非极性有机溶剂对分子内氢键弱化程度的单分子力谱定量研究

利用单分子力谱技术, 以3种不同醇解度的聚乙烯醇(PVA)为模型体系, 定量研究了非极性有机溶剂对分子内氢键强度的影响. 3种PVA样品在非极性有机溶剂中的分子内氢键强度均约为其在真空中强度的48%. 结果表明, 非极性有机溶剂对分子内氢键的弱化作用十分显著, 可削弱其约50%的本征氢键强度. 本文研究结果提示人们需重新审视液相环境对高分子单链弹性和非共价相互作用的影响.     

新化合物阴行草醇的NMR研究

我们从植物阴行草中提取分离到一种新的化合物(1),并将其命名为阴行草醇。利用核磁共振技术辅以其它波谱数据准确无误地确定了该化合物的立体结构,指定了~1H和~(13)C的所有谱线。     

对称双吡咯甲烷的合成与分子内氢键的研究

５－甲基吡咯－２－羧酸酯在磺酰氢，溴或四乙酸铅作用下，生成相应的在５－甲基上含取代基的产物，后者不经分离不便可自缩合得标题化合物，核磁共振氢谱研究和分子构象木匠，当３，３位的取代基为甲酸（酯）基或乙酸（酯）基时，可形成３，３位酯基与另一吡咯环上的氮氢之间的分子内氢键，而３，３位是其它取代基，如乙酰基，丙酸（酯）基，丁酸（酯）基时不能形成类似的分子内氢键。     

基于LFHB 理论模型关联和预测醇+惰性溶剂的1H NMR 化学位移

运用含氢键缔合的格子流体状态方程(LFHB), 仅用一个参数关联了一元醇-惰性溶剂共17个体系29套1H NMR化学位移数据. 并且用关联参数成功预测了不同温度下丁醇+环己烷的化学位移. 所得结果与化学缔合理论的结果进行了比较. 对于某些体系在稀浓度范围LFHB的计算氢键缔合度要低于化学缔合理论的结果. 并且分析了LFHB理论中的物理参数和化学参数对于缔合度计算的不同影响.     

表面活性剂在非极性有机溶剂中的自组装

本文总结了表面活性剂在非极性有机溶剂中复杂反相聚集的研究进展。首先突破了表面活性剂在非极性溶剂(油)中溶解的难题,通过设计合成大头基的新表面活性剂,或引入合适添加剂使之与表面活性剂头基相互作用,由此增大头基有效尺寸,这些均能有效促进表面活性剂形成核-壳完整的聚集体,进而带动表面活性剂分散(溶解)在非极性溶剂中。基于聚集体带动溶解的思路,建立了制备表面活性剂/油均相溶液的直接溶解方法,讨论了制备方法的关键要素,它比文献常用的甲醇预溶解法方便且有效。列举了若干典型的表面活性剂/环己烷均相体系,以此评述了聚集体带动溶解的方法,也展现了丰富多样的反相聚集形貌,讨论了表面活性剂头基尺寸对聚集结构的影响。     

固体NMR研究PAA/PEO共混物中氢键相互作用与结构演化

分子间相互作用是决定材料结构和性能的关键因素之一,而如何在分子水上实现对复杂相互作用分子的检测仍然是一个挑战性课题。本工作首先在不同p H值条下以聚丙烯酸/聚环氧乙烷(PAA/PEO)的混合水溶液制备了系列的固体薄膜,然后采用多种基于连续相调制多脉冲技术的一维和二维~1H多脉冲去耦(CRAMPS)固体NMR新技术,并结合高分辨~(13)C交叉极化魔角旋转(CPMAS)、~(23)Na多量子(MQ)等多核固体NMR实验,对PAA/PEO聚合物共混物的微观结构和动力学进行了原位和系统的研究。通过不同类型的~1H高分辨CRAMPS实验检测到共混物中包含多种不同类型质子:通过氢键相互作用形成二聚体的COOH基团、自由COOH基团、与水结合的COOH基团和主链基团。随着p H值的升高,除主链质子外,大部分其它区域的信号都明显降低,这是由于PAA与PEO以及水的氢键作用减弱所致。这些CRAMPS NMR技术也被用来阐明不同p H值制备的样品中不同基团的分子运动性。此外,二维~1H-~1H自旋交换NMR实验提供了关于聚合物PAA与PEO大分子链间、以及水与聚合物的相互作用。~1H自旋扩散实验表明,在这些共混物中明显存在相微观相分离的结构,并且测定的分散相区尺寸约为17 nm。~(23)Na MQMAS实验揭示了在共混物中存在两种类型~(23)Na位,一种是自由的钠离子,另一种是与大分子相互作用的Na离子。特别是通过~1H-检测的~(23)Na-~1H CPMAS实验揭示了Na~+离子的位置远离PEO而与PAA临近。上述这些SSNMR实验结果在分子水平上提供了氢键相互作用对PAA/PEO共混物微观结构和动力学影响的详细信息,可以获得不同p H值对PAA与PEO的氢键作用、相容性、微观结构、水-聚合物相互作用和不同组分分子运动性的影响。在上述核磁共振研究的基础上,我们提出了一种新的PAA/PEO共混物的结构模型,该模型首次成功地揭示了不同的p H值对PAA/PEO共混物中微观结构和动力学的影响。本工作清楚地表明,固态核磁共振是在分子水平上研究具有复杂相互作用的多相聚合物材料的有力工具。本文的研究工作对于探索检测聚合物弱相互作用的新方法和发展基于氢键相互作用的聚合物新材料的开发具有重要意义。     

