A New Lattice Inclusion Host Involving Double-stranded Columns of Diol Molecules [1]

Abstract

Crystallization of dialcohol 4 from benzene yields an inclusion compound whose crystal structure [(C₁₃H₂₄O₂)₂·(C₆H₆), P2₁/c, a 7.918(2), b 13.505(2), c 14.924(5) Å, β 109.30(1)°, Z 2, R 0.069] shows that the host molecules are present as parallel doubly-stranded columns. Each column is constructed from one strand of (+)-, and a second of (-)-, enantiomers of 4. These two chirally pure strands are linked through a continuous chain of hydrogen bonding …O—H…O—H…O—H… to complete the column, and the benzene guests occupy interstitial sites between the parallel columns.     

Convenient,Solvent-Free Method for Preparation of [Hydroxy(phosphoryloxy)iodo]arenes

A convenient, solvent-free method for preparation of [hydroxy(phosphoryloxy)iodo]arenes is reported. (Diacetoxyiodo)benzene or other hypervalent iodine reagents and phosphates are simply blended and ground for several minutes in an agate mortar, giving good yields of [hydroxy(phosphoryloxy)iodo]arenes with excellent purities.     

Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Studying the self‐assembly of uracil derivatives has great importance for biochemistry and nanotechnology. For example, modification of the sorbent surfaces by 5‐hydroxy‐6‐methyluracil (HMU ) enhances their adsorption activity. It is assumed that these changes are caused by the self‐assembly of the network‐like supramolecular associates of the uracil derivative on the sorbent surface. In the present work, the relative stabilities of 15 hydrogen‐bonded dimers HMU have been studied by the TPSSh /TZVP density functional theory method and the strengths of the noncovalent interactions analyzed in terms of the reduced density gradient and natural bond orbital approaches. It was found that the symmetric dimer stabilized by two intermolecular hydrogen bonds N1 –H∙∙∙O–C2 (dimer 1‐1) is the most stable. This suggests that the self‐assembly of HMU should occur through the intermediate formation of the dimer 1‐1. The results may be useful for understanding the processes of self‐assembly of the uracil derivatives and the rationalized design of the uracil‐based supramolecular structures with specific properties.     

取代基结构-活性关系对电化学降解取代苯胺的影响

以Na2SO4为支持电解质, 使用Ti/PbO2电极, 研究了带有推电子基(—CH3)和吸电子基(—NO2, —Cl)的邻或对位取代基苯胺类化合物的电催化氧化降解过程. 研究结果表明, 带有取代基苯胺类化合物的氧化降解是在羟基自由基进攻下生成氨基酚类化合物, 然后在电极表面失去电子生成苯醌继续氧化的过程. 带有推电子基团苯胺的电催化降解速度比带有吸电子基团的苯胺降解速度快, 这是因为推电子基团使苯环电子云密度提高, 有利于羟基自由基的进攻; 吸电子基团使苯环电子云密度降低, 不利于羟基自由基的进攻. 由于阴极还原反应的作用, 化学反应活性和电化学反应活性并不完全一致. 氯代苯胺在羟基自由基进攻下—Cl离去, 以Cl-离子形式进入溶液中, 被氧化生成有效氯, 加快降解反应速度. 硝基虽然是强吸电子基, 但是可以转化为对苯二胺, 进一步活化苯环, 其降解速度较快.     

Determination of (E)-10-hydroxy-2-decenoic acid content in pure royal jelly: a comparison between a new CZE method and HPLC

