Showing papers on "Hydrogen bond published in 2021"

Copper Catalyzed C(sp3)-H Bond Alkylation via Photoinduced Ligand-to-Metal Charge Transfer.

Abstract: Utilizing catalytic CuCl2 we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp3)-H bonds with electron-deficient olefins The active cuprate catalyst undergoes Ligand-to-Metal Charge Transfer (LMCT) to enable the generation of a chlorine radical which acts as a powerful hydrogen atom transfer reagent capable of abstracting strong electron-rich C(sp3)-H bonds Of note is that the chlorocuprate catalyst is an exceedingly mild oxidant (05 V vs SCE) and that a proposed protodemetalation mechanism offers a broad scope of electron-deficient olefins, offering high diastereoselectivity in the case of endocyclic alkenes The coupling of chlorine radical generation with Cu reduction through LMCT enables the generation of a highly active HAT reagent in an operationally simple and atom economical protocol

Non-Covalent Interactions in Proteins

Abstract: Overview of Protein Structural Elements and Basic Definitions Non-covalent Interactions and Structure-Function Relationships in Proteins Observation of van der Waals Interactions Nature of van der Waals Interactions Potential Functions for Application in Proteins Approximation for Polyatomic Systems Nature of Hydrogen Bonds Geometry and Strength of the Hydrogen Bond Hydrogen Bonds in Proteins Hydrogen Bonds and Protein Stability Nature of Hydrophobic Interactions, Pseudo Forces Water Hydrophobic Effect Hydrophobic Interactions in Proteins Debye-Huckel Theory Ion-Solvent Interactions Calculation of Electrostatic Interactions in Proteins Why Does One Need to Know Ionization Equilibria? Factors Determining Ionization Equilibria in Proteins Combinatorial Problem Cooperative Ionization Allocation Variation of Polar Hydrogen Atoms Examples for pH-Dependent Hydrogen Bonding Conformational Flexibility Involving Non-Hydrogen Atoms Unfolding Induced by pH Modeling of Unfolded Proteins Thermal Stability of Proteins.

Crossover from hydrogen to chemical bonding.

Abstract: Hydrogen bonds (H-bonds) can be interpreted as a classical electrostatic interaction or as a covalent chemical bond if the interaction is strong enough. As a result, short strong H-bonds exist at an intersection between qualitatively different bonding descriptions, with few experimental methods to understand this dichotomy. The [F-H-F]- ion represents a bare short H-bond, whose distinctive vibrational potential in water is revealed with femtosecond two-dimensional infrared spectroscopy. It shows the superharmonic behavior of the proton motion, which is strongly coupled to the donor-acceptor stretching and disappears on H-bond bending. In combination with high-level quantum-chemical calculations, we demonstrate a distinct crossover in spectroscopic properties from conventional to short strong H-bonds, which identify where hydrogen bonding ends and chemical bonding begins.

Polyoxometalate-Based Metal-Organic Framework as Molecular Sieve for Highly Selective Semi-Hydrogenation of Acetylene on Isolated Single Pd Atom Sites.

Abstract: Achieving highly selective acetylene semi-hydrogenation in an ethylene-rich gas stream is of great industrial importance. Herein, we construct isolated single Pd atom in a polyoxometalate-based metal-organic framework (POMOF). The unique internal environment allows this POMOF to separate acetylene from acetylene/ethylene gas mixtures and confine it close to the single Pd atom. After semi-hydrogenation, the resulting ethylene is preferentially discharged from the pores, achieving a selectivity of 92.6 %. First-principles simulations reveal that the adsorbed acetylene/ethylene molecules form hydrogen bond networks with oxygen atoms of SiW12 O404- and create dynamic confinement regions, which preferentially release the produced ethylene. Besides, at the Pd site, the over-hydrogenation of ethylene exhibits a higher reaction energy barrier than the semi-hydrogenation of acetylene. The combined advantages of POMOF and single Pd atom provides an effective approach for the regulation of semi-hydrogenation selectivity.

High-Capacity NH4+ Charge Storage in Covalent Organic Frameworks.