关于键的极性的两个问题

讨论了氢的电负性和键的极性方向问题。通过分析某些氢化物的点电荷分布与电负性关系,得出氢的电负性为1.60左右。键的极性方向取决于原子间是否有反馈键存在.原子间反馈键的存在,有可能导致键极性的反转.     

红外光谱定量法研究醇在正烷烃中的氢键缔合

测定了正十六醇-正己烷烃溶液(0.01～0.20 mol·L~(-1))在不同浓度下的红外光谱, 并用付里叶自去卷积-曲线拟合法(Fourier Self-decon-volution and curve-fitting)对谱图进行了解析。结果将醇羟基峰归属为: (1)单体羟基峰(3646.6 m~(-1))、(2)链状缔合体末端游离羟基峰(3633.8 cm~(-1))、(3)环状二聚体羟基峰(3535.1 cm~(-1))、(4)链式二聚体缔合羟基峰(3474c m~(-1))和(5)链状多聚体组合羟基峰(3337 cm~(-1))五种类型, 并得出它们随浓度的分布规律。     

快速预测分子间氢键强度的新方法

提出了一种快速预测分子间氢键强度的新方法。将其应用于29个分子间氢键体系中,计算单体间的氢键相互作用势能曲线,并与MP2方法得到的结果进行了比较。结果表明本文方法能够准确地预测出氢键键长和氢键能量,其精度可以与包含了BSSE校正的MP2结果相媲美,本文方法更简单,更快捷。本文方法可用于快速预测多肽、蛋白质体系中的氢键强度,应用前景广阔。     

几种分子间氢键络合物体系的振动光谱研究

本文对X·C_2H_2[X=(CH_3)_3N、NH_3、(CH_3)_2O和CH_3(N)及(NH_3)_2·C_2H_2]五种分子间氢键络合物体系进行了振动光谱研究。用MNDO方法对这五种体系进行了几何构型优化,获得了直角坐标力常数;通过力常数变换将其转换成内坐标表达的力常数,用GF矩阵方法作全振动分析,计算了上述体系的振动光谱频率,并对频率作了理论归属,从而得到了分子间氢键的伸缩振动力常数和振动频率。     

Measuring the Relative Hydrogen‐Bonding Strengths of Alcohols in Aprotic Organic Solvents

Voltammetric experiments with 9,10‐anthraquinone and 1,4‐benzoquinone performed under controlled moisture conditions indicate that the hydrogen‐bond strengths of alcohols in aprotic organic solvents can be differentiated by the electrochemical parameter ΔE_p^red=|E_p^red(1)?E_p^red(2)|, which is the potential separation between the two one‐electron reduction processes. This electrochemical parameter is inversely related to the strength of the interactions and can be used to differentiate between primary, secondary, tertiary alcohols, and even diols, as it is sensitive to both their steric and electronic properties. The results are highly reproducible across two solvents with substantially different hydrogen‐bonding properties (CH₃CN and CH₂Cl₂) and are supported by density functional theory calculations. This indicates that the numerous solvent–alcohol interactions are less significant than the quinone–alcohol hydrogen‐bonding interactions. The utility of ΔE_p^red was illustrated by comparisons between 1) 3,3,3‐trifluoro‐n‐propanol and 1,3‐difluoroisopropanol and 2) ethylene glycol and 2,2,2‐trifluoroethanol.     

