嵌段共聚物溶致液晶相中水的2H-NMR动力学分析

采用D₂O 的²H-NMR线型和弛豫分析了PEO-PPO-PEO/D₂O/对二甲苯体系的层状和六角液晶相的动力学行为. 通过实验测得了两个不同体系的自旋 晶格弛豫时间T₁、自旋-自旋弛豫时间T₂和²H-NMR 谱. ²H-NMR 谱均为具有四极劈裂的粉末谱线型，且在谱图的中心，β_LD=54.7°时存在一个倒峰. 倒峰的出现直接表明引起体系中弛豫的主要动力学过程处于极窄化区域. 采用NMR弛豫模型，通过调节动力学参数，使理论模拟的²H-NMR谱、弛豫时间、倒峰的大小与实验的对应量相吻合，求得了体系的动力学参数.     

水溶液中组氨酸的14N NMR研究

用NMK法测得不同pH值条件下组氨酸的¹⁴N谱,用反转恢复法测得¹⁴N的T1值。根据¹⁴N谱及T₁值快速且准确地证实了组氨酸在不同电离情况下的结构。     

丙烯腈γ辐射聚合的NMR研究

用¹H NMR、¹³C NMR谱、自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）研究了丙烯腈在⁶⁰Co γ射线辐射聚合后的大分子结构变化与大分子链的运动. 结果表明随着辐射剂量增大，在单体形成聚合物的过程中，聚合物主链上出现了少量的-OH基团，继续增大辐射剂量， -OH部分被氧化. 对聚合物溶液的变温氢谱的研究表明，溶剂中的残余水与上述-OH形成氢键，且随着温度升高氢键被破坏，同时H₂O与-OH之间还存在着质子交换. 利用¹³C NMR谱对丙烯腈辐射聚合的产物进行了序列结构分析. 对T₁和T₂的研究表明，辐射剂量的增大并未影响到聚丙烯腈的链运动，证明了在丙烯腈的辐射聚合过程交联反应未发生.     

电池正极材料中Li+运动特性的7Li NMR研究

利用变温⁷LiNMR实验对Li-电池正极材料LiMn₂O₄和LiCoO₂中Li⁺的运动特性进行了研究,结果表明,随实验温度的提高,LiMn₂O₄的⁷LiNMR谱线窄化,表明其中Li⁺迁移能力增加,而LiCoO₂的谱线无变化.此外随温度提高,LiMn₂O₄的⁷Li的T₁变短,而LiCoO₂的T₁变长,产生这种不同变化趋势的原因在于LiMn₂O₄和LiCoO₂晶相结构的差异造成其中Li⁺迁移能力的差别,它们各自的相关时间τ_c使⁷Li核的T₁分别位于T₁-τ_c曲线极小点两侧.     

水/甲醇混合溶剂中PNIPAAM相变行为的NMR研究

通过液体核磁共振（NMR）谱以及动力学参数测量研究了聚N-异丙基丙烯酰胺（PNIPAAM）在水和甲醇的混合溶液中的相变行为. 通过PNIPAAM在水和甲醇混合溶剂中¹H核磁共振谱、纵向弛豫时间T₁、横向弛豫时间T₂和自扩散系数D随甲醇含量的变化发现,大分子在发生相变时,在¹H核磁共振谱中伴随有宽峰的出现和消失,同时弛豫时间和自扩散系数均有显著变化. 实验结果表明,¹H NMR谱图以及弛豫时间和自扩散系数等多种核磁共振参数可以用来灵敏表征PNIPAAM在水和甲醇混合溶液中的相变行为     

14N核四极共振自旋系统自旋-晶格弛豫时间的测量

¹⁴N核四极共振自旋系统的自旋-晶格弛豫是一种双指数弛豫。本文介绍了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间的3种测量方法,利用可变多面体方法对实验数据进行拟合,获得了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间T_1s和T₁₁,对有关文献中关于核四极共振弛豫时间的测量的3个观点提出了质疑。     

