Structure Regulation of Electric Double Layer via Hydrogen Bonding Effect to Realize High-Stability Lithium-Metal Batteries

The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition.Based on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 h.In addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.

Optimizing extractants selection for efficient separation of phenols and nitrogen-containing heteroaromatics using hydrogen bond interaction strategies

Focusing on the use of imidazolium ionic liquids and quaternary ammonium salts-based deep eutectic solvents for the separation of phenols and nitrogen-containing heteroaromatics,the role of heteroaromatics as specific sites for hydrogen bond-based separation has been investigated.These environmentally friendly solvents are known for their ability to form hydrogen bonds with heteroatoms,a key aspect in separation processes.We quantified the hydrogen bond interaction energy to reach the threshold energy for efficient O-and N-heteroaromatics separation.This article provides an in-depth study of the structural nuances of different hydrogen bonding sites and their affinity properties while conducting a comparative evaluation of the separation efficiency of ionic liquids and deep eutectic solvents from a thermodynamic perspective.Results showed that phenols with dual hydrogen bonding recognition sites were easier to separate than nitrogen-containing heteroaromatics.Imidazolium ionic liquids were more suitable for the extraction of nonbasic nitrogen-containing heteroaromatics,and quaternary ammonium salts-based deep eutectic solvents are more effective for phenols and basic nitrogen-containing heteroaromatics,which was confirmed by Fourier transform infrared spectroscopy and empirical tests.Therefore,this study provides a theoretical basis for the strategy design and selection of extractants for the efficient separation of O-and N-containing aromatic compounds.

Machine-Learning-Assisted Design of Deep Eutectic Solvents Based on Uncovered Hydrogen Bond Patterns

Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.

The role of hydrogen bonding in solubilizing camptothecin in hydrophilic and hydrophobic ionic liquids

Utilizing ionic liquid(IL)-water mixtures as selective extraction solvents for raw materials from natural sources represents an efficacious approach;however,elucidating the underlying mechanisms inherent in various types of IL-aqueous solutions continues to pose a significant challenge.In this study,molecular dynamics simulations and density functional theory calculations are employed to illuminate the influence of the functional anion within ILs and the water content on the solvation mechanism and phase separation phenomena observed during the extraction of camptothecin(CPT)using aqueous IL solutions.The simulation results show that the anions in ILs preferentially dissolve CPT through hydrogen bonding at low water concentrations.As the water concentration increases,the hydrophobic IL binds more tightly to CPT,enabling the water to self-aggregate.The anions in hydrophilic IL form hydrogen bonds with water instead,further enhancing the dissolution of CPT.This work reveals the mechanism of phase separation and solvation of different types of IL aqueous solutions,which is helpful in developing new drug extraction and purification technologies.

Luminescence regulation of Sb^(3+)in 0D hybrid metal halides by hydrogen bond network for optical anti-counterfeiting

The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.

Pd^(0)-O v-Ce^(3+) Interfacial Sites with Charge Redistribution for Enhanced Hydrogenation of Methyl Oleate to Methyl Stearate

Improving the efficiency of metal/reducible metal oxide interfacial sites for hydrogenation reactions of unsaturated groups(e.g.,C=C and C=O)is a promising yet challenging endeavor.In our study,we developed a Pd/CeO_(2) catalyst by enhancing the oxygen vacancy(O V)concentration in CeO_(2) through high-temperature treatment.This process led to the formation of an interface structure ideal for supporting the hydrogenation of methyl oleate to methyl stearate.Specifi cally,metal Pd^(0) atoms bonded to the O V in defective CeO_(2) formed Pd^(0)-O v-Ce^(3+)interfacial sites,enabling strong electron transfer from CeO_(2) to Pd.The interfacial sites exhibit a synergistic adsorption eff ect on the reaction substrate.Pd^(0) sites promote the adsorption and activation of C=C bonds,while O V preferably adsorbs C=O bonds,mitigating competition with C=C bonds for Pd^(0) adsorption sites.This synergy ensures rapid C=C bond activation and accelerates the attack of active H*species on the semi-hydrogenated intermediate.As a result,our Pd/CeO_(2)-500 catalyst,enriched with Pd^(0)-O v-Ce^(3+)interfacial sites,dem-onstrated excellent hydrogenation activity at just 30℃.The catalyst achieved a Cis-C18:1 conversion rate of 99.8% and a methyl stearate formation rate of 5.7 mol/(h·g metal).This work revealed the interfacial sites for enhanced hydrogenation reactions and provided ideas for designing highly active hydrogenation catalysts.

