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The 1 H nuclear magnetic resonance ( 1 H-NMR) spectrum is a useful tool for characterizing the hydrogen bonding (H-bonding) interactions in ionic liquids (ILs). As the main hydrogen bond (H-bond) donor of imidazolium-based ILs, the chemical shift (δ H2 ) of the proton in the 2-position of the imidazolium ring (H2) exhibits significant and complex solvents, concentrations and anions dependence. In the present work, based on the dielectric constants (ϵ) and Kamlet-Taft (KT) parameters of solvents, we identified that the δ H2 are dominated by the solvents polarity and the competitive H-bonding interactions between cations and anions or solvents. Besides, the solvents effects on δ H2 are understood by the structure of ILs in solvents: 1) In diluted solutions of inoizable solvents, ILs exist as free ions and the cations will form H-bond with solvents, resulting in δ H2 being independent with anions but positively correlated with β S . 2) In diluted solutions of non-ionzable solvents, ILs exist as contact ion-pairs (CIPs) and H2 will form H-bond with anions. Since non-ionizable solvents hardly influence the H-bonding interactions between H2 and anions, the δ H2 are not related to β S but positively correlated with β IL ., (© 2023 Wiley-VCH GmbH.)

Background: In this study we investigated hydrogen bonding interactions in hydrated and frozen solutions of different cryoprotective agents (CPAs) including dimethyl sulfoxide, glycerol, ethylene glycol, propylene glycol, and trehalose. We also investigated the effect of CPAs on ice crystal growth during storage and correlated this with storage stability of liposomes., Methods: FTIR spectroscopy was used to study hydrogen bonding interactions in CPA solutions in H 2 O and D 2 O, and their thermal response was analyzed using van 't Hoff analysis. The effect of CPAs on ice crystal growth during storage was investigated by microscopy and correlated with storage stability of liposomes encapsulated with a fluorescent dye., Results: Principal component analyses demonstrated that different CPAs can be recognized based on the shape of the OD band region only. Chemically similar molecules such as glycerol and ethylene glycol closely group together in a principal component score plot, whereas trehalose and DMSO appear as condensed separated clusters. The OH/OD band of CPA solutions exhibits an overall shift to higher wavenumbers with increasing temperature and changed fractions of weak and strong hydrogen interactions. CPAs diminish ice crystal formation in frozen samples during storage and minimize liposome leakage during freezing but cannot prevent leakage during frozen storage., Conclusions: CPAs can be distinguished from one another based on the hydrogen bonding network that is formed in solution. DMSO-water mixtures behave anomalous compared to other CPAs that have OH groups. CPAs modulate ice crystal formation during frozen storage but cannot prevent liposome leakage during frozen storage., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing interests., (Copyright © 2022 Elsevier B.V. All rights reserved.)