Abstract: Ammonium ions (NH4+), as non-metallic charge carriers, have spurred great research interest in the realm of aqueous batteries. Unfortunately, most inorganic host materials used in these batteries are still limited by the sluggish diffusion kinetics. Here, we report a unique hydrogen bond chemistry to employ covalent organic frameworks (COFs) for NH4+ ion storage, which achieves a high capacity of 220.4 mAh g-1 at a current density of 0.5 A g-1. Combining the theoretical simulation and materials analysis, a universal mechanism for the reaction of nitrogen and oxygen bridged by hydrogen bonds is revealed. In addition, we explain the solvation behavior of NH4+, leading to a relationship between redox potential and desolvation energy barrier. This work provides a new insight into NH4+ ion storage in host materials based on hydrogen bond chemistry. This mechanism can be leveraged to design and develop COFs for electrochemical energy storage.

Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds

Abstract: Proton activity at the electrified interface is central to the kinetics of proton-coupled electron transfer (PCET) reactions for making chemicals and fuels. Here we employ a library of protic ionic liquids in an interfacial layer on platinum and gold to alter local proton activity, where the intrinsic oxygen-reduction reaction (ORR) activity is enhanced up to fivefold, exhibiting a volcano-shaped dependence on the pKa of the ionic liquid. The enhanced ORR activity is attributed to strengthened hydrogen bonds between ORR products and ionic liquids with comparable pKas, resulting in favourable PCET kinetics. This proposed mechanism is supported by in situ surface-enhanced Fourier-transform infrared spectroscopy and our simulation of PCET kinetics based on computed proton vibrational wavefunctions at the hydrogen-bonding interface. These findings highlight opportunities for using non-covalent interactions between hydrogen-bonded structures and solvation environments at the electrified interface to tune the kinetics of ORR and beyond. Understanding the role of hydrogen bonds at the electrode interface is important for controlling the kinetics of the oxygen-reduction reaction. Here the authors modify gold and platinum surfaces with a series of protic ionic liquids to show that pKa can be used to optimize proton-coupled electron transfer through hydrogen bonding.

Pathway and Length Control of Supramolecular Polymers in Aqueous Media via a Hydrogen Bonding Lock

Abstract: Programming the organization of π-conjugated systems into nanostructures of defined dimensions is a requirement for the preparation of functional materials. Herein, we have achieved high-precision control over the self-assembly pathways and fiber length of an amphiphilic BODIPY dye in aqueous media by exploiting a programmable hydrogen bonding lock. The presence of a (2-hydroxyethyl)amide group in the target BODIPY enables different types of intra- vs. intermolecular hydrogen bonding, leading to a competition between kinetically controlled discoidal H-type aggregates and thermodynamically controlled 1D J-type fibers in water. The high stability of the kinetic state, which is dominated by the hydrophobic effect, is reflected in the slow transformation to the thermodynamic product (several weeks at room temperature). However, this lag time can be suppressed by the addition of seeds from the thermodynamic species, enabling us to obtain supramolecular polymers of tuneable length in water for multiple cycles.

Nitrene-mediated intermolecular N-N coupling for efficient synthesis of hydrazides.

Abstract: N-N linkages are found in many natural compounds and endow fascinating structural and functional properties. In comparison to the myriad methods for the construction of C-N bonds, chemistry for N-N coupling, especially in an intermolecular fashion, remains underdeveloped. Here, we report a nitrene-mediated intermolecular N-N coupling of dioxazolones and arylamines under iridium or iron catalysis. These reactions offer a simple and efficient method for the synthesis of various hydrazides from readily available carboxylic acid and amine precursors. Although the Ir-catalysed conditions usually give higher N-N coupling yield than the Fe-catalysed conditions, the reactions of sterically more demanding dioxazolones derived from α-substituted carboxylic acids work much better under the Fe-catalysed conditions. Mechanistic studies revealed that the nitrogen atom of Ir acyl nitrene intermediates has strong electrophilicity and can undergo nucleophilic attack with arylamines with the assistance of Cl···HN hydrogen bonding to form the N-N bond with high efficiency and chemoselectivity.

Porous Carbon Nitride Thin Strip: Precise Carbon Doping Regulating Delocalized π-Electron Induces Elevated Photocatalytic Hydrogen Evolution.

