STUDY ON THE CARDANOL-ALDEHYDE CONDENSATION POLYMER CONTAINING BORON-NITROGEN COORDINATE BOND

Cardanol-aldehyde condensation polymer containing boron-nitrogen co-ordinate bond (CFBN) has been synthesized and characterized by IR, XPS, HPLC andDTA-TG. Its properties were also investigated. The results show that the coating filmof CFBN has excellent physico-mechanical properties, good anticorrosive properties andstable at high temperature.     

The standard enthalpies of formation of some dibenzoannelated cycloalkanols

The heats of combustion of trans-9,10-bis-hydroxymethyl-9,10-dihydrophenanthrene, trans-5-hydroxymethyl-5,6-dihydro-7H-dibenzo[a,c]cyclohepten-6-ol, 5-hydroxymethyl-5,6-dihydro-7H-di-benzo[a,c]cycloheptene, 6-hydroxymethyl-5,6-dihydro-7H-dibenzo[a,c]cycloheptene, 5H-dibenzo-[a,d]cyclohepten-5-ol and 5H-10,11-dihydrodibenzo[a,d]cyclohepten-5-ol were measured by means of a Gallenkamp adiabatic bomb calorimeter. Uncertainties in the determination of the heats of combustion ranged between 0.2 and 0.3%. The enthalpies of formation and atomization for the six compounds were derived. The experimental values of the heats of atomization were compared with those calculated using the Allen–Skinner bond energy scheme. Conclusions about energetic contributions which stabilize the structure of the investigated compounds were drawn.     

A Raman technique applicable for the analysis of the working principle of promoters and inhibitors of gas hydrate formation

We report a Raman technique applicable for the in situ analysis of the development of hydrogen bonds in the liquid water‐rich phase just before the onset of gas hydrate formation. Herewith, the phase transition as well as the working principle of hydrate formation inhibitors and promoters can be analyzed. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd.     

基于环己酮氧化脱氢构建碳-碳与碳-杂键

环己酮是一种廉价易得的大宗有机化工产品,被广泛用作有机合成反应的原料和中间体。脱氢芳构化是合成功能化芳烃的有效途径,使用环己酮作为反应底物,经过亲核加成、脱水和催化脱氢可以将非芳香的有机分子转化为芳香化合物。与传统的芳基化反应相比,该策略避免了苛刻的反应条件和含卤化合物的生产,克服了化学和区域选择性难以控制的难题,为功能化芳烃的合成提供了一条温和、环保的途径。本文就近年来以环己酮为原料,进行氧化脱氢、直接构建碳-碳和碳-杂键,及通过碳-杂键的形成合成杂环化合物的研究现状进行介绍。     

咪唑-氰基合铁(Ⅲ)氢键型超分子晶体的合成、相变及介电性质

通过溶剂蒸发法,咪唑、18-冠醚-6和铁氰酸在甲醇溶液内反应,获得了氰基合铁配合物氢键型笼状超分子晶体材料(C3H5N2)3[Fe(CN)6]·2(18-crown-6)·2H2O(1)。通过变温X射线单晶衍射、红外光谱、元素分析、热重分析(TG)、差示扫描量热法(DSC)和变温-介电常数测试等对该晶体进行了结构、热能及电性能分析。该晶体的空间群为P21/c,属于单斜晶系,结构显示氰基合铁阳离子、水分子和咪唑阳离子在空间内通过氢键的相互作用形成以铁原子为顶点的三维笼状结构。温度变化触发笼状结构突变,同时引起[Fe(CN)6]3-框架内超分子发生动态摆动,从而引起晶体结构发生相变,该结构相变温度区间伴随介电物理特性阶梯状变化,从220到280 K,介电常数由38变为43,且可逆。温度在270 K之后的介电突然跃升是水汽影响导致。     

Recognition of Guanine by a Designed Triazine-based Fluorescent Probe through Intermolecular Multiple Hydrogen Bonding

A new fluorescent probe with a long-wavelength emission and multiple hydrogen bond sites for guanine, 3-(4-chloro-6-p-nitrophenoxy-1,3,5-triazinylamino)-7-dimethylamino-2-methylphenazine (CNTDP), was designed and synthesized by using cyanuric chloride as a molecular scaffold, neutral red as a fluorophore and p-nitrophenol as an assistant unit. The recognition behavior of CNTDP for guanine and its spectroscopic properties in different solvents were investigated. It was found that the probe's fluorescence can be selectively quenched by guanine instead of thymine, indicating that fully complementary hydrogen bonding plays a key role in such a recognition process. In addition, the fluorescence quenching mechanism of the probe by guanine and the electronic effects of neutral red, triazine ring and p-nitrophenol moieties on the fluorescence of the whole molecule were also discussed.     

