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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 (δH2 ) 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 δH2 are dominated by the solvents polarity and the competitive H-bonding interactions between cations and anions or solvents. Besides, the solvents effects on δH2 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 δH2 being independent with anions but positively correlated with ßS . 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 δH2 are not related to ßS but positively correlated with ßIL .

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The development of new polymer-based room-temperature phosphorescence materials is of great significance. By a special molecule design and a set of feasible property-enhancing strategies, coumarin derivatives (CMDs, Ma-Mf) were doped into polyvinyl alcohol (PVA), polyacrylamide (PAM), corn starch, and polyacrylonitrile (PAN) as information anti-counterfeiting. CMDs-doped PVA and CMDs-doped corn starch films showed long-lived phosphorescence emissions up to 1246 ms (Ma-PVA) and 697 ms (Ma-corn starch), reaching over 10 s afterglow under naked eye observation under ambient conditions. Significantly, CMDs-doped PAM films can display long-lived phosphorescence emissions in a wide temperature range (100-430 K). For example, the Me-PAM film has a phosphorescence lifetime of 16 ms at 430 K. The use of PAM with the strong polarity and rigidity has expanded the temperature range of long-life polymer-based phosphorescent materials. The present long-lived phosphorescent systems provide the possibility for developing new polymer-based organic afterglow materials with robust phosphorescence.

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Novel bacterial topoisomerase inhibitors (NBTIs) are a new class of antibacterial agents that target bacterial type II topoisomerases (DNA gyrase and topoisomerase IV). Our recently disclosed crystal structure of an NBTI ligand in complex with DNA gyrase and DNA revealed that the halogen atom in the para position of the phenyl right hand side (RHS) moiety is able to establish strong symmetrical bifurcated halogen bonds with the enzyme; these are responsible for the excellent enzyme inhibitory potency and antibacterial activity of these NBTIs. To further assess the possibility of any alternative interactions (e.g., hydrogen-bonding and/or hydrophobic interactions), we introduced various non-halogen groups at the p-position of the phenyl RHS moiety. Considering the hydrophobic nature of amino acid residues delineating the NBTI's binding pocket in bacterial topoisomerases, we demonstrated that designed NBTIs cannot establish any hydrogen-bonding interactions with the enzyme; hydrophobic interactions are feasible in all respects, while halogen-bonding interactions are apparently the most preferred.

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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 H2O and D2O, 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.

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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 Tgs 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-d6, 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.

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The two-dimensional (2D) Ruddlesden-Popper (RP) CsPbI3 with hydrophobic organic spacers can significantly improve the environmental and phase stability of photovoltaic devices by suppressing ion migration and inducing steric hindrance. However, due to the multiple-quantum-well structure, these spacer cations lead to weak interactions in 2D RP CsPbI3, which seriously affect the carrier transport. Here, a novel N-H-group-rich phenylhydrazine spacer, namely, PHA, was developed for 2D RP CsPbI3 perovskite solar cells (PSCs). A series of characterizations confirm that the 2D perovskites using PHA spacers enhanced the N-H···I hydrogen-bonding interaction between the organic spacer cations and the [PbI6]4- inorganic layer and accelerated the crystallization rate of the perovskite film, which was beneficial to the preparation of high-quality films with preferred vertical orientation, large grain size, and dense morphology. Meanwhile, the trap state density of the as-prepared 2D RP perovskite films is significantly reduced to enable efficient charge carrier transport. As a result, the (PHA)2Cs4Pb5I16 PSCs achieved a performance of 16.23% with good environmental stability. This work provides a simple organic spacer selection scheme to realize interaction optimization in 2D RP CsPbI3 to develop efficient and stable PSCs.

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A drug-drug multicomponent crystal consisting of metformin (MET) and dobesilate (DBS) was prospectively connected by solvent cooling and evaporating co-crystallization using the multicomponent crystal strategy, not only to optimize the physicochemical properties of single drugs, but also to play a role in the cooperative effect of DBS with the potential vascular protective effects of MET against diabetic retinopathy (DR). The crystal structure analysis demonstrated that MET and DBS were coupled in a 3D supramolecular structure connected by hydrogen-bonding interactions with a molar ratio of 1:1. Almost all hydrogen bond donors and receptors of MET and DBS participated in the bonding, which hindered the combination of remaining potential hydrogen bond sites and water molecules, resulting in a lower hygroscopicity property than MET alone.

