On the Possibility of Using UV Spectroscopy as a Measure of the Low-Barrier Hydrogen Bond

In many enzyme-catalyzed biochemical pathways, a short, strong hydrogen bond between an enzyme and substrate is an important structural feature. These bonds are termed low-barrier hydrogen bonds. In this paper, we show that UV spectra can be used as an experimental technique to determine if a system contains a low-barrier hydrogen bond (LBHB). We simulate, using the time-dependent view of UV spectroscopy, several different UV spectra: absorption, photodissociation, and emission, on systems containing a low-barrier hydrogen bond. We find several distinguishing spectral features in these UV spectra for systems that possess a LBHB.     

Theoretical infrared line shapes of H‐bonds within the strong anharmonic coupling theory and Fermi resonances effects

In this article, we extend a previous work toward presenting a theoretical study of the effects of Fermi resonances and the fundamental anharmonic coupling parameter α between the high‐frequency mode and the H‐bond bridge. The model incorporates (i) both intrinsic anharmonicities of the fast mode (double well potential) and the H‐bond Bridge (Morse potential), (ii) strong anharmonic coupling theory, (iii) Fermi resonances by the aid of an anharmonic coupling between the fast mode and one or several harmonic bending modes, (iv) quadratic modulation of both the angular frequency and the equilibrium position of the X? …Y stretching mode on the intermonomer ? H… motions, and (v) the quantum direct (fast and bending modes) and indirect dampings (slow mode). The IR spectral density is obtained by Fourier transform of the autocorrelation function of the transition dipole moment operator of the X? H bond. The numerical calculation shows that Fermi resonances generate very complicated profiles with multisubstructure and also provide a direct evidence of Fermi resonances which were predicted to be a major feature of H‐bonds. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

An FT-IR demonstration of the occurrence of satellite bands in the spectra of hydrogen bonds in crystals

OH stretching fundamentals in the spectra of hydrogen-bonded crystals are accompanied by satellite bands due to sum and difference transitions involving one quantum of the OH stretching vibration and one or more quanta of the low-frequency vibration of the hydrogen bond. Such satellites were detected in the FT-IR spectra of two hydrogen-bonded crystals, ice and methanol.NRCC No. 29006     

环烷酸酸盐体系的红外光谱研究──Ⅰ.环烷酸钠和环烷酸钾酸盐体系

本文测量了一系列不同组成的环烷酸－环烷酸钠（钾）酸盐体系的红外光谱，结果表明酸盐体系并不是简单的混合物，而是存在较强的相互作用，包括酸与盐之间的氢键作用和配位作用，体系中存在着组成为ＫＡ·ＨＡ和ＮａＡ·ＨＡ及更多种类的酸盐缔合物．     

半固态汽油添加剂低温下的溶解

一种市售汽油添加剂,常温下是半固态。加少量到一定量汽油中,轻摇即可溶解。但当温度降低到10℃,小晶体颗粒陆续开始析出。温度降到0℃时,溶质基本完全析出,且逐渐形成较大的颗粒团,严重影响了此添加剂在低温环境下的使用。为此我们进行了其延时降凝研究。发现溶液中加入少量具有较强极性可与溶质形成氢键、同时具有与溶剂部分相似结构的化合物异丙醇二甲基甲酰胺等,可使溶质在-15℃以下不析出,保持为均匀溶液。1　实验部分此添加剂的主要成份是分子量较大的软脂酸甘油酯,凝固点19℃。据此,在含溶质5%的条件下加入尽可能少的不同溶剂(下…     

原子间的另一种作用力——氢键

从氢键定义的延伸、键能大小及其共价性质的表现,认为氢键内容的发展已经可以将之称为\"原子间的另一种作用力\"。在此基础上,尝试推动氢键教学内容的改革,这样不但可以丰富基础无机化学中\"氢键\"的内容,而且可以有效增进学生从基础课教学提高科学研究的意识。     

An Experimental Exploration of C−H⋅⋅⋅X Hydrogen Bond in [CHCl3−X(CH3)2] Complexes (X=O,S, and Se)

