应用核磁共振测定有机化合物绝对构型的方法

综述了应用核磁共振测定有机化合物绝对构型的各种方法. 根据方法的原理，将方法分为两类，一类是应用芳环抗磁屏蔽效应测定有机化合物绝对构型的NMR方法，包括M os her法，改进的Mosher法，MPA以及其他AMAs手性试剂方法；另一类是应用配糖位移效应测定有机化合物绝对构型的NMR方法，包括4-O-苯甲酰基葡萄吡喃糖甙方法和岩藻呋喃糖甙 方法等. 本综述包括各种方法的原理，测定绝对构型的步骤等.     

A Simple Systematical Law of E2＋ Values for Heavy Nuclei in the NpNn Scheme and the Evolution of the Z=64 Shell Gap

A systematics of excitation energy of the first 2^＋ state E2＋ in even-even heavy nuclei （A ≥ 120） is studied in the NpNn scheme. It is found that a simple exponential function describes the dependence of E2＋ values on NpNn values very well. In addition, the Z = 64 shell gap is reexamined by investigating the systematics of the 52 ≤ Z ≤66 region. It is found that the Z = 64 shell gap is largest at N = 82 and becomes smMler with either increasing or decreasing of neutron numbers. The effects of this shell gap become negligible for counting the valence proton numbers when N ≥ 92 or N ≤ 72.     

氨基酸合成方法研究—(XI)N-取代亚氨酸酯与芳醛缩合产物—去氢氨基酸衍生物的构型及其NMR研究

通过~1H NMR、NOE差谱和门控去偶~(13)C NMR等的研究确定了新合成的五对α-去氢氨基酸衍生物的构型,并利用部分弛豫、APT~(13)C NMR二维碳氢相关谱及~(13)C-~(19)F偶合常数等对NMR谱线进行了归属.     

2D NMR研究呋喃糖Grignard加成产物的绝对构型

通过对相应呋喃糖进行Grignard亲和加成合成了苯基及苄基取代呋喃糖.所得主要产物的结构和绝对构型通过二维核磁共振进行了研究.其结果通过计算机分子模拟优化,并进行了比较和确认.     

平面五体中心构型的稳定性

用牛顿力学在转动参照系中的动力学方程描述天体的运动,采用线性稳定性分析方法讨论平面五体中心构型的稳定性。结果表明:当中心天体的质量大于或者等于顶点天体质量的9.64倍时,平面五体的正四边形构型是线性稳定的;反之则是不稳定的。平面五体的正五边形构型总是不稳定的。     

氨基酸合成方法研究-(XI)N-取代亚氨酸酯与芳醛缩合产物-去氢氨基酸衍生物的构型及其NMR研究

通过¹H NMR、NOE差谱和门控去偶¹³C NMR等的研究确定了新合成的五对α-去氢氨基酸衍生物的构型,并利用部分弛豫、APT ¹³C NMR二维碳氢相关谱及¹³C-¹⁹F偶合常数等对NMR谱线进行了归属.     

2D NMR研究D-葡萄糖衍生的手性配体的绝对构型

应用二维NOSEY技术，对以D-葡萄糖为手性源合成的3种新型手性配体的结构和绝对构型进行了研究，并对此类化合物进行了计算机分子模拟，取得与NOSEY一致的结果. 此项研究对进一步研究手性配体在不对称催化反应中的构效关系提供了有力的帮助.     

玻璃化液体中构型熵与展宽弛豫函数关系的研究

运用Adam Gibbs关于构型重排区域的构型熵理论和极值动力学模型得到的弛豫时间的理论公式,提出了KWW型弛豫函数中的非指数展宽因子等于液体中构型重排区域的相对构型熵;并与一个构型重排区域内构型变换的临界分子数成反比,从而赋予了展宽因子新的关于玻璃化结构的物理意义,建立了结构弛豫与构型熵之间的关联.为了消除Vogel Fulcher Tamann方程拟合粘度实验数据在高温区的偏差,用温度的高阶项修正展宽因子与温度的关系,其结果在低于200K时符合得很好,其修正项等效于等压与等容热容量之差对构型熵的修正.     

