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 H-1 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.

Effect of lanthanum ions on tRNA(Phe) structure: Imino proton NMR spectroscopy

The effect of lanthanum ions on the structural and conformational change of yeast tRNA(Phe) was studied by H-1 NMR. The results suggest that the tertiary base pair (G-15)(C-48), which was located in the terminal in the augmented dihydrouridine helix (D-helix), was markedly affected by adding La3+ and shifted 0.33 downfield. Based pair (U-8)(A-14), which is associated with a tertiary interaction, links the base of the acceptor stem to the D-stem and anchors the elbow of the L structure, shifted 0.20 upfield. Another imino proton that may be affected by La3+ in tRNA(Phe) is the tertiary base pair (G-19)(C-56). The assignment of this resonance is tentative since it is located in the region of highly overlapping resonances between 12.6 and 12.2. This base pair helps to anchor the D-loop to the T psi C loop.

A novel electrochemical method for simultaneously measuring diffusion coefficient and ion transference number

This paper introduces a new method to estimate the diffusion coefficient and transference number of a salt or an electroactive ion in a solution with little or no supporting electrolyte. The above two parameters can be obtained from a single potential step experiment without previous knowledge of either one. It would appear that the method could also be used in the study of ion transport in a high viscosity solvent or a solid electrolyte. (C) 1998 Elsevier Science S.A.

A study on the diffusion of quinhydrone in polymer electrolyte

The diffusion coefficients (D) of quinhydrone were estimated in polymer electrolytes by using non-steady-state chronoamperometry and steady-state current voltammetry. The D values have been estimated in polyethylene glycol (PEG) containing different concentrations, and cations of supporting electrolytes, and in different solvents over a range of temperatures. The dependencies of electroactive probe diffusion coefficients on temperature, supporting electrolyte concentration and polymer chain length are discussed. The results show that D increases with increasing temperature and decreasing concentration of supporting electrolyte. The diffusion coefficient depends strongly on the length of polymer chain and decreases sharply with increasing polymer chain length. The contribution of electron self-exchange has been explored and it seems to be negligible here. (C) 1998 Elsevier Science S.A.

Studies of ferrocene derivative diffusion and heterogeneous kinetics in polymer electrolyte by using microelectrode voltammetry

The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.

Compatibilization effect of graft copolymer on immiscible polymer blends: 1. LLDPE/SBS/LLDPE-g-PS systems

compatibilizing effect of graft copolymer, linear low density polyethylene-g-polystyrene (LLDPE-g-PS), on immiscible blends of LLDPE with styrene-butadiene-styrene triblock copolymer (SBS) has been investigated by means of C-13 CPMAS n.m.r. and d.s.c. techniques. The results indicate that LLDPE-g-PS is an effective compatibilizer for LLDPE/SBS blends. It was found that LLDPE-g-PS chains connect two immiscible components, LLDPE and SBS, through solubilization of chemically identical segments of LLDPE-g-PS into the amorphous region of LLDPE acid PS block domain of SBS, respectively. It was also found that LLDPE-g-PS chains connect the crystalline region of LLDPE by isomorphism, with serious effects on the supermolecular structure of LLDPE. The effect of LLDPE-g-PS on the supermolecular structure of LLDPE in the LLDPE/SBS blends obviously depends on the composition of the blends, but has little dependence on the PS grafting yields of LLDPE-g-PS. (C) 1998 Elsevier Science Ltd. All rights reserved.

High resolution solid-state NMR and DSC study of poly(ethylene glycol) silicate hybrid materials via sol-gel process

Hybrid materials incorporating poly(ethylene glycol) (PEG) with tetraethoxysilane (TEOS) via a sol-gel process were studied for a wide range of compositions of PEG by DSC and high resolution solid-state C-13- and Si-29-NMR spectroscopy. The results indicate that the microstructure of the hybrid materials and the crystallization behavior of PEG in hybrids strongly depend on the relative content of PEG. With an increasing content of PEG, the microstructure of hybrid materials changes a lot, from intimate mixing to macrophase separation. It is found that the glass transition temperatures (T-g) (around 373 K) of PEG homogeneously embedded in a silica network are much higher than that (about 223 K) of pure PEG and also much higher in melting temperatures T-m (around 323 K) than PEG crystallites in heterogeneous hybrids. Meanwhile, the lower the PEG content, the more perfect the silica network, and the higher the T-g of PEG embedded in hybrids. An extended-chain structure of PEG was supposed to be responsible for the unusually high T-g of PEG. Homogeneous PEG-TEOS hybrids on a molecular level can be obtained provided that the PEG. content in the hybrids is less than 30% by weight. (C) 1998 John Wiley & Sons, Inc.

镧离子对tRNA~(Phe)结构的影响:亚胺质子NMR谱

采用1HNMR方法研究了镧离子对酵母tRNAPhe分子结构和构象变化的影响 .结果表明位于扩大二氢尿嘧啶螺旋 (D 螺旋 )的端梢三级碱基对 (G_15) (C_4 8)明显受加入La3+ 的影响 ,向低场位移 0 33;与三级相互作用相关 ,连接D 茎和接受茎起固定L结构转折的 (U_8) (A_14)碱基对向高场位移 0 2 0 ;另一可能受La3+影响的亚胺质子碱基对为 (G_19) (C_56 ) ,由于该碱基对位于高度叠加的 12 6和 12 2之间 ,其归属仅供参考 ,该碱基对有助于D 环对TΨC环的连接.