Intramolecular Hydrogen Bond Improved Durability and Kinetics for Zinc‑Organic Batteries

Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.

Genetic Analysis of Two Novel GPI Variants Disrupting H Bonds and Localization Characteristics of 55 Gene Variants Associated with Glucose-6-phosphate Isomerase Deficiency

Objective:Glucose-6-phosphate isomerase(GPI)deficiency is a rare hereditary nonspherocytic hemolytic anemia caused by GPI gene variants.This disorder exhibits wide heterogeneity in its clinical manifestations and molecular characteristics,often posing challenges for precise diagnoses using conventional methods.To this end,this study aimed to identify the novel variants responsible for GPI deficiency in a Chinese family.Methods:The clinical manifestations of the patient were summarized and analyzed for GPI deficiency phenotype diagnosis.Novel compound heterozygous variants of the GPI gene,c.174C>A(p.Asn58Lys)and c.1538G>T(p.Trp513Leu),were identified using whole-exome and Sanger sequencing.The AlphaFold program and Chimera software were used to analyze the effects of compound heterozygous variants on GPI structure.Results:By characterizing 53 GPI missense/nonsense variants from previous literature and two novel missense variants identified in this study,we found that most variants were located in exons 3,4,12,and 18,with a few localized in exons 8,9,and 14.This study identified novel compound heterozygous variants associated with GPI deficiency.These pathogenic variants disrupt hydrogen bonds formed by highly conserved GPI amino acids.Conclusion:Early family-based sequencing analyses,especially for patients with congenital anemia,can help increase diagnostic accuracy for GPI deficiency,improve child healthcare,and enable genetic counseling.

Hydrogen-bond mediated and concentrate-dependent NaHCO_(3) crystal morphology in NaHCO3–Na2CO3 aqueous solution: Experiments and computer simulations

Adding Na_(2)CO_(3) to the NaHCO_(3) cooling crystallizer, using the common ion effect to promote crystallization and improve product morphology, is a new process recently proposed in the literature. However, the mechanism of the impact of Na_(2)CO_(3)on the crystal morphology is still indeterminate. In this work, the crystallization of NaHCO_(3)in water and Na_(2)CO_(3)–NaHCO_(3) aqueous solution was investigated by experiments and molecular dynamics simulations(MD). The crystallization results demonstrate that the morphology of NaHCO_(3) crystal changed gradually from needle-like to flake structure with the addition of Na_(2)CO_(3). The simulation results indicate that the layer docking model and the modified attachment energy formula without considering the roughness of crystal surface can obtain the crystal morphology in agreement with the experimental results, but the lower molecules of the crystal layer have to be fixed during MD. Thermodynamic calculation of the NaHCO_(3) crystallization process verifies that the common ion effect from Na^(+)and the ionization equilibrium transformation from CO_(3)^(2-) jointly promote the precipitation of NaHCO_(3) crystal. The radial distribution function analysis indicates that the oxygen atoms of Na_(2)CO_(3) formed strong hydrogen bonds with the hydrogen atoms of the(0 1 1) face, which weakened the hydration of water molecules at the crystal surface, resulting in a significant change in the attachment energy of this crystal surface. In addition, Na+and CO_(3)^(2-) are more likely to accumulate on the(011) face,resulting in the fastest growth rate on this crystal surface, which eventually leads to a change in crystal morphology from needle-like to flake-like.

Halogen Bonding or Hydrogen Bonding between 2,2,6,6-Tetramethyl- piperidine-noxyl Radical and Trihalomethanes CHX3 （X=CI, Br, I）

The halogen and hydrogen bonding complexes and trihalomethanes （CHX3, X=C1, Br, I） are between 2,2,6,6-tetramethylpiperidine-noxyl simulated by computational quantum chem- istry. The molecular electrostatic potentials, geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained. The results indicate that both halogen and hydrogen bonding interactions obey the order CI〈Br〈I, and hydrogen bonding is stronger than the corresponding halogen bond- ing. So, hydrogen bonding complexes should be dominant in trihalomethanes. However, it is possible that halogen bonding complex is competitive, even preponderant, in triiodomethane due to the similar interaction energy. This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.