There is strong interest to develop affordable treatments for the infection-associated rheumatoid arthritis (RA). Here, we present a drug-drug co-amorphous strategy against RA and the associated bacterial infection by the preparation and characterization of two co-amorphous systems of sinomenine (SIN) with platensimycin (PTM) or sulfasalazine (SULF), two potent antibiotics. Both of them were comprehensively characterized using powder X-ray diffraction, temperature-modulated differential scanning calorimetry, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The co-amorphous forms of SIN-PTM and SIN-SULF exhibited high T s at 139.10 ± 1.0 and 153.3 ± 0.2 °C, respectively. After 6 months of accelerated tests and 1 month of drug-excipient compatibility experiments, two co-amorphous systems displayed satisfactory physical stability. The formation of salt and strong intermolecular interactions between SIN and PTM or SULF, as well as the decreased molecular mobility in co-amorphous systems, may be the intrinsic mechanisms underlying the excellent physical stability of both co-amorphous systems. In dissolution tests, two co-amorphous systems displayed distinct reduced SIN-accumulative releases (below 20% after 6 h of release experiments), which may lead to its poor therapeutic effect. Hence, we demonstrated a controlled release strategy for SIN by the addition of a small percentage of polymers and a small-molecule surfactant to these two co-amorphous samples as convenient drug excipients, which may also be used to improve the unsatisfactory dissolution behaviors of the previously reported SIN co-amorphous systems. Several hydrogen bonding interactions between SIN and PTM or SULF could be identified in NMR experiments in DMSO- g s at 139.10 ± 1.0 and 153.3 ± 0.2 °C, respectively. After 6 months of accelerated tests and 1 month of drug-excipient compatibility experiments, two co-amorphous systems displayed satisfactory physical stability. The formation of salt and strong intermolecular interactions between SIN and PTM or SULF, as well as the decreased molecular mobility in co-amorphous systems, may be the intrinsic mechanisms underlying the excellent physical stability of both co-amorphous systems. In dissolution tests, two co-amorphous systems displayed distinct reduced SIN-accumulative releases (below 20% after 6 h of release experiments), which may lead to its poor therapeutic effect. Hence, we demonstrated a controlled release strategy for SIN by the addition of a small percentage of polymers and a small-molecule surfactant to these two co-amorphous samples as convenient drug excipients, which may also be used to improve the unsatisfactory dissolution behaviors of the previously reported SIN co-amorphous systems. Several hydrogen bonding interactions between SIN and PTM or SULF could be identified in NMR experiments in DMSO- d 6 , which may be underlying reasons of decreased dissolution behaviors of both co-amorphous forms. These drug-drug co-amorphous systems could be a potential strategy for the treatment of infection-associated RA.

Nano-ZnO were in situ prepared and permanently embedded in regenerated cellulose (RC) films by chemical precipitation to endow antibacterial of films and simultaneously strengthen tensile strength. ZnCl 2 was selected as a promoter of 1-allyl-3-methylimidazolium chloride for cellulose dissolution and as a precursor for nano-ZnO synthesis. Zn 2+ -absorbed cellulose solution was reacted with NaOH under ultrasonic to obtain nano-ZnO embedded RC films. The results indicated that RC films treated with the longest sonication time, highest regeneration solution basicity, and highest cellulose concentration were demonstrated to be the most effective against S. aureus, which agreed well with the dense and homogeneous distribution of high content of nano-ZnO on the film surface. The nanocomposite films achieved particularly high mechanical strength of 202.0 MPa with improved thermal stability. Strong H-bonding formed between nano-ZnO and cellulose, which contributed to high tensile strength and thermal stability of films. This work affords a simple approach to prepare cellulose nanocomposite with outstanding performance for potential application in packaging., (Copyright © 2021. Published by Elsevier B.V.)

Self-polarized piezoelectric devices have attracted significant interest owing to their fabrication processes with low energy consumption. Herein, novel poling-free piezoelectric nanogenerators (PENGs) based on self-polarized polyvinylidene difluoride (PVDF) induced by the incorporation of different surface-modified barium titanate nanoparticles (BTO NPs) were prepared via a fully printing process. To reveal the effect of intermolecular interactions between PVDF and NP surface groups, BTO NPs were modified with hydrophilic polydopamine (PDA) and hydrophobic 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) to yield PDA-BTO and PFD-BTO, respectively. This study demonstrates that the stronger hydrogen bonding interactions existed in PFD-BTO/PVDF composite film comparative to the PDA-BTO/PVDF composite film induced the higher β-phase formation (90%), which was evidenced by the XRD, FTIR and DSC results, as well as led to a better dispersion of NPs and improved mechanical properties of composite films. Consequently, PFD-BTO/PVDF-based PENGs without electric poling exhibited a significantly improved output voltage of 5.9 V and power density of 102 μW cm -3 , which was 1.8 and 2.9 times higher than that of PDA-BTO/PVDF-based PENGs, respectively. This study provides a promising approach for advancing the search for high-performance, self-polarized PENGs in next-generation electric and electronic industries.

