不同浓度FeCl3·6H2O,CuSO4·5H2O和MnCl2·4H2O溶液核磁共振横向弛豫时间研究

利用核磁共振技术,测量了不同浓度的FeCl3.6H2O,CuSO4.5H2O和MnCl2.4H2O水溶液的核磁共振信号及横向弛豫时间.实验结果表明横向弛豫时间T2与顺磁离子浓度成反比关系,并由实验结果获得了通过核磁共振横向弛豫时间测量离子浓度的方法.     

利用核磁共振测量乙醇汽油溶液浓度

利用核磁共振成像分析仪测量了不同汽油体积含量的乙醇汽油溶液的核磁共振信号,分析了横向弛豫时间、信号强度与汽油浓度的关系.结果表明乙醇汽油溶液中汽油的体积含量与信号强度呈线性关系,因此利用低磁场核磁共振可以测量乙醇汽油浓度.     

核磁共振实验教学内容的重组与优化

探索研究了一种将连续核磁共振和脉冲核磁共振有机融合的实验教学方法.在实验中,利用多媒体课件展示核磁共振的物理原理,学生分别采用连续和脉冲核磁共振方法测量同样浓度的CuSiO4水溶液的表观弛豫时间和横向弛豫时间,了解样品浓度、磁场非均匀度等因素对横向弛豫时间测量的影响.     

不同浓度氯化钠水溶液核磁共振特性的实验研究

为了认识氯化钠水溶液的核磁共振特性,配制了浓度在0%~24%范围内的氯化钠水溶液,采用CPMG自旋回波法测量了横向弛豫时间和信号强度,文章分析了氯化钠水溶液浓度与横向弛豫时间及信号强度之间的关系和影响机理。结果表明,氯化钠水溶液的横向弛豫时间随着浓度增加而减小,二者存在较好的线性关系;单位质量氯化钠水溶液的核磁共振信号强度随着浓度增加而减小,二者之间也存在着较好的线性关系。利用这两种关系均可实现氯化钠水溶液浓度的核磁共振测量。     

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     

核磁共振弛豫时间与溶液浓度关系的实验研究

利用小型核磁共振成像仪可以测量样品弛豫时间的功能，设计方案，实验测定了硫酸铜水溶液中氢原子核的核磁共振弛豫时间T1、T2随硫酸铜浓度的变化关系，得到T1与T2随溶质浓度的增大而减小的实验结果．在误差允许的范围内，验证了T1与溶液浓度成反比的规律，并进行了分析和理论解释．     

核磁共振技术测量生物骨密度的设备及方法

诊断骨质疏松症多采用双能X射线吸收方法测得的骨密度数据作为依据,但是该方法存在一定量的辐射,且准确性不高.该文设计并改进了一套核磁共振装置,通过在发射和接收线圈之间增加快速切换开关(Q-switch),使得核磁共振自旋回波的回波时间缩短至80μs的超短回波时间范围,实现了对T_2弛豫时间很短的骨组织核磁共振自旋回波信号的采集;将T_2弛豫时间谱和双能X射线方法测量的骨密度数据进行了对比研究,发现核磁共振T_2弛豫时间谱上300~500μs之间的峰值与骨密度之间具有良好的线性关系,随着骨密度的增大,相应的T_2弛豫时间峰值缩短;利用核磁共振T_2弛豫时间谱技术,结合双能X射线吸收方法,提出了一种测量生物离体骨骼样本骨密度的方法.该测量方案具有测量速度快、对人体完全无害、跨时期比较性强等优点,很好的弥补了现有测量方法的不足,在骨质疏松症的诊断和疗效评估中有着良好的应用前景.     

基于差分进化算法的核磁共振T2谱多指数反演

提出了一种基于差分进化(DE)算法的核磁共振弛豫信号多指数反演新方法.将核磁共振T2谱反演问题转化为带非负约束的非线性优化问题,不需要预先给定横向弛豫时间T2分布,直接利用差分进化算法进行反演计算.在测量信号低信噪比的情况下,计算机模拟和实验数据反演鄙表明了该方法在分析处理NMR弛豫信号中的有效性.     