A new CZE method was developed and compared with HPLC for the determination of (E)-10-hydroxy-2-decenoic acid (10-HDA) in royal jelly (RJ) samples of different geographical origin. The results obtained with the CZE method were highly correlated with those of HPLC (p < 0.01). Under optimized conditions, CZE employed minimal amounts of 50 mM tetraborate buffer as BGE, without the addition of organic solvents, EOF or pH modifiers. The CZE method showed a wide linear response range (0.006-0.808 mg 10-HDA/mL), a good sensitivity (LOD and LOQ were 0.002 and 0.004 mg/mL, respectively) and a satisfactory instrumental repeatability with respect to migration time and peak area (RSD% less than 1.0 and 2.0% on migration time for intra- and interday assay, respectively and less than 2.0 and for 4.0% on peak area for intra- and interday assay, respectively). The 10-HDA content in RJ ranged from 0.8 to 3.2 g/100 g of RJ and a significant difference (p < 0.05) was found between the Italian and extra-European average values: 2.5 and 1.6 g/100 g of RJ, respectively, according to the CZE data. The possibility of application of CZE for routine analyses on RJ and RJ based products to verify their authenticity is highlighted here.     

Synthesis and vibrational spectroscopic characterisation of synthetic hydrozincite and smithsonite

Hydrozincite and smithsonite were synthesised by controlling the partial pressure of CO₂. Previous crystallographic studies concluded that the structure of hydrozincite was a simple one. However both Raman and infrared spectroscopy show that this conclusion is questionable. Multiple bands are observed in both the Raman and infrared spectra in the (CO₃)²⁻ antisymmetric stretching and bending regions of hydrozincite showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the hydrozincite structure. Multiple OH stretching vibrations centred in both the Raman and infrared spectra show that the OH units in the hydrozincite structure are non-equivalent. The Raman spectrum of synthetic smithsonite is a simple spectrum characteristic of carbonate with Raman bands observed at 1408, 1092 and 730 cm⁻¹.     

Fast Efficient and General PASE Approach to Medicinally Relevant 4H,5H‐Pyrano‐[4,3‐b]pyran‐5‐one and 4,6‐Dihydro‐5H‐pyrano‐[3,2‐c]pyridine‐5‐one Scaffolds

The general ‘on‐solvent’ PASE approach was found to be medicinally relevant for 4H,5H‐pyrano[4,3‐b]pyran‐5‐one and 4,6‐dihydro‐5H‐pyrano[3,2‐c]pyridine‐5‐one scaffolds. Ammonium acetate‐catalyzed multicomponent reaction of aldehydes and two different C–H acids in the presence of small amounts of EtOH results in fast (3 – 15 min) and efficient formation of scaffolds, promising for many diverse oriented medical applications.     

冠醚化合物的合成(ⅩⅤ)——羟基冠醚的合成及其异构体分离

羟基冠醚作为碱金属阳离子的载体显示出极好的性能,它们还可以转化成双冠醚、套索冠醚和具有高络合能力的碳桥三维空间的大环聚醚等许多衍生物,近年来对羟基冠醚及其衍生物的合成和应用研究十分活跃^[1～4]。     

通过Boltzmann拟合方程定量计算Al(Ⅲ)盐强制水解聚合溶液中的羟基多核铝型体

在表征聚合铝的3种传统测试方法中,只有酸碱电位滴定法至今还没有用于定量计算羟基多核铝。本文依据Al(Ⅲ)盐强制水解聚合过程的电位滴定实验结果,利用铝盐水解聚合电位滴定曲线的三个临界特征点,同时利用Origin软件自备的Boltzmann方程对滴定曲线拟合,可以很方便地计算出铝盐强制水解聚合溶液中聚合铝的含量。模式计算结果与Al-Ferron逐时络合比色法的测试结果线性符合较好,为研究Al(Ⅲ)盐水解聚合过程及其聚合铝形态的定量测定尝试了一种新的方法。     

2－（2＇－羟基苯基）苯并噁唑在高分子介质中的激发态分子内质子转移和光谱

首次报道了２－（２＇－羟基苯基）苯并ｆ唑（ＨＢＯ）分子在若干高分子固体膜中的电子光谱和激发态分子内质子转移（ＥＳＩＰＴ）的特性，并与溶液体系中的相应特性进行了比较，揭示了新的吸收和发射带，并讨论了高分子基质对这些特性的影响和作用机制。