Single crystals of (E)-N'-(4-isopropylbenzylidene)isonicotinohydrazide monohydrate (IBIHM) were grown from ethanol by the slow evaporation from solution growth technique at room temperature. The structure was elucidated by single-crystal X-ray diffraction analysis and crystallized in the orthorhombic system with noncentrosymmetric space group P2 1 2 1 2 1 . Optical studies reveal that the absorption was minimum in the visible region and the band-gap energy was estimated using the Kubelka-Munk algorithm. The functional groups were identified by Fourier transform infrared spectral analysis. A scanning electron microscopy study revealed the surface morphology of the grown crystal. Investigation of the intermolecular interactions, crystal packing using Hirshfeld surface analysis and single-crystal X-ray diffraction confirm that the close contacts were associated with molecular interactions. Fingerprint plots of Hirshfeld surfaces are used to locate and analyze the percentage of hydrogen-bonding interactions. The second-harmonic generation efficiency of the grown specimen was superior to that of the reference material, potassium dihydrogen phosphate. The grown crystals were further characterized by mass spectrometry and elemental analysis. Theoretical studies using density functional theory (DFT) greatly substantiated the experimental observations. Large first-order molecular hyperpolarizability (β) of about ∼70× was observed for IBIHM. The efficiency of IBIHM in terms of nonlinear optical response was verified and the molecule displayed greater chemical stability and reactivity.

The aim of this work is to shed light on the origins of unique properties by studying the relationship between viscosity and hydrogen-bonding interactions of terpene-based natural deep eutectic solvents (NADES). Five systems including camphor/formic acid, menthol/acetic acid, menthol/β-citronellol, menthol/lactic acid, and thymol/β-citronellol are prepared (molar ratio 1:1). Their structures and nature of the associated hydrogen bonds are investigated through multiple methods and theories. The viscosity of NADES is consistent with the product of hydrogen-bond number and lifetime. Through visualization of non-covalent interactions, terpene-acid-based NADES with single sites show the lowest viscosity among the studied systems because of weak and unstable hydrogen bonding. Inversely, multi-site terpene-acid-based NADES possess relatively high viscosity. Owing to the stability of hydrogen bonds in the network, the terpene-terpene-based system is in the middle level of viscosity. In-depth analysis of these hydrogen bonds shows that they can be classified as "weak to medium" and are mainly derived from electrostatic interactions. Moreover, there is an obvious connection between viscosity and hydrogen-bonding strength (integrated core-valence bifurcation index) in the networks. The discovery of intrinsic rules between viscosity and hydrogen-bonding interactions is beneficial for the design of novel low-viscosity NADES in the future., Competing Interests: The authors declare no conflict of interest., (© 2021 The Authors. Global Challenges published by Wiley‐VCH GmbH.)