Among the conglomeration of hydrogen bond donors, the C−H group is prevalent in chemistry and biology. In the present work, CHCl₃ has been selected as the hydrogen bond donor and are X(CH₃)₂ are the hydrogen bond acceptors. Formation of C−H⋅⋅⋅X hydrogen bond under the matrix isolation condition is confirmed by the observation of red-shift in the C−H stretching frequency of CHCl₃ and comparison with the simulated spectra. Stabilisation energy of all the three complexes is almost equal although the observed red-shift for the C−H⋅⋅⋅O complex is less compared to the C−H⋅⋅⋅S/Se complexes. The nature and origin of the hydrogen bond have been delineated using Natural Bond Orbital, Atoms in Molecules, Non-Covalent Interaction analyses, and Energy Decomposition Analysis. Charge transfer is found to be proportional to the observed red-shift. This work provides the first impression of C−H⋅⋅⋅Se hydrogen bond and its comparison with C−H⋅⋅⋅O/S hydrogen bond interaction under experimental condition.     

Studies on the Effect of Structure to Property Stability of Glucomannan

1 INTRODUCTION Directive action of hydrogen bond paves the way for new fields of biological activity, molecular re- cognition and crystal engineering[1]. Hydrogen bond plays an important role in the physical and chemical properties, such as melting point, boiling point, solu- bility, acid strength, viscosity and hardness degree[2]. At present, the popular tools used to investigate hy- drogen bond include wet melting point method, chromatography analysis method, spectrum method and diffract…     

Conformers and intramolecular hydrogen bonding of the oxalic acid monomer and its anions

Density functional theory, B3LYP/6‐31G** and B3LYP/6‐311+G(2d,p), and ab initio MP2/6‐31G** calculations have been carried out to investigate the conformers, transition states, and energy barriers of the conformational processes of oxalic acid and its anions. QCISD/6‐31G** geometrical optimization is also performed in the stable forms. Its calculated energy differences between the two most stable conformers are very near to the related observed value at 7.0 kJ/mol. It is found that the structures and relative energies of oxalic acid conformers predicted by these methods show similar results, and that the conformer L1 (C_2h) with the double‐interfunctional‐groups hydrogen bonds is the most stable conformer. The magnitude of hydrogen bond energies depends on the energy differences of various optimized structures. The hydrogen bond energies will be about 32 kJ/mol for interfunctional groups, 17 kJ/mol for weak interfunctional groups, 24 kJ/mol for intra‐COOH in (COOH)₂, and 60 kJ/mol for interfunctional groups in (COOH)COO⁻¹ ion if calculated using the B3LYP/6‐311+G(2d,p) method. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 76: 541–551, 2000     

PROTONATED LIGAND OUTER-SPHERE COMPLEX FORMED IN THE REACTION OF 6-METHYLPYRIDINE-2-CARBOXALDEHYDE PHENYLHYDRAZONE WITH Ph2SnCl2. A TRUE CASE OF HYDROGEN BONDING INVOLVING AN Sn-CI BOND

Abstract

The reaction of 6-methylpyridine-2-carboxaldehyde phenylhydrazone (L) with Ph₂SnCl₂ has resulted in the formation of a complex salt [LH⁺]₂[Ph₂SnCl₄]^2-. X-ray diffraction studies on the salt reveal the structure of the [Ph₂SnCl₄] dianion to be centrosymmetric with the tin atom in a distorted octahedral trans-C₂Cl₄ environment; Sn-Cl(1) 2.598(2), Sn-Cl(2) 2.5875(7) and Sn-C(1) 2.146(3) Å. Associated with the dianion are two [PhN(H)NC(H)C₅H₃(Me)N(H)] cations via two hydrogen bonding contacts apiece, unusually involving a true Sn-Cl bond.     

L-谷氨酸与维多利亚绿S作用机理及应用研究

用紫外-可见光度法、共振散射光谱法探讨了在弱酸性介质中,碱性染料维多利亚绿S与酸性氨基酸L-谷氨酸相互作用机理,认为L-谷氨酸分子通过盐键和氢键相互结合成含有亲水性基团的分子链,这条分子链可以将维多利亚绿S的疏水性基团包在里面,使其亲水性基团朝外,并通过盐键和氢键与维多利亚绿S作用形成大的聚合体,其聚合体体积远远大于染料自身聚集体的体积,使溶液颜色变深,分子光谱吸收值增加.并优化了反应体系酸度、反应物用量、反应时间、加试剂顺序等影响反应速度的因素,确定了最佳实验条件,建立了测定L-谷氨酸的方法.线性范围为10mg/L～100 mg/L,相关系数为0.9989.直接测定样品中谷氨酸获得满意结果.     