Abstract: The photocatalytic efficiency of polymeric carbon nitride is hampered by high carrier recombination rate and low charge transfer. Herein, these issues are addressed by constructing 1D strip-like carbon nitride with a large π-electron conjugated system from carbon-doping, realizing the synchronization control of its electronic structure and morphology. Nicotinic acid, a monomer with the carboxyl group and pyridine ring, and melamine are selected for assembling the strip-like supramolecular via hydrogen bond under hydrothermal process. Both peripheral pyridine unit and hydrogen bond have significant effect on self-assembly process of nicotinic acid and melamine along one dimension to form a strip-like precursor. Subsequently, 1D thin porous strip-like carbon nitride is obtained by calcination treatment of precursor. The as-prepared 1D strip-like carbon nitride with effective π delocalization from carbon-doping and porous structure can accelerate charges and mass transfer and provide extra active sites. Both theoretical and experimental results demonstrate that carbon doping (pyridine heterocycle) narrows the bandgap via manipulating the band position and increases the π electron density. Thus, the 1D porous thin strip-like carbon nitride realizes compelling hydrogen evolution rate (126.2 µmol h-1 ), far beyond (≈18 fold) the value of polymeric carbon nitride (PCN) (7.2 µmol h-1 ) under visible light irradiation.

Single crystals of mechanically entwined helical covalent polymers.

Abstract: Double helical conformation of polymer chains is widely observed in biomacromolecules and plays an essential role in exerting their biological functions, such as molecular recognition and information storage. It has remained challenging, however, to prepare synthetic helical polymers, and those that exist have mainly been limited to single-stranded polymers or short oligomeric double helices. Here, we report the synthesis of covalent helical polymers, with a high molecular weight, from the achiral monomer hexahydroxytriphenylene through to spiroborate formation. Polymerization and crystallization occurred simultaneously under solvothermal conditions to form single crystals of the resulting helical covalent polymers. Characterization by single-crystal X-ray diffraction showed that each crystal consisted of pairs of mechanically entwined polymers. No strong non-covalent interactions were observed between the two helical polymers that formed a pair; instead, each strand interacted with neighbouring pairs through hydrogen bonding. Each individual crystal was made up of helical polymers of the same handedness, but the crystallization process produced a racemic conglomerate, with equal amounts of right-handed and left-handed crystals.

Research on synthesis and self-healing properties of interpenetrating network hydrogels based on reversible covalent and reversible non-covalent bonds

Abstract: First of all, we will provide a brief background on the self-healing hydrogels we produced which are suitable for the complex environment of nature. In this paper, disulfide bonds and acylhydrazone bonds can be combined in SH-WPU and hydrogen bonds existed in PAMAM. And the hydrogel can achieve self-healing under acid, alkaline, neutral or light environment.Self-healing for 1 h, 24 h and 48 h, the self-healing efficiency is 31.58%, 49.84% and 87.35% respectively. This effect achieved the desired effect and the repair effect is more obvious than previous research results. The hydrogels have potential applications in the field of biomaterials.

Hydrogen-Bond-Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second-Harmonic Generation

Abstract: Four chiral coordination polymers (CPs), M[(S,S)-C14 H14 N2 O6 ] and M[(R,R)-C14 H14 N2 O6 ] (M=Zn or Cd), have been exclusively synthesized in high yields with the aid of newly designed chiral ligand under hydrothermal condition. The CPs crystallizing in the orthorhombic nonpolar space group, C2221 , reveal three-dimensional framework structures composed of MO4 tetrahedra and the corresponding homochiral linkers. Powder second-harmonic generation (SHG) measurements indicate that the nonpolar CPs reveal very strong SHG efficiency of ca. 5-9 times that of KH2 PO4 and exhibit type-I phase-matching behavior. Density functional theory calculations suggest that the unusually large SHG efficiency found from the nonpolar CPs should be attributable to the synergistic effect of polarizable metal cations and enhanced hyperpolarizability in the donor-acceptor system originating from the hydrogen bonding in the coordinated linkers.

Hydrogen Bond Interpenetrated Agarose/PVA Network: A Highly Ionic Conductive and Flame-Retardant Gel Polymer Electrolyte.

