NMR titration and molecular model MOPAC calculation of protonation processes of two MRI ligands

The protonation process of two DTPA bis(amide) derivatives,DTPA-BDMA and DTPA-BDEA,was studied by using 1H NMR titration and MOPAC calculation.Their protonation process was proposed in the order of the central amine,the terminal amines,the central carboxyl,the terminal carboxyl,the other terminal carboxyl and central amine.During the protonation of the terminal amine,there existed a large fraction of proton transfer from the central amine to the other terminal amine.     

等离子体聚合膜的电学性质研究——Ⅱ.腈类单体结构的影响

等离子体聚合膜多为具有高电阻的绝缘体。但是,近年来的研究结果表明,选择合适的单体及采取一些措施,可使等离子体聚合膜从绝缘体至半导体乃至导体的宽范围变化。本文将一些具有不同化学结构的腈类单体进行了等离子体聚合,研究了单体化学结构对所得聚合膜结构及电学性质的影响。聚合方法等同前报。     

Study on the Methyl Migration of 10-Methoxy-5,10-dihydrophenophosphazine 10-oxide

The title compound (1) was treated with NaH at room temperature in anhydrous DMF to give a sodium salt (containing nitrogen anion)which could shift the methyl group from oxygen to nitrogen atom to form N-methyl phosphinic acid as the reaction temperature was increased to 120 ℃.Three nitro derivatives containing 5,10-dihydrophenophosphazine ring system were prepared for the investigation on the above reaction mechanism which would be possible regarded as a special inter-molecular substitution.viz.,the nucleophilic nitrogen anion from one molecule of 1 attacked the cabon atom of the O-methyl of another 1.In addition,the chemical structures of seven compounds containing 5,10-dihydrophenophosphazine ring system involved in the experiment were confirmed by IR,^1 H NMR,^31P NMR and mass spectroscopy.     

大孔吸附树脂提取穿心莲总内酯的研究

研究了大孔吸附树脂提取和纯化穿心莲总内酯的方法，采用HPLC法测定了穿心莲内酯的含量；考查了乙醇浓度对浸提效果的影响，并经动态吸附筛选了4种树脂；最后确定以ADS－7作为提取分离穿心莲总内酯的树脂，此树脂吸附量较高，脱附容量且能与杂质分离，有利于得到质量较好的穿心莲总内酯产品。     

Study on the inclusion compound of β-cyclodextrin with (η5-cyclopentadienyl)tricarbonylmanganese(0)

The supramolecular inclusion compound of β-cyclodextrin (β-CD, host) with (η5-cyclopentadienyl)tricarbonylmanganese [MnCp(CO)3, guest] was obtained in a crystalline state. The host-guest compound is thermally stable and do not liberate the guest on heating at 100$ in vacuum. It was characteried by elemental analysis,1H NMR, differential scanning thermal (DSC) analysis and TLC. Continueous variation plot by NMR method shows that β-CD formed 1:1 inclusion compound with MnCp(CO)3. On the basis of 1H NMR spectra and the model building with Corey Pauling Koltum (CPK) models, the most probable inclusion mode is proposed.     

Mg_(32)(Al,Zn)_(49)合金准晶结构及向晶体转化过程的研究

我们通过用电子衍射和高分辨电子显微术对Mg_(32)(Al,Z_n)_(49)合金准晶I相及相应晶体R相结构的研究对比,提出了此合金准晶I相的双三十面体原子团基本结构单元的随机准垛结构模型。进一步,用此随机准垛结构模型分析了合金处于准晶态与晶态之间过渡状态的内部结构,研究了准晶I相到晶体R相的转化过程。最后,对准晶态的结构特性进行了探讨。     

COPU／PMMA AB交联聚合物的性能

AB交联聚合物(ABCP)是由聚合物A链与化学组成不同的聚合物B链交联构成。它的网络结构不同于IPN。IPN是由两个独立的网络构成,而在ABCP中仅存在一个聚合物网络。目前人们对它远不及对IPN了解得多。 本文选用蓖麻油为原料,与甲基丙烯酸甲酯共聚,合成了一种ABCP。研究了它的力学性能,转变与松弛,相容性及形态结构与组成及交联密度的关系。     

Sterols from the Fungus Catathelasma imperiale

Eight ergostane-type sterols and three their derivatives (one mono-linoleate and two mono-glucosides) were isolated from the ethyl acetate soluble fraction of the fungus Catathelasma imperi.a/e. Two of them are novel compounds, namely 22E,24R-er-gosta-7,22-diene-3β ,5α-diol-6β-linoleate (1) and 22E, 24R-er-gosta-7,22-diene-3β, 5β, 6α-triol (5) with an uncommon c/s-fused A/B ring. Structures of these compounds were demon-strated on the basis of their chemical evidences and spectroscop-ic methods, especially 2D NMR techniques.     

Co-existing Intermolecular Halogen Bonding and Hydrogen Bonding in the Compound Trans-5,10-bis（1-bromodifluoro-acetyl-1-ethoxycarbonyl-methylidene）thianthrene

Trans-5,10-bis(1-bromodifluoroacetyl-l-ethoxycarbonyl-methylidene)thianthrene (1b) was prepared from the reaction of BrCF2COC(N2)CO2Et with thianthrene. X-ray single crystal diffraction analysis showed that the intermolecular halogen bonding and hydrogen bonding coexisted in this compound. The bromine atom acted as an electron acceptor in the halogen bond and an electron donor in the hydrogen bond. It is the first example that the bromine atom acted as such a dual role in the hydrogen and halogen bond.     

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologeu group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)9V2+(CH2)8SH,where V2+ is N,N'-diaIkylbipyridinium (i.e.a viologen group),onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated by Ac voltammetry and square wave voltam-metry,which have the high sensitivity against background charging.The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are-360 mV and-750 mV (vs.Ag/AgCl) in 0.1mol/L phosphate buffer solutions (pH 6.96) respectively,and the standard electron transfer rate constant is 9.0s-1 The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.