天然孕甾烷-17(20)-烯中C-17位双键构型的快速测定

天然孕甾烷-17(20)-烯中C-17位双键的构型对分子的药理性质有重要的影响,但是采用化学位移比较等方法判断其构型存在费时以及区分模糊等缺点. 该文以E-和Z-guggulsterone为模型化合物,利用一维选择性NOE实验来进行天然孕甾烷-17(20)-烯中C-17位双键的构型测定. 由于空间相对位置受到构型影响,选择反转20位的质子时,如果选择性NOE谱中仅能检测到21位甲基氢,表明该化合物为E-构型;如果除了21位甲基氢外,18位甲基氢和12位氢也存在于选择性NOE谱中,则表明该化合物为Z-构型. 实验结果表明该方法具有区分度大,简单快速等优点,可以普遍适用于这些孕甾烷类化合物17位双键构型的确定.     

B2H6分子的几何构型

采用Gaussian 98程序中B3P86，BP86，B3LYP，BLYP，UHF，HF及LSDA等方法，对B_{2Ｈ6分子可能的D3d，D3h，D2d和D2h平面型状态及立体型状态 的几何构型五种情况的1重态及3重态进行了优化，得到该分子基态为1重态，它的电子状态 是^lＡg,B2H6的几何构型仍然是传统的对 称性为乙烯式的D2h结构 ，其构型如图9所示，其能量最低，是－53．5865H.a.u..两个硼原子与四个H原子所在平面 垂直于两个硼原子及另外二个H原子所在平面，二个硼原子之间的距离是R12=0 ．17542nm，B原子及H原子之间的距离是R17=0．13149nm，R13=0． 1188 4nm,它们之间的夹角分别是，∠314=∠526=121．93°，∠817=∠827=96．3°，B2Ｈ6中硼原子采用不等性的sp³轨道和另一硼原子的不等性的sp< sup>3轨道 及氢原子的1s轨道 交互重叠生成桥式三中心双电子键.三中心双电子键比双中心双电子键更为稳定，计算结果 也证实了这一点. 关键词： 2H6')" href="#">B2H6 密度泛函 几何构型 优化}     

Role of N/Z in Pre-scission Neutrons as an Observable of Nuclear Friction

A dynamical Langevin model is employed to evaluate the excess of the neutron emission in the fission of heavy nuclei ^240Cf, ^246 Cf, ^254Cf, ^240U relative to the standard statistical-model prediction at various saddle-to-scission friction strengths. It is shown that when the neutron-to-proton ratio N/Z of the system increases, the sensitivity of the excess to the friction decreases substantially, and it almost disappears for ^240U. We suggest that using those compound systems with low N/Z favors an accurate determination for the saddle-to-scission friction strength based on the measurement of the pre-scission neutron multiplicity.     

Role of N/Z in Pre-scission Neutrons as an Observable of Nuclear Friction

A dynamical Langevin model is employed to evaluate the excess of the neutron emission in the fission of heavy nuclei ²⁴⁰Cf, ²⁴⁶Cf, ²⁵⁴Cf, ²⁴⁰U relative to the standard statistical-model prediction at various saddle-to-scission friction strengths. It is shown that when the neutron-to-proton ratio N/Z of the system increases, the sensitivity of the excess to the friction decreases substantially, and it almostdisappears for ²⁴⁰U. We suggest that using those compound systems with low N/Z favors an accurate determination for the saddle-to-scission friction strength based on the measurement of the pre-scission neutron multiplicity.     