Thermochemistry of Benzene Solution in Alcohols, Aprotic Solvents, and Mixtures of Aprotic Solvents with Methanol

The standard enthalpies of solution of benzene at 25°C in alcohols (methanol, 1-propanol, 1-pentanol, 1-decanol), aprotic solvents (1,4-dioxane, acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, propylene carbonate), and mixtures of methanol with these aprotic solvents were determined. Multiple regression analysis revealed the role of specific and nonspecific interactions in solvation of benzene in these solvents.     

FTIR Study of Hydrogen Bonding Between Acrylic Esters and Alcohols

Hydrogen bonding between acrylic esters and alcohols has been studied in carbon tetrachloride by using the FTIR spectroscopic method. Utilizing the Nash method, the formation constant of the 1:1 complexes has been calculated. The formation constant and Gibbs energy change values vary with alcohol and ester chain length, which suggests that the proton donating ability of alcohols is in the order: 1-propanol < 1-butanol < 1-pentanol, and the accepting ability of acrylic esters is in the order: methyl methacrylate < ethyl methacrylate < butyl methacrylate.     

N-甲基甲酰胺与醇的氢键相互作用

The hydrogen bonding interactions between N-methylformamide and primary, secondary, and tertiary alcohols have been studied using the FT1R spectroscopic method. The most likely association complex between alcohol and N-methylformamide is the 1:1 stoichiometric complex formed between the hydroxyl group of alcohol and the carbonyl group of N-methylformamide. The formation constant of the 1:1 complexes has been calculated using the Nash method. It appears that the primary alcohols have larger formation constant compared with the secondary and tertiary alcohols. The results showed that the proton-donating ability of the alcohols decreased in the order: primary＞secondary＞tertiary, and that the association constant increased with the increase in carbon chain of the alkyl group of alcohols.     

N-甲基甲酰胺与醇的氢键相互作用

Amides are used as synthetic reagents and as starting mate- rials for the preparation of insecticides and pharmaceuticals products[1]. Alcohols are industrially and scientifically important organic compounds, and their physical and chemical properties are…     

Hydrogen Bonding in Aprotic Solvents,a New Strategy for Gelation of Bioinspired Catecholic Copolymers with N‐Isopropylamide

Copolymers of N‐isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self‐healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV–vis and ¹H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self‐healing properties are tested rheologically. The produced reversible organogel can self‐encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual‐targeted and controlled drug delivery and release—by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.

     

几种二醇与非质子溶剂相互作用的红外光谱研究

测定了1，2-乙二醇、1，2-丙二醇、1，4-丁二醇和1，6-己二醇在CCl4中分别与十几种非质子溶剂相互作用的红外光谱，通过考察频率位移的变化，定量地研究了二醇分子内氢键与分子间氢键的协同效应．在四氯化碳介质中，乙二醇、1，2-丙二醇和1，4-丁二醇体系中存在明显的氢键协同效应。利用红外光谱数据，估算了常温下二醇分子内缔体与非质子溶剂的交叉缔合常数，其数值大于一元正链醇与相应溶剂的交叉缔合常数．     

Nuclear Magnetic Resonance Study on Hydrogen Bonding of Butyl Alcohols

Nuclear magnetic resonance of hydroxyl proton of four butyl alcohols have been measured as a function of alcohol concentration in carbon tetrachloride solvent. Assuming equilibria among monomer, open-dimer and cyclic dimer for alcohol association, the chemical shifts of the hydroxyl proton both at the bonded state and at the non-bonded state and also the equilibrium constants were determined from the observation at a moderate dilution. The results were tabulated in Table 1 and shown in Fig. 1.     

Effect of Hydrogen Bonding on Cellulose Solubility in Aqueous and Nonaqueous Solvents

Interrelation between the hydrogen bonding energy in cellulose, its solubility in aqueous and nonaqueous solvents is examined. Factors controlling the solubility and selection criteria for nonaqueous solvents for cellulose are analyzed.     

Enantioselective Discrimination of Alcohols by Hydrogen Bonding: A SERS Study

Efficient and generic enantioselective discrimination of various chiral alcohols is achieved by using surface‐enhanced Raman scattering (SERS) spectroscopy through charge–transfer (CT) contributions. The relative intensities of the peaks in the SERS spectra of a chiral selector are strongly dependent on the chirality of its surroundings. This highly distinct spectral discrepancy may be due to the tendency of chiral isomers to form intermolecular hydrogen‐bonding complexes with the chiral selector in different molecular orientations, resulting in different CT states and SERS intensities of the adsorbates in the system. This study opens a new avenue leading to the development of novel enantiosensing strategies. A particular advantage of this approach is that it is label‐free and does not employ any chiral reagents, including chiral light.