Extensive atomistic simulations demonstrated that a gradual substitution of hexyl chains with phenyl groups in tetraalkylphosphonium cations results in remarkable changes in hydrogen bonding interactions, liquid structures and scattering structural functions, and rotational dynamics of hexyl chains and phenyl groups in tetraalkylphosphonium bis(trifluoromethylsulfonyl)imide ionic liquids. Hydrogen donor sites in hexyl chains present competitive characteristics with those in phenyl groups in coordinating anions, as well as their continuous and intermittent hydrogen bonding dynamics. Cation-cation and anion-anion spatial correlations show concomitant shift to short distances with decreased peak intensities with variations of cation structures, whereas cation-anion correlations have a distinct shift to large radial distances due to decreased associations of anions with neighboring cations. These microstructural changes are qualitatively manifested in shifts of prominent peaks for prevalent charge alternations and adjacency correlations between ion species in scattering structural functions. Meanwhile, rotational dynamics of hexyl chains speed up, which, in turn, slow down rotations of phenyl groups, whereas anions exhibit imperceptible changes in their rotational dynamics. These computational results are intrinsically correlated with conformational flexibilities, molecular sizes, and steric hindrance effects of phenyl groups in comparison with hexyl chains, and constrained distributions of anions around cations in heterogeneous ionic environments., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanoparticular system of a model small molecular drug curcumin (CUR) was prepared using a novel method, namely, flash nanocomplexation by hydrogen bonding interactions. The CUR-loaded nanoparticles (NPs) were fabricated by mixing CUR, tannic acid and polyvinyl alcohol (PVA) in aqueous solutions under turbulent condition through a three-inlet confined impinging jet (CIJ) device. Compared to bulk mixing, FNC has the advantage of scalability, reproducibility and without causing the variations by different mixing sequences. Three NPs with different drug loading levels were prepared by tuning the CUR feeding amount. In human prostate cancer PC3 cells, both cellular uptake and cytotoxicity of these NPs were negatively correlated with the drug loading level. These findings indicate that FNC is an easy and feasible method for small molecular drug delivery by hydrogen bonding interactions., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Oxydiacetic acid (Oda) and iminodiacetic acid (Ida) have been combined with two diamines, namely ethylenediamine (en) and o-phenylenediamine (o-phen), to give three molecular crystals of compositions [(Oda 2- )(en 2+ )]·H 2 O (Odaen), [(Ida - )(0.5en + )] (Idaen) and [(Oda - )(o-phen + )] (Odaophen). Single crystal X-ray structure determination of the three molecular salts revealed that the hydrogen bonding interactions form distinct supramolecular chains. In Odaen, water molecules and Oda 2- anions generate one-dimensional supramolecular chains where two chains overlap each other in zigzag form. In Odaophen, Oda - anions generate a one-dimensional linear supramolecular chain. In Idaen, both intermolecular and intramolecular proton transfer occurs. Ida - anions generate a one-dimensional zigzag chain. These one-dimensional supramolecular chains extend to form different two-dimensional supramolecular chains by the interaction of diaminium and monoaminium cations. Intermolecular close contacts are also examined using Hirshfeld analysis to reveal similarities and differences in the crystal structures.

Crystal structure of the protrusion domain (P-domain) of the grouper nervous necrosis virus (GNNV) shows the presence of three-fold trimeric protrusions with two asymmetrical calcium cations along the non-crystallographic three-fold axis. The trimeric interaction natures of the interacting residues and the calcium cations with the neighboring residues within the trimeric interface have been studied by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses in the framework of the density-functional theory (DFT) approach. The results revealed that residues Leu259, Val274, Trp280, and Gln322 of subunit A, Arg261, Asp275, Ala277, and Gln322 of subunit B, Leu259, Asp260, Arg261, Ala277, Val278, and Leu324 of subunit C are the main residues involved in the trimeric interactions. Charge-dipole, dipole-dipole, and hydrogen bonding interactions make the significant contributions to these trimeric interactions. Among different interacting residues within trimeric interface, residue pair Arg261 B-Leu259C forms the strongest hydrogen bond inside the interface between subunits B and C. It was also found that calcium cations interact with residues Asp273, Val274, and Asp275 of subunits A, B, and C through charge-charge and charge transfer interactions., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Poly(sodium styrenesulfonate)⁻ block ⁻poly(acrylic acid) (PNaSS⁻ b ⁻PAA) and poly(sodium styrenesulfonate)⁻ block ⁻ poly( N -isopropylacrylamide) (PNaSS⁻ b ⁻ PNIPAM) were prepared via reversible addition⁻fragmentation chain transfer (RAFT) radical polymerization using a PNaSS-based macro-chain transfer agent. The molecular weight distributions (M w /M n ) of PNaSS⁻ b ⁻PAA and PNaSS⁻ b ⁻ PNIPAM complexes were formed as a result of hydrogen bonding interactions between the pendant carboxylic acids in the PAA block and the pendant amide groups in the PNIPAM block. The complex was characterized by ¹H NMR, dynamic light scattering, static light scattering, and transmission electron microscope measurements. The light scattering intensity of the complex depended on the mixing ratio of PNaSS⁻ b ⁻ PNIPAM were mixed under acidic conditions, water-soluble PNaSS⁻ b -isopropylacrylamide (NIPAM) and acrylic acid (AA) units was near unity, the light scattering intensity reached a maximum, indicating stoichiometric complex formation. The complex dissociated at a pH higher than 4.0 because the hydrogen bonding interactions disappeared due to deprotonation of the pendant carboxylic acids in the PAA block.⁻ PAA/PNaSS⁻ b ⁻ PNIPAM complexes were formed as a result of hydrogen bonding interactions between the pendant carboxylic acids in the PAA block and the pendant amide groups in the PNIPAM block. The complex was characterized by ¹H NMR, dynamic light scattering, static light scattering, and transmission electron microscope measurements. The light scattering intensity of the complex depended on the mixing ratio of PNaSS⁻ b ⁻PAA and PNaSS⁻ b ⁻ PNIPAM. When the molar ratio of the N -isopropylacrylamide (NIPAM) and acrylic acid (AA) units was near unity, the light scattering intensity reached a maximum, indicating stoichiometric complex formation. The complex dissociated at a pH higher than 4.0 because the hydrogen bonding interactions disappeared due to deprotonation of the pendant carboxylic acids in the PAA block., Competing Interests: The authors declare no conflict of interest.