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Three palladium(II) complexes with amino-amidato-phenolato-type tridentate ligands were synthesized and characterized by 1H NMR spectroscopy and X-ray crystallography. The strategic arrangement of a hydrogen-bond donor and acceptor adjacent to the substitution site of the PdII complex allowed the selective coordination of nucleosides. Among two pyrimidine-nucleosides, cytidine and 5-methyluridine, cytidine was successfully coordinated to the PdII complex while 5-methyluridne was not. On the other hand, both purine-nucleosides, adenosine and guanosine, were coordinated to the PdII complex. As purines have several coordination sites, adenosine afforded three kinds of coordination isomers expected from the three different donors. However, guanosine afforded a sole product according to the ligand design such that the formation of double intramolecular hydrogen-bond strongly induced the specific coordination by N1-position of guanine moiety. Furthermore, the preference of the nucleosides was evaluated by scrambling reactions. It was found that the preference of guanosine is nearly twice as high as adenosine and cytidine, owing to the three-point interaction of a coordination bond and two hydrogen bonds. These results show that the combination of a coordination and hydrogen bonds, which is reminiscent of the Watson-Crick base pairing, is an effective tool for the precise recognition of nucleosides.

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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 ß-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.

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A new selection of supramolecular liquid crystal complexes based on complementary molecules formed via hydrogen-bonding interactions is reported. All prepared complexes were prepared from 4-n-alkoxybenzoic acid (An) and N-4-cyanobenzylidene-4-n-(hexyloxy)benzenamine (I). FT-IR, temperature gradient NMR, Mass Spectrometer and Chromatography spectroscopy were carried out to confirm the -CN and -COOH H-bonded complexation by observing their Fermi-bands and the effects of the 1H-NMR signals as well as its elution signal from HPLC. Moreover, binary phase diagrams were established for further confirmation. All formed complexes (I/An) were studied by the use of differential scanning calorimetry and their phase properties were validated through the use of polarized optical microscopy Results of mesomorphic characterization revealed that all presented complexes exhibited enantiotropic mesophases and their type was dependent on the terminal lengths of alkoxy chains. Also, the mesomorphic temperature ranges decreased in the order I/A6 > I/A8 > I/A10 > I/A16 with linear dependency on the chain length. Finally, the density functional theory computational modeling has been carried out to explain the experimental findings. The relation between the dimensional parameters was established to show the effect of the aspect ratio on the mesophase range and stability. The normalized entropy of the clearing transitions (∆S/R) was calculated to illustrate the molecular interaction enhancements with the chain lengths.

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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. ZnCl2 was selected as a promoter of 1-allyl-3-methylimidazolium chloride for cellulose dissolution and as a precursor for nano-ZnO synthesis. Zn2+-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.

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Organic spacers play an important role in 2D/3D hybrid perovskites, which could combine the advantages of high stability of 2D perovskites and high efficiency of 3D perovskites. Here, a class of aromatic formamidiniums (ArFA) was developed as spacers for 2D/3D perovskites. It is found that the bulky aromatic spacer ArFA in 2D/3D perovskites could induce better crystalline growth and orientation, reduce the defect states, and enlarge spatially resolved carrier lifetime thanks to the multiple NH···I hydrogen-bonding interactions between ArFA and inorganic [PbI6]4- layers. As a result, compared to the control device with efficiency of 19.02%, the 2D/3D perovskite device based on such an optimized organic salt, namely benzamidine hydrochloride (PhFACl), exhibits a dramatically improved efficiency of 22.39% along with improved long-term thermal stability under 80 °C over 1400 h. Importantly, a champion efficiency of 23.36% was further demonstrated through device engineering for PhFACl-based 2D/3D perovskite solar cells. These results indicate the great potential of this class of ArFA spacers in highly efficient 2D/3D perovskite solar cells.

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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 P212121. 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 (ß) 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.

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Polybenzimidazoles are engineering plastics with superb thermal stability and this specificity has sparked a wide-ranging research to explore proton-conducting materials. Nevertheless, such materials encounter challenging issues owing to phosphoric acid proton carrier leakage and slow proton transport. We report a strategy for designing porous polybenzimidazole frameworks to address these key fundamental issues. The built-in channels are designed to be one-dimensionally extended, unidirectionally aligned, and fully occupied by neat phosphoric acid, while the benzimidazole walls trigger multipoint, multichain, and multitype interactions to spatially confine a phosphoric acid network in pores and facilitate proton conduction via deprotonation. The materials exhibit ultrafast and stable proton conduction for low proton carrier content and activation energy-a set of features highly desired for proton transport. Our results offer a design strategy for the fabrication of porous polybenzimidazoles for use in energy conversion applications.

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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/ß-citronellol, menthol/lactic acid, and thymol/ß-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.

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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.