H, V and N nuclear magnetic resonance studies of structure and properties of vanadia supported on TiOx/SiO2

¹H magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra of TiO_x/SiO₂ catalysts suggest the interaction of surface TiO_x. species with Si-OH groups of the silica. Simultaneously, Ti-OH groups from surface titania species appear. The distribution of TiO_x species over SiO₂ is non-uniform, since a considerable part of surface OH groups remains unreacted with supported titania. Supported vanadia species interact both with Si-OH and Ti-OH groups. ⁵¹V NMR spectra suggest the interaction of vanadia with supported titania species and show the non-uniform distribution of titania over the SiO₂ surface. Deposition of titania as well as vanadia produces strong electron-accepting (Lewis) sites which interact with the terminal N atom of adsorbed N₂O molecules, resulting in a downfield shift of the resonance in ¹⁵N NMR spectra. The acid strength of electron-accepting sites is similar in both cases. Only about 10% of the total amount of supported titania and vanadia create Lewis sites.     

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (¹H‐¹³C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), ¹H‐¹⁵N HMBC, ¹H‐¹H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of N/Z on Spin Distribution of Evaporation Residue Cross Section as a Probe of Nuclear Dissipation

The spin distribution of the evaporation residue cross section of nuclei ^194pb, ^200Pb, ^206Pb, and ^200 Os are calculated via a Langevin equation coupled with a statistical decay model. It is shown that with increasing the neutronto-proton ratio （N/Z） of the system, the sensitivity of the significantly. Moreover, for ^200Os this spin distribution is no spin distribution to the nuclear dissipation is decreased longer sensitive to the nuclear dissipation. These results suggest that to obtain a more accurate pre-saddle viscosity coefficient through the measurement of the evaporation residue spin distribution, it is best to yield those compound systems with low N/Z.     

Effects of N/Z on Spin Distribution of Evaporation Residue Cross Section as a Probe of Nuclear Dissipation

The spin distribution of the evaporation residue cross section of nuclei ¹⁹⁴Pb, ²⁰⁰Pb, ²⁰⁶Pb, and ²⁰⁰Os are calculated via a Langevin equation coupled with a statistical decay model. It is shown that with increasing the neutron-to-proton ratio (N/Z) of the system, the sensitivity of the spin distribution to the nuclear dissipation is decreased significantly. Moreover, for ²⁰⁰Os this spin distribution is no longer sensitive to the nuclear dissipation. These results suggest that to obtain a more accurate pre-saddle viscosity coefficient through the measurement of the evaporation residue spin distribution, it is best to yield those compound systems with low N/Z.     

利用高温超导直流量子干涉器件进行10$lt;sup$gt;-6$lt;/sup$gt; T量级磁场下核磁共振的研究

研究了水样品在10^-6 T量级磁场下的核磁共振谱.核磁共振信号由一个工作在液氮温度的高温超导直流量子干涉仪记录,测量在一个简易磁屏蔽室中进行.在7—70 μT的磁场范围内都观察到了15 ml水样品的核磁共振信号.相应的^1H的核磁共振频率为300—3000 Hz.在实验中获取的单次测量信噪比约为4,通过对信号的100次平均,信噪比可达到约40.进一步讨论了剩余磁场、预极化时间和采样时间对结果的影响.最后用数字滤波之后平均的方法初步得到了时域的自由感应衰减信号. 关键词： 超导量子干涉仪 核磁共振     

A new sequence for the MQMAS/HETCOR experiment

Two-dimensional (2D) multiple quantum MAS (magic angle spinning) spectroscopy has been combined with cross-polarisation to obtain a heteronuclear correlation spectrum between a quadrupolar spin-3/2 and a spin-1/2 nucleus. The advantage over the conventional correlation experiment is the increased resolution obtained in the multiple quantum dimension. Pure absorption 2D spectra can be obtained by implementing a zero quantum filter between the evolution of multiple quanta and the subsequent cross-polarisation step. The current experiment shows a considerable improvement in sensitivity compared to a previously introduced sequence.     

Projection Operator on Rational Noncommutative OrbifoldT2/Z4

In this paper, we introduce the reduced matrix in kq representation and provide the reduced matrix elements of a projection operator \hat{P} on the rational noncommutative orbifold T²/Z₄. we give the closed form for the projector by Jacobi elliptical functions. Since projectors correspond to soliton solutions of the field theory on the noncommutative orbifold, we thus present a corresponding soliton solution.