CaSO_4·(1/2)H_2O粉末中结晶水与吸附水1~H的Goldman-Shen实验

本文利用Goldman-Shen脉冲序列测量了CaSO_4·(1/2)H_2O样品中结晶水与吸附水~1H的交叉弛豫时间为55.1ms。在实验中,发现剩余窄线的磁化矢量随时间的衰减有三个过程。本文对此现象作了一些分析讨论。     

离子导体LiCl(Al_2O_3)的核磁共振研究

本文报道了含分散第二相粒子的离子导体LiCl(或LiI)中~7Li核磁共振的观测结果,测量了~7Li核磁共振吸收谱线的线宽和自旋-晶格弛豫时间(T_1)。实验发现,在LiCl(Al_2O_3)中,~7Li的核磁共振吸收谱线上叠加了一小峰,且随第二相粒子的类型、含量和温度而变化。~7Li核磁共振信号的信噪比显著提高,自旋-晶格弛豫时间变短,且也随第二相粒子的类型、含量和温度而变化。结果表明,离子电导率的提高和附加小峰的出现都是由第二相粒子引起的,从而提出:靠近第二相粒子的LiCl界面附近的空间电荷区中高的离子传导是离子电导率提高和附加小峰出现的可能机理。     

Amide proton relaxation measurements employing a highly deuterated protein

Proton NMR longitudinal and transverse relaxation rates of unlabelled proteins are generally dominated by the many 1H-1H dipolar interactions so that spin diffusion, rather than molecular or internal motions, governs longitudinal relaxation. Here, relaxation measurements of backbone amide proton (1H(N)) magnetisations have been carried out employing the 99% 2H, 98% 15N labelled, small 2F2 protein domain in 10%/90% H(2)O/D(2)O solution. Under these conditions, the longitudinal relaxation rates exhibit time constants, T(1)*=1/R(1)* if described by a mono-exponential, within the range of 3.0 to 18.7s-a wide range which indicates that the phenomenon of spin diffusion has been greatly reduced. The majority of 1H(N) nuclei in this sample (pH 4.0 and 5 degrees C) exhibit chemical exchange with solvent that couples their longitudinal relaxation to that of the solvent. For the subset of 1H(N) nuclei not undergoing detectable solvent chemical exchange, the R(1)* rates correlate well with their individual 1H(N,O)/2H(N,O) structural environments. The correlation for corresponding transverse relaxation rates, R(2)* was found to be less good. Longitudinal relaxation measurements in 1%/99% H(2)O/D(2)O solution identify a further subset of 1H(N) nuclei which exhibit essentially indistinguishable R(1)* rates in both 1% and 10% H(2)O, implying that averaging of rates from spin diffusion processes and different 2F2 isotopomer populations are negligible for these 1H(N) sites. In addition to a high sensitivity to structural parameters, model calculations predict 1H(N) relaxation rates to exhibit pronounced sensitivity to internal dynamics.     

单甲基化及双乙基化大豆苷元磺酸锰的合成及晶体结构

以大豆苷元为先导化合物,合成了两种水溶性异黄酮磺酸锰：7-甲氧基-4′-羟基异黄酮-3′-磺酸锰（1）和4′,7-二乙氧基异黄酮-3′-磺酸锰（2）,并采用1HNMR、IR光谱、元素分析和X-射线单晶衍射法对它们的结构进行了表征。X-射线单晶衍射分析表明：1的分子组成为[Mn（H2O）6]（C16H11O4SO3）2.10H2O,其中Mn（II）位于对称中心并被6分子水所配位。[Mn（H2O）6]^2＋,C16H11O4SO3-和H2O之间存在多种氢键;2的分子组成为[Mn（H2O）6]（C19H17O4SO3）2.8H2O,两个异黄酮骨架构象不同。6个配位水分子分别与2个异黄酮骨架中磺酸根上的4个氧原子及8个结晶水上的8个氧原子形成12条氢键。1,2的晶体结构中均存在着π…π堆积作用,氢键以及π…π堆积作用共同将1或2组装成具有三维网格结构的超分子。     