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The monocation product of the oxidative condensation-cyclization between two mol-ecules of pyridine-2-carbaldehyde and one mol-ecule of CH3NH2·HCl in methanol, 2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridinium, was isolated in the presence of metal ions as bis-[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] tetra-iodo-cadmate, (C13H12N3)2[CdI4], (I), and the mixed chloride/nitrate salt, bis-[2-methyl-3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2-ium] 1.5-chlor-ide 0.5-nitrate trihydrate, 2C13H12N3 +·1.5Cl-·0.5NO3 -·3H2O, (II). Hybrid salt (I) crystallizes in the space group P21/n with two [L]2[CdI4] mol-ecules in the asymmetric unit related by pseudosymmetry. In the crystal of (I), layers of organic cations and of tetra-halometallate anions are stacked parallel to the ab plane. Anti-parallel L + cations disposed in a herring-bone pattern form π-bonded chains through aromatic stacking. In the inorganic layer, adjacent tetra-hedral CdI4 units have no connectivity but demonstrate close packing of iodide anions. In the crystal lattice of (II), the cations are arranged in stacks propagating along the a axis; the one-dimensional hydrogen-bonded polymer built of chloride ions and water mol-ecules runs parallel to a column of stacked cations.

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The 2'-substituents distinguish DNA from RNA nucleosides. 2'-O-methylation occurs naturally in RNA and plays important roles in biological processes. Such 2'-modifications may alter the hydrogen-bonding interactions of the nucleoside and thus may affect the conformations of the nucleoside in an RNA chain. Structures of the protonated 2'-O-methylated pyrimidine nucleosides were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy, assisted by electronic structure calculations. The glycosidic bond stabilities of the protonated 2'-O-methylated pyrimidine nucleosides, [Nuom+H]+, were also examined and compared to their DNA and RNA nucleoside analogues via energy-resolved collision-induced dissociation (ER-CID). The preferred sites of protonation of the 2'-O-methylated pyrimidine nucleosides parallel their canonical DNA and RNA nucleoside analogues, [dNuo+H]+ and [Nuo+H]+, yet their nucleobase orientation and sugar puckering differ. The glycosidic bond stabilities of the protonated pyrimidine nucleosides follow the order: [dNuo+H]+ < [Nuo+H]+ < [Nuom+H]+. The slightly altered structures help explain the stabilization induced by 2'-O-methylation of the pyrimidine nucleosides.

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Gas-phase conformations of the sodium-cationized forms of the 2'-deoxycytidine and cytidine mononucleotides, [pdCyd+Na]+ and [pCyd+Na]+, are examined by infrared multiple photon dissociation action spectroscopy. Complimentary electronic structure calculations at the B3LYP/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory provide candidate conformations and their respective predicted IR spectra for comparison across the IR fingerprint and hydrogen-stretching regions. Comparisons of the predicted IR spectra and the measured infrared multiple photon dissociation action spectra provide insight into the impact of sodium cationization on intrinsic mononucleotide structure. Further, comparison of present results with those reported for the sodium-cationized cytidine nucleoside analogues elucidates the impact of the phosphate moiety on gas-phase structure. Across the neutral, protonated, and sodium-cationized cytidine mononucleotides, a preference for stabilization of the phosphate moiety and nucleobase orientation is observed, although the details of this stabilization differ with the state of cationization. Several low-energy conformations of [pdCyd+Na]+ and [pCyd+Na]+ involving several different orientations of the phosphate moiety and sugar puckering modes are observed experimentally.

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The adsorption behaviour of the CdII-MOF {[Cd(L)2(ClO4)2]·H2O (1), where L is 4-amino-3,5-bis[3-(pyridin-4-yl)phenyl]-1,2,4-triazole, for butan-2-one was investigated in a single-crystal-to-single-crystal (SCSC) fashion. A new host-guest system that encapsulated butan-2-one molecules, namely poly[[bis{µ3-4-amino-3,5-bis[3-(pyridin-4-yl)phenyl]-1,2,4-triazole}cadmium(II)] bis(perchlorate) butanone sesquisolvate], {[Cd(C24H18N6)2](ClO4)2·1.5C4H8O}n, denoted C4H8O@Cd-MOF (2), was obtained via an SCSC transformation. MOF 2 crystallizes in the tetragonal space group P43212. The specific binding sites for butan-2-one in the host were determined by single-crystal X-ray diffraction studies. N-H...O and C-H...O hydrogen-bonding interactions and C-H...π interactions between the framework, ClO4- anions and guest molecules co-operatively bind 1.5 butan-2-one molecules within the channels. The adsorption behaviour was further evidenced by 1H NMR, IR, TGA and powder X-ray diffraction experiments, which are consistent with the single-crystal X-ray analysis. A 1H NMR experiment demonstrates that the supramolecular interactions between the framework, ClO4- anions and guest molecules in MOF 2 lead to a high butan-2-one uptake in the channel.