油井样品NMR T2谱的影响因素及T2截止值的确定方法

T₂ 谱是核磁共振（NMR）测、录井技术应用与解释、评价的基础. 岩样T₂ 谱受仪器测量参数、样品性质（岩性、颗粒大小、样品粒度、样品干湿状态、孔隙流体含量及性质、磁化率、润湿性）及地层水矿化度等因素的影响. T₂ 截止值是T₂ 谱中最重要的参数之一,选取的科学性与准确性直接影响到核磁共振测量结果. 通过文献查询,对T2 谱的影响因素及T₂ 截止值的确定方法进行了分析.     

1-甲基环氧乙烷-1-丙炔醚的结构测定及其核磁图谱

以¹H-NMR谱和¹³C双自旋回波的APT脉冲序列测定文献中尚未曾发表的化合物HC≡C-CH₂-O-C^CH₃-_O-CH₂文中计算了峰强度与脉冲间隔时间的关系,讨论了各谱线的相位并区分出-CH₃、-CH₂、-CH和季碳。     

有机磷化合物的NMR研究——Ⅱ0,0-二烷基膦酸酯的1H、13C和31PNMR谱

本文报道了21个0,0一二烷基膦酸酯类化合物的¹H、¹³C和³¹P NMR参数。研究和讨论了不等价的二烷基¹H、¹³C化学位移和磷碳偶合常数与立体化学的关系。测定了(CH₃CH₂O)₂P(O)CH(CH₂NO₂)(p-OCH₃C₆H₄)的¹³C自旋一晶格弛豫时间T₁,二乙基¹³C T₁间的差别,说明在类似化合物中,含有化学位移各向异性对弛豫的贡献。     

间接测量1H-13CT1和T2的方法

本文提出了间接测量¹H-¹³CT₁和T₂的新方法,这些方法能用于测量¹H谱不能很好分辨的分子。并对直接测量和间接测量结果进行分析比较。     

Estimation of free copper ion concentrations in blood serum using T(1) relaxation rates

The water proton relaxation rate constant R(1)=1/T(1) (at 60 MHz) of blood serum is substantially increased by the presence of free Cu2+ ions at concentrations above normal physiological levels. Addition of chelating agents to serum containing paramagnetic Cu2+ nulls this effect. This was demonstrated by looking at the effect of adding a chelating agent-D-penicillamine (D-PEN) to CuSO4 and CuCl2 aqueous solutions as well as to rabbit blood serum. We propose that the measurement of water proton spin-lattice relaxation rate constants before and after chelation may be used as an alternative approach for monitoring the presence of free copper ions in blood serum. This method may be used in the diagnosis of some diseases (leukaemia, liver diseases and particularly Wilson's disease) because, in contrast to conventional methods like spectrophotometry which records the total number of both bound and free ions, the proton relaxation technique is sensitive solely to free paramagnetic ions dissolved in blood serum. The change in R(1) upon chelation was found to be less than 0.06 s(-1) for serum from healthy subjects but greater than 0.06 s(-1) for serum from untreated Wilson's patients.     

Magnetic field dependence of spin-lattice relaxation enhancement using piperidinyl nitroxyl spin-labels

We examined the magnetic resonance properties of 12 paramagnetic piperidinyl nitroxyls in water and plasma solutions. Paramagnetic contributions to proton relaxation times were measured using 10.7 and 100 MHz spectrometers. Proton relaxation enhancement from nitroxyls increased with ascending molecular weight, in plasma solutions versus equimolar aqueous solutions, and with measurements at 10.7 MHz compared to 100 MHz. Relaxation rates were observed to approximately double at 10.7 MHz compared to 100 MHz and from water to plasma solutions. The data indicate that proton spin-lattice relaxation enhancement is magnetic field-dependent, and increases using nitroxyls of large molecular weight and with chemical substitutents that increase the microviscosity of solvent water molecules. The development of nitroxyls for diagnostic MRI will be aided by understanding these in vitro physical characteristics and trends.     