新型发光材料磷酸锌钾纳米片的制备

以ZnSO4·7H2O和K3PO4·3H2O为原料采用固相反应合成磷酸锌钾,应用均匀设计和数据挖掘技术设计实验方案,采用XRD、SEM和EDS等方法对产物进行表征,并对产物的长余辉发光性能进行了研究。结果表明,根据产物的产率和锌的含量进行回归分析可以建立2个数学模型,对模型进行优化处理可以得到固相法合成磷酸锌钾的最优工艺条件。在n(K3PO4·3H2O)∶n(ZnSO4·7H2O)=1.01、研磨时间31 min、保温温度750℃、保温时间3.2 h的最优条件下制备的KZnPO4纳米片,在紫外光照后可产生蓝绿色长余辉发光,最强发光峰的波长范围为415～530 nm。     

Practical aspects of (1)H transverse paramagnetic relaxation enhancement measurements on macromolecules

The use of (1)H transverse paramagnetic relaxation enhancement (PRE) has seen a resurgence in recent years as method for providing long-range distance information for structural studies and as a probe of large amplitude motions and lowly populated transient intermediates in macromolecular association. In this paper we discuss various practical aspects pertaining to accurate measurement of PRE (1)H transverse relaxation rates (Gamma(2)). We first show that accurate Gamma(2) rates can be obtained from a two time-point measurement without requiring any fitting procedures or complicated error estimations, and no additional accuracy is achieved from multiple time-point measurements recorded in the same experiment time. Optimal setting of the two time-points that minimize experimental errors is also discussed. Next we show that the simplistic single time-point measurement that has been commonly used in the literature, can substantially underestimate the true value of Gamma(2), unless a relatively long repetition delay is employed. We then examine the field dependence of Gamma(2), and show that Gamma(2) exhibits only a very weak field dependence at high magnetic fields typically employed in macromolecular studies. The theoretical basis for this observation is discussed. Finally, we investigate the impact of contamination of the paramagnetic sample by trace amounts (5%) of the corresponding diamagnetic species on the accuracy of Gamma(2) measurements. Errors in Gamma(2) introduced by such diamagnetic contamination are potentially sizeable, but can be significantly reduced by using a relatively short time interval for the two time-point Gamma(2) measurement.     

耐高温型4-卤代(氟、氯)苯甲酸铽配合物的合成及荧光性能研究

以4-氟苯甲酸(4-FBA)、4-氯苯甲酸(4-ClBA)为配体制备了具有良好热稳定性的稀土配合物Tb(4-FBA)3·2H2O和Tb(4-ClBA)3·2H2O,与前期工作中合成的Tb(4-BrBA)3的紫外及荧光光谱进行了分析比较。紫外-可见光吸收光谱表明,相同浓度下,3种配合物的紫外吸收能力以Tb(4-FBA)3·2H2O、Tb(4-ClBA)3·2H2O、Tb(4-BrBA)3顺序依次增大。液体荧光光谱表明,Tb(4-ClBA)3·2H2O的荧光发射强度最强。从配体的能级、配合物的紫外吸收能力及能量传递过程中的热振动损耗等方面对实验结果进行了讨论分析。热重分析表明,Tb(4-FBA)3·2H2O和Tb(4-ClBA)3·2H2O在450℃出现快速分解。将2种配合物放置于马弗炉中350℃加热1 h后,发现Tb(4-FBA)3·2H2O的荧光发射强度降低了24%,Tb(4-ClBA)3·2H2O荧光发射强度仅降低了13%左右,表明2种配合物高温条件下分子结构保持稳定,加热后2种配合物的红外光谱也表明2种配合物在高温条件下未发生分解。     