Abstract: The gel polymer electrolyte (GPE) is the key to assembling high-performance solid-state supercapacitors (SSCs). The commercial poly(vinyl alcohol) (PVA) GPE has developed a reputation due to low ionic conductivity endowed by its high crystallinity and poor water retention capacity. In this work, density functional theory (DFT) calculations first revealed that the high crystallinity of PVA can be greatly disrupted by forming hydrogen bonds with natural agarose macromolecules. The hydrogen bond interpenetrated three-dimensional agarose/PVA network offers high water retention and large amounts of channels for movement of Li+ on hydroxyl oxygen atoms. So, an optimized formation of the Li-O coordinate bond (gLi-O(r) = 8.78) and improved diffusion coefficient of Li+ (DLi+) (71 × 10-6 cm2 s-1) were obtained in the agarose/PVA model. When assembled into SSCs, agarose/PVA-GPE with 2 M LiOAc (AP-GPE) exhibits an outstanding specific capacitance (697.22 mF cm-2 at 5 mA cm-2). The high water retention of agarose and large amounts of -OH groups in the agarose macromolecular can generate H2O by dehydration reaction, reducing the flammability of PVA and greatly enhancing the safety of SSCs.

Direct observation of ultrafast hydrogen bond strengthening in liquid water

Abstract: Water is one of the most important, yet least understood, liquids in nature. Many anomalous properties of liquid water originate from its well-connected hydrogen bond network1, including unusually efficient vibrational energy redistribution and relaxation2. An accurate description of the ultrafast vibrational motion of water molecules is essential for understanding the nature of hydrogen bonds and many solution-phase chemical reactions. Most existing knowledge of vibrational relaxation in water is built upon ultrafast spectroscopy experiments2–7. However, these experiments cannot directly resolve the motion of the atomic positions and require difficult translation of spectral dynamics into hydrogen bond dynamics. Here, we measure the ultrafast structural response to the excitation of the OH stretching vibration in liquid water with femtosecond temporal and atomic spatial resolution using liquid ultrafast electron scattering. We observed a transient hydrogen bond contraction of roughly 0.04 A on a timescale of 80 femtoseconds, followed by a thermalization on a timescale of approximately 1 picosecond. Molecular dynamics simulations reveal the need to treat the distribution of the shared proton in the hydrogen bond quantum mechanically to capture the structural dynamics on femtosecond timescales. Our experiment and simulations unveil the intermolecular character of the water vibration preceding the relaxation of the OH stretch. Liquid ultrafast electron scattering measures structural responses in liquid water with femtosecond temporal and atomic spatial resolution to reveal a transient hydrogen bond contraction then thermalization preceding relaxation of the OH stretch.

Urea Derivatives as Functional Molecules: Supramolecular Capsules, Supramolecular Polymers, Supramolecular Gels, Artificial Hosts, and Catalysts

Abstract: Urea, which has both hydrogen bond acceptor and donor moieties, is an ideal structure for a supramolecular synthon. Various supramolecules having ureido group(s) have been widely developed. This article summarizes recent developments of urea derivatives that exhibit various functions: i) supramolecular capsules that form discrete urea-urea intermolecular hydrogen bonds, ii) supramolecular polymers that form continuous urea-urea intermolecular hydrogen bonds, iii) supramolecular gels that form continuous urea-urea intermolecular hydrogen bonds, iv) artificial host molecules based on the molecular recognition ability of the ureido group, and v) catalytic reactions developed by utilizing the molecular recognition ability of the ureido group.

Comparison of non-covalent binding interactions between three whey proteins and chlorogenic acid: Spectroscopic analysis and molecular docking

Abstract: Non-covalent binding interactions between three whey proteins β-lactoglobulin (β-Lg), α-lactalbumin (α-La) and bovine serum albumin (BSA) with chlorogenic acid (CA) were investigated using spectroscopic analysis and molecular docking Fluorescence study showed that CA quenched the fluorescence of three whey proteins through static mode The binding number was equal to 1 for three proteins and binding affinity in declined order was: α-La > β-Lg > BSA Thermodynamic parameters revealed contribution of hydrophobic force in three systems Fluorescence resonance energy transfer (FRET) measurements indicated that energy transfer occurs between three proteins and CA in probability of α-La > BSA > β-Lg Variation in surface charge indicated the involvement of electrostatic interaction Surface hydrophobicity (H0) were declined with decrease degree of α-La > β-Lg > BSA α-La and β-Lg were unfolded with more flexible structure while BSA skeleton was more compact after interacting with CA Modeling study revealed that the most likely binding sites for the three proteins were outer surface, cleft and subdomain I for β-Lg, α-La and BSA respectively Docking results also suggested the contribution of hydrophobic interaction and hydrogen bond (β-Lg, α-La) for formation of molecular nano complexes between whey proteins and CA