铕离子对tRNA~(Phe)结构影响的NMR研究

采用ＮＭＲ波谱方法研究了溶液中铕离子对酵母苯丙氨酸转移核糖核酸（ｐｈｅｎｙｌａｌａ－ｎｉｎｅｔｒａｎｓｆｅｒｒｉｂｏｎｕｃｌｅｉｃａｃｉｄ，简称ｔＲＮＡＰｈｅ）结构和构象变化的影响．Ｅｕ３＋离子对ｔＲＮＡＰｈｅ亚胺质子范围的１ＨＮＭＲ谱具有特殊的影响，酵母ｔＲＮＡＰｈｅ亚胺质子谱作为Ｅｕ３＋浓度函数的研究表明位于扩大二氢尿嘧啶螺旋（Ｄ－螺旋）的端梢三级碱基对Ｇ１５·Ｃ４８明显地受加入Ｅｕ３＋的影响（向低场位移０．８５）；堆积在Ｇ１５·Ｃ４８上的Ｕ８·Ａ１４碱基对在存有１～２个Ｍｇ２＋离子下亦受加入Ｅｕ３＋的影响．酵母ｔＲＮＡＰｈｅ中可能受到Ｅｕ３＋影响的另一亚胺质子为Ｇ１９·Ｃ５６三级碱基对，由于Ｇ１９·Ｃ５６的亚胺质子共振位于高度叠加的１２．６与１２．２之间，其归属仅供参考．该碱基对有助于Ｄ－环对ＴΨＣ环的联接．配位Ｅｕ３＋引起ｔＲＮＡ分子构象的变化并且导致一些谱峰向高场或低场位移.

NMR方法表征联萘衍生物 I2,2′-二(对氨苯氧基)-1,1′-联萘

用１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ和二维核磁共振技术研究了２，２′－二（对氨苯氧基）－１，１′－联萘的结构，并通过１Ｈ－１Ｈ质子同核相关及１３Ｃ－１Ｈ异核相关谱提供的信息确定了其１Ｈ谱和１３Ｃ谱中各谱峰的归属，为聚合物的表征提供了依据。

NMR探测苯丙氨酸转移核糖核酸中镧离子的键合

用ＮＭＲ谱研究了溶液中镧离子对苯丙氨酸转移核糖核酸（简称ｔＲＮＡＰｈｅ）结构和构象变化的影响。研究表明Ｌａ３＋对ｔＲＮＡＰｈｅ亚胺质子范围的１ＨＮＭＲ谱具有特殊的影响，位于扩大二氢尿嘧啶螺旋（Ｄ螺旋）的端梢三级碱基对Ｇ１５·Ｃ４８明显受Ｌａ３＋的影响（向低场位移０３５）；堆积在Ｇ１５·Ｇ４８上的Ｕ８·Ａ１４碱基对在存有１～２个Ｍｇ２＋时亦受Ｌａ３＋的影响。酵母ｔＲＮＡＰｈｅ中可能受到Ｌａ３＋影响的另一亚胺质子为Ｇ１９·Ｃ５６三级碱基对，由于Ｇ１９·Ｃ５６的亚胺质子共振位于高度叠加的１２６～１２２之间。该碱基对有助于Ｄ环对ＴΨＣ环的联接。Ｌａ３＋引起ｔＲＮＡ分子构象的变化并且导致一些谱峰向高场或低场位移。

长期服用硝酸镧对大鼠机体影响的~1H NMR研究

随着稀土应用的日益扩大,稀土将有可能越来越多地进入生态环境和生物体内,但其作用机理及对生物体正常生理功能的影响还不清楚,因此研究稀土的生物效应是一个迫切需要解决的重要基础课题。本文采用现代核磁共振技术,通过分析灌胃给药0．2,2．0,10,20mg/kg 剂量的 La(NO_3)_3六个月后大鼠血清中某些内源性化合物的变化研究了稀土化合物在动物体内的作用情况及长期毒性,同时对20mg/kg 剂量组三个月后大鼠尿液的 H NMR 谱图进行了分析,并通过血液中一些重要生化指标的测定对结果进行了验证。图1(a)为正常大鼠血清的 H NMR 谱,图1(b)为给药(10mg La(NO_3)_3/kg)六个月后大鼠血清的 H NMR 谱图。从图中一些内源性化合物的物种和浓度的变化可以看出,稀土在体内长期作用后,可能导致动物肝脏和肾脏物特定部位受到了一定程度的损害,并使体内酶代谢发生紊乱,且随着稀土量的增多,损害程度也越严重。另外通过20mg La(NO_3)_3/kg 组三个月后大鼠尿液的 H NMR 分析及血液中生化指标的检测结果也可得出动物机体受损的信息。本方法也可应用于非先天疾病的异常代谢的临床检测及其它药...

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .2. Effect of the ionic size of supporting electrolytes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene in MPEG/salt electrolytes were determined by using steady-state voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equation. The effect of the ionic size of six supporting electrolytes on diffusion and electron transfer dynamics of ferrocene was discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .3. Effect of the polymer solvents

The diffusion coefficients(D-app) and the heterogeneous electron transfer rate constants(k(s)) for ferrocene in several polymer solvents were determined by using steady-state voltammetry. The temperature dependence of the two parameters indicates Arrhenius behavior, The polymer solvent effects on diffusion and electron transfer dynamics of ferrocene were discussed.

Physical diffusion and electron-transfer dynamics of electroactive solutes in polymer electrolytes .1. Effect of the nature of electroactive solutes

The diffusion coefficients(D-app) and the heterogeneous electron-transfer rate constants(k(s)) for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steady-state voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on D-app, k(s), and the half-wave potentials(E-1/2) are discussed.