Novel hot-melting hyperbranched poly(ester-amine) bearing self-complementary quadruple hydrogen bonding units

Hyperbranched poly（amine-ester）s bearing self-complementary quadruple hydrogen bonding units display excellent mechanical and temperature-dependent melt rheological properties, which make them suitable as novel hot-melting materials.

π-π Stacking, Hydrogen Bonding and Magnetic Coupling Mechanism on a Mono-nuclear Cu^Ⅱ Complex

A new mono-nuclear CuII complex [Cu（DPP）（DP）Br]（ClO4）H2O （DPP = 2-（3,5- dimethyl-1H-pyrazol-1-yl）-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole） has been syn- thesized with 2-（3,5-dimethyl-1H-pyrazol-1-yl）-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765（2）, b = 17.044（3）, c = 10.9044（16）, β= 97.112（2）°, V = 2538.5（6）3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F（000） = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.

Investigation of inter-molecular hydrogen bonding in the binary mixture (acetone+water) by concentration dependent Raman study and ab initio calculations

This paper reports that vibrational spectroscopic analysis on hYdrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6-311＋G（d,p） basis set. Changes in wavenumber position and linewidth （fullwidth at half maximum） have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.

Hydrogen Bonding-Assisted Synthesis of Silica/Oxidized Mesocarbon Microbeads Encapsulated in Amorphous Carbon as Stable Anode for Optimized/Enhanced Lithium Storage

The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work,a novel silica/oxidized mesocarbon microbead/amorphous carbon(SiO2/O’MCMB/C)hierarchical structure in which SiO2 is sandwiched between spherical graphite and amorphous carbon shell was succes sfully fabricated through hydrogen bonding-assisted self-assembly and post-carbon coating method.The obtained three-layer hierarchical structure effectively accommodates the volumetric expansion of SiO2 and significantly enhances the electronic conductivity of composite materials.Moreover,the outer layer of amorphous carbon effectively increases the diffusion rate of lithium ions and promotes the formation of stable SEI film.As a result,the SiO2/O’MCMB/C composite exhibits superior electrochemical performance with a reversible capacity of 459.5 mA h/g in the first cycle,and the corresponding Coulombic efficiency is 62.8%.After 300 cycles,the capacity climbs to around 600 mA h/g.This synthetic route provides an efficient method for preparing SiO2 supported on graphite with excellent electrochemical performance,which is likely to promote its commercial applications.

Hydrogen-bonding Interaction of 1,2,3-triazine-waters Complexes

Density functional theory B3LYP method with 6-31＋＋G＊＊ basis was used to optimize the geometries of the ground states for 1,2,3-triazine-（H2O）n（n=1,2,3） complexes. All calculations indicate that the 1,2,3- triazine-water complexes in the ground states have strong hydrogen-bonding interaction, and the complex having a N… .H-O hydrogen bond and a chain of water molecules which is terminated by a O. … .H-C hydrogen bond is the most stable. The H-O stretching modes of complexes are red-shifted relative to that of the monomer. In addition, the Natural bond orbit （NBO） analysis indicates that the intermolecular charge transfer between 1,2,3-triazine and water is 0.0222e, 0.0261e and 0.0273e for the most stable 1：1, 1：2 and 1：3 complexes, respectively. The first singlet （n, π＊） vertical excitation energy of the monomer 1,2,3-triazine and the hydrogen-bonding complexes of 1,2,3-triazine-（H2O）n were investigated by time-dependent density functional theory.