(H2O)m（HBr）n（m+n≤4）团簇的结构与性质

利用杂化密度泛函方法B3LYP结合6-311++g(2df,2p)基组研究了(H2O)m(HBr)n(m+n≤4)混合团簇的结构及红外光谱.确定了团簇的稳定结构以及键能,发现分子间以红移氢键的形式结合形成混合团簇,且H2O分子个数为3时HBr发生解离.理论模拟了稳定结构的红外光谱,并分析了红外光谱主要吸收峰所对应的振动模式.通过自然键轨道(NBO)分析发现了红移氢键是由质子供体与质子受体间的超共轭作用决定的.     

用核磁共振技术研究氢键的键合方式

为了了解怎样利用核磁共振技术研究氢键的键合方式,本文以联酰胺衍生物为例,分别运用变温核磁共振氢谱和变浓度核磁共振氢谱分析了羰基(CO)与氨基(H—N)之间形成氢键的形式。结果表明,本文举例中联酰胺基团中的CO与H—N以分子间氢键形式存在。     

过氧化氢光化学的理论研究

介绍了研究过氧化氢光解离的重要意义及目前的理论研究现状,分析了存在的问题,并对今后该领域的理论研究进行了展望.     

Reconsideration on hydrogen bond strengthening or cleavage of photoexcited coumarin 102 in aqueous solvent: a DFT/TDDFT study

In this work, the excited-state hydrogen bonding dynamics of photoexcited coumarin 102 in aqueous solvent is reconsidered. The electronically excited states of the hydrogen bonded complexes formed by coumarin 102 (C102) chromophore and the hydrogen donating water solvent have been investigated using the time-dependent density functional theory method. Two intermolecular hydrogen bonds between C102 and water molecules are considered. The previous works (Wells et al., J Phys Chem A 2008, 112, 2511) have proposed that one intermolecular hydrogen bond would be strengthened and the other one would be cleaved upon photoexcitation to the electronically excited states. However, our theoretical calculations have demonstrated that both the two intermolecular hydrogen bonds between C102 solute and H(2)O solvent molecules are significantly strengthened in electronically excited states by comparison with those in ground state. Hence, we have confirmed again that intermolecular hydrogen bonds between C102 chromophore and aqueous solvents are strengthened not cleaved upon electronic excitation, which is in accordance with Zhao's works.     

Study of geometrical parameters in N-H...N type of hydrogen bonds

Geometrical parameters associated with N-H ... N types of hydrogen bonds have been analysed using crystal structure data on nucleic acids, amino acids and related compounds. Histograms depicting the frequency distribution of N-H ... N length (l) and H-N ... N angle (θ) have been drawn and conclusions on the favoured geometry of such bonds have been arrived at. The distribution ofl shows a pronounced maximum in the range between 2.9? and 3.0? with an overall average of 2.98 ?. The θ distribution shows a pronounced maximum for the hydrogen bond angle in the range 0°-10°, with a rapid fall-off in frequency for nonlinear hydrogen bonds. The frequency shows a cos⁶θ dependence as compared to cos²θ dependence term used earlier to predict the angular dependence of hydrogen bond potential energy in proteins and polypeptides.     

Geometric H/D isotope effects and cooperativity of the hydrogen bonds in porphycene.

We investigate the primary, secondary, and vicinal hydrogen/deuterium (H/D) isotope effects on the geometry of the two intramolecular hydrogen bonds in porphycene. Multidimensional potential energy surfaces describing the anharmonic motion in the vicinity of the trans isomer are calculated for the different symmetric (HH/DD) and asymmetric (HD) isotopomers. From the solution of the nuclear Schr?dinger equation the ground-state wavefunction is obtained, which is further used to determine the quantum corrections to the classical equilibrium geometries of the hydrogen bonds and thus the geometric isotope effects. In particular, it is found that the hydrogen bonds are cooperative, that is, both expand simultaneously even in the case of an asymmetric isotopic substitution. The theoretical predictions compare favorably with NMR chemical-shift data.