMO–LUMO, UV–Vis, NLO, Z-scan, and TG/DTA values were compared with other already studied NLO active compounds. While comparing with other studied NLO active compounds, the present compound 2AD4AB shows more NLO activity. [ABSTRACT FROM AUTHOR]

To study an effective removal method of residual cephalosporin antibiotics in water, taking the ceftriaxone sodium (CFS) as a research object, the adsorption effects of the resins with different characteristic parameters for CFS were investigated in the pH range of 2.0–5.0. MTS9570, a sorbent containing sulfonic-phosphoric acid bi-functional group, was optimally selected and further to study the adsorption removal behavior to CFS in depth for the first time. Owning to the highest fitness of the pseudo-second-order and intra-particle diffusion (R2 > 0.99), two models can better describe the process of CFS onto MTS9570, indicating that the process is controlled by the chemi-sorption and intra-particle diffusion together. Compared with Freundlich and Temkin isotherm, Langmuir isotherm is the best fitness with highest R2 and lowest AIC values, indicating that there exists a monolayer adsorption on the surface of MTS9570 sorbent to CFS. ∆H < 0, ∆S > 0 and ∆G < 0, imply that the adsorption is an exothermic spontaneous process with increased randomness at the solid–liquid interface. The adsorption ability of MTS9570 after six adsorption–desorption cycles can still reach 90.13% of the initial adsorption capacity, indicating that the adsorbent has good reusability. Combining the above results with the bi-functional group of the adsorbent as well as the molecular structure of CFS, we speculate that the potential adsorption mechanism of MTS9570 to CFS may be mainly controlled by electrostatic interaction and supplemented by hydrogen bonding. [ABSTRACT FROM AUTHOR]

Enzymes turnover substrates into products with amazing efficiency and selectivity and as such have great potential for use in biotechnology and pharmaceutical applications. However, details of their catalytic cycles and the origins surrounding the regio‐ and chemoselectivity of enzymatic reaction processes remain unknown, which makes the engineering of enzymes and their use in biotechnology challenging. Computational modelling can assist experimental work in the field and establish the factors that influence the reaction rates and the product distributions. A popular approach in modelling is the use of quantum mechanical cluster models of enzymes that take the first‐ and second coordination sphere of the enzyme active site into consideration. These QM cluster models are widely applied but often the results obtained are dependent on model choice and model selection. Herein, we show that QM cluster models can give highly accurate results that reproduce experimental product distributions and free energies of activation within several kcal mol−1, regarded that large cluster models with >300 atoms are used that include key hydrogen bonding interactions and charged residues. In this tutorial review, we give general guidelines on the set‐up and applications of the QM cluster method and discuss its accuracy and reproducibility. Finally, several representative QM cluster model examples on metal‐containing enzymes are presented, which highlight the strength of the approach. [ABSTRACT FROM AUTHOR]