Syntheses, Crystal Structures and Hydrogen-bonding Motif of Two Glycoluril Derivatives

The synthesis and aggregation behavior of two glycoluril derivatives were descrybed.The crystal of compound 1 belongs to the triclinic system,space group ■,with a=8.946（1）,b=13.445（2）,c=20.361（3）?,α=89.517（3）,β=84.405（3）,γ=86.325（3）°,Z=2,V=2432.1（6）?3,Dc=1.293 g·cm-3,C48H34N6O6·2DMSO,Mr=947.07,F（000）=992,μ=0.170 mm-1,the final R=0.1606 and wR=0.2410 for 4382 observed reflections（Ⅰ>2σ（Ⅰ））.The crystal of compound 2belongs to the monoclinic system,space group P21/c,with a=9.500（3）,b=24.522（8）,c=17.997（6）?,Z=2,V=4054（2）?3,Dc=1.296 g·cm-3,C48H34N6O6,Mr=790.81,F（000）=1648,μ=0.087mm-1,the final R=0.2146 and wR=0.2535 for 2878 observed reflections（Ⅰ>2σ（Ⅰ））.Unlike the highly conserved R22（8）hydrogen-bonding amide···amide homosynthon,the structural analysis indicated that compound 1 selected the C（20）hydrogen-bonding motif and 2 selected the R22（34）hydrogen-bonding motif,which revealed the competition from remote solvent molecule and the interference of the molecular hydrocarbon core in crystal packing.The supramolecular structure revealed molecule 1 is further linked into a one-dimensional chain and 2 into a two-dimensional interwoven plane by N–H···N hydrogen bonds.

SYNTHESIS AND CHARACTERIZATION OF WELL-DEFINED BLOCK COPOLYMERS CONTAINING PENDANT,SELF-COMPLEMENTARY QUADRUPLE HYDROGEN BONDING SITES

The title block copolymer (defined as PSUEA) containing pendant,self-complementary quadruple hydrogen bonding sites has been prepared successfully by three steps.First,poly(styrene-b-2-hydroxyethyl acrylate) (defined as PSHEA) was prepared by living radical polymerizing 2-hydroxyethyl acrylate (HEA) initiated by polystyrene (PSt) macro- initiator,which was prepared via nitroxide-mediated polymerization (NMP) technique.After treated by excessive 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI),...

Synthesis and Structure of a Hydrogen-bonding Assembled Three-dimensional Supramolecular Indium(III) Compound Involving One-dimensional Helices

The title compound [In（H2ip）（pdc）（H2O）] （H3ip = 5-hydroxyisophthalic acid, H2Pdc = pyridine-2,6-dicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 13.830（8）, b = 6.488（4）, c = 17.632（10）A^°, β = 92.510（10）°, C15H10InNO10, Mr= 479.06, V = 1580.6（15）A^°3, Z = 4, De= 2.013 g/cm^3, F（000） = 944,μ = 1.557 mm^-1, the final R = 0.0413 and wR = 0.0793 for 2950 observed reflections with I 〉 2σ（I）. The In（Ⅲ） ion is seven-coordinated in a slightly distorted penta-bipyramidal geometry. The mixed ligands connect the In（Ⅲ） ions into 21 helical chains along the [010] direction, and the hydrogen bonds assemble the chains into a three-dimensional supramolecular network.

An Extended Cu(Ⅱ) Complex Structure Sustained by Hydrogen Bonding and C-H…π Interactions

The title complex [Cu（L1）（L2）（H2O）]·H2O（1,HL1 = N-（imino（pyridin-2-yl）me-thyl）picolinamidine）,HL2 = salicylic acid） has been obtained by volatilization method with L1 prepared from 2,4,6-tripyridyl-1,3,5-triazine in situ.1 was fully characterized by single-crystal X-ray diffraction,elemental analysis and FT-IR.This complex exhibits a three-dimensional frame-work constructed through hydrogen bonding and C-H···π stacking interactions.The cyclic voltametric behavior of complex 1 was also investigated.1 belongs to the monoclinic system,space group P21/c with a = 15.112（5）,b = 7.115（2）,c = 19.899（6） ,β = 112.32°,V = 1979.4（11） 3,Mr = 460.94,Dc = 1.540 g/cm3,F（000） = 948,μ = 1.146 mm-1,Z = 4,the final R = 0.0612 and wR = 0.1813 for 2510 observed reflections with I 2σ（I）.

Synthesis of a New Porphyrin-fluorescein Hybrid and its Supramolecular Self-assembly with Amino-porphyrinatomanganese(Ⅲ) by Hydrogen-bonding

A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomanganese [Mn (p-APTPP)Cl] by hydrogen-bonding was studied using fluorescence spectroscopic titration and ESI-MS.