Nitroxide radicals

The proton hyperfine constants have been measured, using N.M.R., for a series of sterically hindered alkyl aryl nitroxides. Computer reconstructions of the electron resonance spectra show that the coupling constants obtained from the pure radical are very similar to those obtained from the electron resonance spectra of dilute solutions. Comparison of methyl and proton splittings in identical positions suggests that the radicals are σ in character although the molecular-orbital calculations are unable to distinguish between σ or π radicals.     

Determination of the effective correlation time modulating 1H NMR relaxation processes of bound water in protein solutions

The relaxation in protein solutions has mainly been studied by nuclear magnetic relaxation dispersion (NMRD) techniques. NMRD data have mostly been analyzed in terms of fast chemical exchange of water between free water and water bound to proteins. Several approaches were used for the estimation of correlation time modulating the relaxation mechanism of bound water. On the other hand, in a nuclear magnetic resonance experiment, the relaxation rates of protein solutions (1/T1 and 1/T2) and also those of free water (1/T1f and 1/T2f) are measurable. However, the relaxation rates of bound water (1/T1b and 1/T2b) are not. Despite this, equating (1/T1-1/T1f)/2(1/T2-1/T2f) to (1/T1b)/2(1/T2b) leads to an expression involving only an effective tau that is related to the rotational correlation time (tau r) of proteins. Equating the ratios may therefore give a simple alternative method for the determination of tau r even if this method is limited to a single resonance frequency. In this work, a formula was derived for the solution of the effective tau. Then, the 1/T1 and 1/T2 in solutions of two globular proteins (lysozyme and albumin) and one nonglobular protein (gamma-globulin) were measured for different amounts of each protein. Next, the values of 1/T1 and 1/T2 were plotted vs. protein concentrations, and then the slopes of the fits were used in the derived equation for determining the effective tau values. Finally, the rotational correlation time tau r, calculated from tau, was used in the Stokes-Einstein relation to reproduce relevant radii. The effective tau values of lysozyme, albumin and gamma-globulin were found to be 5.89 ns, 7.03 ns and 8.8 ns, respectively. tau r values of albumin and lysozyme produce their Stokes radii. The present data suggest that use of the measurable ratio in the derived formula may give a simple way for the determination of the correlation times of lysozyme and albumin.     

Weakly bonded cluster structures of N,N′-dimethylethyleneurea and water

Intermolecular interactions between a single water and two N,N′-dimethylethyleneurea (DMEU) molecules have been investigated using ab initio quantum chemistry method. The local and density-fitting approximations of the standard Møller-Plesset perturbation theory (DF-LMP2) have been employed together with the aug-cc-pVTZ basis set. Several trimeric systems were built where the water molecule, through the O-H?N hydrogen bond interactions, played the role of the bridge between the two DMEU molecules. The results show that the presence of the water molecule does not increase the stability of the trimeric systems. In the first three configurations the water molecule intercalates between two DMEU molecules, forming stable clusters. In the next three configurations, the water molecule is attached to a plane-parallel stacked DMEU dimer through the C=O?H-O hydrogen bond, and these structures are more stable than the first three. Small-angle neutron scattering data show clustering of DMEU molecules in their dilute aqueous solutions, and the ab initio results suggest that DMEU molecules could form contact pairs in dilute aqueous solutions.     

Studies on Trace Labelling of Bromsulphalein (BSP) with Radioiodine

Two methods have been studied for high specific activity trace iodination of Bromsulphalein (BSP) with radioiodine (¹³¹I). In the first method, BSP in aqueous solution is reacted with iodine and an oxidising agent – hydrogen peroxide or chloramine T. In the second method, iodination is carried out by electrolytically liberated iodine. The electrolytic method gives labelled BSP free from any labelled degradation products. The stability of ¹³¹I-labelled BSP in aqueous solution has been studied. The product has been found to remain more stable in aqueous solutions at a slightly acid pH (4…6.5) than in dilute alkaline solutions (pH 7…9.5).     