光助Fenton法降解水中间氨基苯酚的研究

采用光助Fenton氧化法处理间氨基苯酚模拟废水,考察了光强、Fenton试剂的用量、初始pH、反应时间对降解效果的影响,初步探讨了其降解动力学规律。结果表明:在不同光源下(闭光、高压汞灯照射以及较强太阳光照射),450W高压汞灯照射以及较强太阳光照射的条件均可以明显加快Fenton法催化氧化降解间氨基苯酚溶液的过程。选择1.5mL2.5g.L-1FeSO4.7H2O,1.0mL6%H2O2,初始pH=3.5,太阳光照射下降解间氨基苯酚效果较好,反应40min后降解率高达99%;降解过程符合准一级反应动力学方程。     

The interpretation of multi-exponential water proton transverse relaxation in the human and porcine eye lens

We report results of 1H NMR transverse relaxation experiments on human and porcine eye lenses. Several authors have reported that transverse relaxation is not mono-exponential when observed by the Carr-Purcell-Meiboom-Gill (CPMG) sequence and have interpreted the results by postulating the presence of "pools" of water molecules in different binding environments that do not exchange rapidly on the NMR timescale. We have compared CPMG data for intact lenses with results for lens homogenates and have combined a CPMG spectroscopic pulse train with NMR micro-imaging to study the nature of the transverse relaxation process in human and porcine lenses. Fast exchange of water protons with the lens proteins (crystallins) leads to an enhanced transverse relaxation rate that varies linearly with protein concentration. At the resolution of NMR micro-imaging the transverse relaxation process is mono-exponential. The results show that the multi-exponential CPMG data observed spectroscopically for whole lenses reflect spatial variations in crystallin content through the lens rather than the presence of distinct "bound" and "free" water pools.     

Diffusion-weighted spatial information from1H relaxation in restricted geometries

Summary NMR relaxation of water¹H confined in restricted geometries, whatever is the nature of the system (porous media saturated by water as well as biological tissues), exhibits common characteristics. Artificial microporous media saturated by water have been chosen as model systems to study the longitudinal and transverse relaxation of¹H magnetization of water molecules diffusing in restricted geometries. These systems are very stable, easy to prepare, with well-characterized pore size distribution and connections, and with highly homogeneous surface properties. The response was compared with that from more complex natural porous media. Scanning Electron Microscopy techniques demonstrated spatial characteristics and surface properties of the samples. The information content of longitudinal relaxation curves associated with spatial structure and due to restricted diffusion is shown in these samples. The effect on transverse relaxation of self-diffusion in the presence of spatially varying magnetic fields due to susceptibility differences is shown. A simple linear relationship has been found in all samples between the transverse relaxation rate and the interpulse delay in CPMG experiments, in spite of the variety of pore shapes and sizes. In general, one can say that relaxation curves beardiffusion-weighted information on the pore space framework. The role of the investigated relaxation mechanisms is important also in the response of biological tissues, including in the presence of MR Imaging contrast agents inducing microscopic magnetic-field gradients. Work partially supported by CNR and MURST Grants.     

尖晶石型纳米铁酸镍的制备与磁性研究

以Fe（NO3）3·9H2O和Ni（NO3）2·6H2O为原料,用柠檬酸为还原剂,采用燃烧法制备了NiFe2O4纳米粉体,用X射线粉末衍射仪（XRD）、透射电子显微镜（TEM）、红外光谱（IR）和振动样品磁强计（VSM）等手段对样品进行了表征,结果表明,样品为立方晶系尖晶石铁酸镍纳米粉体,其粒径在20—40nm之间,具有超顺磁性,并探讨了焙烧温度、焙烧时间对样品磁性的影响。