Unsaturated bond existing in tetrafluoroethylene-propylene-vinylidene fluoride terpolymer

Infrared and nuclear magnetic resonance (NMR) spectroscopies have been applied for quantitative comparison on unsaturated bonds in tetrafluoroethylene (TFE)-propylene (P)-vinylidene fluoride (VdF) terpolymers. These spectroscopies have led to consistent results while they are based on completely different principles. It is shown that the absolute concentration can be evaluated from NMR measurements. The behavior of unsaturation has been discussed in terms of after-treatment such as wet and dry treatments. The result obtained here can give the important information to improve the performance of fluoroelastomer based on TFE-P-VdF terpolymers.     

DFT study on the intermolecular interactions between Aun (n = 2–4) and thymine

Density functional B3LYP method with 6-31++G** basis set is applied to optimize the geometries of the luteolin, water and luteolin–(H₂O)_n complexes. The vibrational frequencies are also studied at the same level to analyze these complexes. We obtained four steady luteolin–H₂O, nine steady luteolin–(H₂O)₂ and ten steady luteolin–(H₂O)₃, respectively. Theories of atoms in molecules (AIM) and natural bond orbital (NBO) are used to investigate the hydrogen bonds involved in all the systems. The interaction energies of all the complexes corrected by basis set superposition error, are within −13.7 to −82.5 kJ/mol. The strong hydrogen bonding mainly contribute to the interaction energies, Natural bond orbital analysis is performed to reveal the origin of the interaction. All calculations also indicate that there are strong hydrogen bonding interactions in luteolin–(H₂O)_n complexes. The OH stretching modes of complexes are red-shifted relative to those of the monomer.     

肾上腺素与二甲亚砜氢键作用的理论研究

The hydrogen bond is one of the most important intermolecular interactions playing an important role in intermolecular recognition processes essential to most biological systems. Adrenaline is an important catecholamine neurotransmitter in the mammalian central nervous system. Dimethyl sulphoxide can carry with it drugs across membranes. The geometries of adrenaline and six stable 1 : 1 complexes formed between adrenaline and dimethyl sulphoxide were optimized by Berny method at PM3 level and thus were optimized by density functional theory（B3LYP method）at the 6-31G,6-31G*,and 6-31+G* level respectively to obtain accurate structures. Single-point energies of all optimized molecular geometries were calculated to discuss the energies and structural parameters between reactants and products. All the binding energies have been corrected by the zero point vibrational energies（ZPVE）at varied basis set levels from 6-31G to 6-31 + G*. The results indicated that stronger hydrogen-bonded complexes were formed by molecular interaction between adrenaline and dimethyl sulphoxide. The calculation results can be better used to explain some experimental phenomena.     

紫外-可见光谱法研究二茂铁衍生物与血红素的相互作用

采用紫外-可见光谱法(UV-Vis)研究三种二茂铁衍生物[Fc(COOH)₂(λ_max=286 nm), Fc(OBt)₂(λ_max=305 nm), Fc(Cys)(λ_max=289 nm)]与血红素(heme, λ_max=386 nm)的相互作用。实验结果表明：当固定heme浓度时,heme的吸光度随着Fc(COOH)₂和Fc(Cys)浓度的增加而增大,而heme的吸光度随着Fc(OBt)₂的浓度的增加几乎没有增大;当分别固定Fc(COOH)₂, Fc(Cys)和Fc(OBt)₂的浓度时,Fc(COOH)₂和Fc(Cys)的吸光度随着heme浓度的增加而增大,而Fc(OBt)₂的吸光度随着heme浓度的增加没有变化,说明Fc(COOH)₂和Fc(Cys)与heme存在分子间的相互作用,主要是由于Fc(COOH)₂和 Fc(Cys)与heme能形成氢键,分子链增长,吸收的能量增加,导致吸光度增大;而Fc(OBt)₂与heme没有分子间的相互作用,是由于Fc(OBt)₂没有自由的氢,不能与heme形成分子间的氢键。同时考察了三种二茂铁衍生物与heme 的吸光度随时间的变化,Fc(COOH)₂和 Fc(Cys)与heme的吸光度随着时间的增加而减少,而Fc(OBt)₂与heme的吸光度随时间的变化几乎没有变化。Fc(COOH)₂与Fc(Cys)和heme的反应时间为0.5,18和48 h,当固定Fc(COOH)₂浓度时,在λ_max=384 nm处的吸光度由2.64分别变为2.53和2.51;当固定heme的浓度时,在λ_max=384 nm处的吸光度由1.76分别变为1.72和1.68;当固定Fc(Cys)浓度时,在λ_max=397 nm处的吸光度由2.74分别变为2.63和2.55;当固定heme的浓度时,在λ_max=397 nm处的吸光度由1.82分别变为1.58和1.49。