A Modified Technique for the Determination of Hydration Numbers of Metal Ions in Concentrated Aqueous Solutions by Means of Proton Magnetic Resonance

Quite recently much attention has been devoted to the direct determination of hydration numbers of cations in both aqueous solutions and in mixed solvent systems by means of PMR (proton magnetic resonance).^1-10     

Cesium adsorption in hydrated iron oxide particles suspensions: an NMR study

137Cs is an important component of nuclear waste which may pollute water. Its migration in natural environments is slowed down by adsorption on minerals. Cesium adsorption on akaganeite (beta-FeOOH) particles, dextran-coated ferrihydrite (5 Fe(2)O(3)-9H(2)O) particles, and ferritin in aqueous solutions is studied with (133)Cs nuclear magnetic resonance measurements. The longitudinal relaxation time (T(1)) of (133)Cs in the presence of such magnetic particles depends on whether the ions bind to the particle or not. T(1) of (133)Cs ions in aqueous solutions containing the same amount of magnetized particles will not depend on cesium concentration if relaxation is governed by diffusion (when cesium is not able to bind), but it will depend on cesium concentration if exchange governs relaxation (when cesium is able to bind). The method is successfully tested using TEMPO, a nitroxide stable free radical whose relaxation is due to diffusion. (133)Cs relaxation in solutions of ferritin, akaganeite, and dextran-coated ferrihydrite particles is found to result from a cationic exchange of cesium ions between particles surface and bulk ions, owing to adsorption. The effect of pH on (133)Cs relaxation in solutions of the particles is consistent with the adsorption properties of cations on hydrated iron oxides.     

高场强核磁共振下测量水的自旋晶格弛豫时间

在反转恢复脉冲序列中增加双极性梯度场脉冲以压制辐射阻尼效应,从而使之能够在高场强核磁共振波谱仪(Bruker AV600)中较为准确测量水的自旋-晶格时间.这一方法应用于商品化成像对比剂Gd-DTPA的弛豫率测试,得到的结果和文献相似,证实了该方法的可靠性.进一步应用于新合成成像对比剂TEMDP-EMFs性能的评价.     

NMR relaxometry and imaging of water absorbed in biodegradable polymer scaffolds

Porous substrates made of poly(3-hydroxybutyrate-3-hydroxyvalerate) (PHBHV) were prepared by a particulate leaching method. After removing the salt by extraction in water, proton nuclear magnetic resonance (NMR) relaxometry and imaging were performed on sets of PHBHV substrates immersed in phosphate-buffered solution during 3 months at different time points. Polarized optical microscopy studies were performed on thin sections, 25 and 5 mum, of the PHBHV samples. The results of NMR relaxometry showed two (1)H nuclei populations, well distinguishable on the free induction decay (FID), due to the different decay time constants, a factor of 10(2) apart. Thus, it was possible to separate the two populations, giving separate distributions of T(1) relaxation times. One population could be associated with water protons in the pores and the other to macromolecular protons. The distributions of T(1) and T(2) of the water proton shifted to lower values with increasing immersion time to a constant value after 30 days. The results obtained by NMR imaging showed an initial increase in the apparent porosity, reaching a plateau after 25 days of immersion. This increase is attributed mainly to the absorption of water in the microporosity as supported by the results of the relaxometry measurements and shown by scanning electron microscopy. The average porosity measured by NMR imaging at the plateau, 78+/-3%, is slightly higher than that determined by optical microscopy, 73+/-9%, which may be due to the fact that the latter method did not resolve the microporosity. Overall, the results suggest that at early stages after immersing the scaffolds in the aqueous medium, first 30 days approximately, NMR imaging could underestimate the porosity of the substrate.