In this study, we used density functional theory (DFT) to predict polymer-drug interactions, and then evaluated the ability of poly (vinyl pyrrolidone) (PVP) to inhibit crystallization of amorphous solid dispersions by experimental-verification. Solid dispersions of PVP/resveratrol (Res) and PVP/griseofulvin (Gri) were adopted for evaluating the ability of PVP to inhibit crystallization. The density functional theory (DFT) with the B3LYP was used to calculate polymer-drug and drug-drug interactions. Fourier transform infrared spectroscopy (FTIR) was used to confirm hydrogen bonding interactions. Polymer-drug miscibility and drug crystallinity were characterized by the modulated differential scanning calorimetry (MDSC) and X-ray powder diffraction (XRD). The release profiles were studied to investigate the dissolution advantage. DFT results indicated that E PVP-Res >E Res-Res (E: represents hydrogen bonding energy). A strong interaction was formed between PVP and Res. In addition, Fourier transform infrared spectroscopy (FTIR) analysis showed hydrogen bonding formed between PVP and Res, but not between PVP and Gri. MDSC and XRD results suggested that 70-90wt% PVP/Res and PVP/Gri solid dispersions formed amorphous solid dispersions (ASDs). Under the accelerated testing condition, PVP/Res dispersions with higher miscibility quantified as 90/10wt% were more stable than PVP/Gri dispersions. The cumulative dissolution rate of 90wt% PVP/Res dispersions still kept high after 90days storage due to the strong interaction. However, the cumulative dissolution rate of PVP/Gri solid dispersions significantly dropped because of the recrystallization of Gri., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The vibrational frequencies of 4-Phenylpyridinium hydrogen squarate (4PHS) in the ground state have been investigated by using B3LYP/6-311++G(d,p) level. The analysis of molecular structure, natural bond orbitals and frontier molecular orbitals was also performed. The IR spectra were obtained and interpreted by means of potential energies distributions (PEDs) using MOLVIB program. NBO analysis proved the presence of C-H⋯O and N-H⋯O hydrogen bonding interactions, which is consistent with the analysis of molecular structure. The dipole moments and first-order hyperpolarizability (βtot) are calculated and are 5.856 D and 4.72×10(-30) esu, respectively. The high βtot value and the low HOMO-LUMO energy gap (4.062eV) are responsible for the optical and electron-transfer properties of 4PHS molecule. The photoresponse-related results indicate that 4PHS molecule is an excellent organic candidate of photon-responsive materials., (Copyright © 2015 Elsevier B.V. All rights reserved.)