盐酸氯丙嗪1H NMR、 13C NMR谱的归属及结构表征

通过运用¹H-¹H COSY(¹H-¹H COrrelation SpectroscopY)、TOCSY(TOtal Correlation SpectroscopY)、HSQC(Heteronuclear Single Quantum Correlation)、HMBC (Heteronuclear Multiple Bond Correlation)、NOESY(Nuclear Overhauser Enhancement SpectroscopY)等多种二维核磁技术,对盐酸氯丙嗪（Chlorpromazine hydrochloride CPZ· HCl）在CDCl₃、CD₃COCD₃和D₂O三种溶剂中的¹H、¹³C NMR谱进行了准确归属（重点集中于谱峰重叠程度较高的芳香族区域）．实验表明：杂环上N与苯环存在部分共轭;在CDCl₃、CD₃COCD₃中,侧链卷曲至芳环上方处于屏蔽区,且侧链上N为较稳定的四面体构型;比较了CPZ· HCl在不同溶剂与浓度下的¹H NMR谱的变化,对文献中其核磁共振谱（特别是芳香区的谱峰）归属的争议作了解释．量子化学计算结果与实验结果相吻合．     

阿普唑仑的波谱学数据和结构确证

阿普唑仑是一种临床上广泛应用的具有抗抑郁作用的药物. 本文对阿普唑仑进行了¹H、¹³C NMR检测,通过DEPT和¹H-¹H COSY、¹³C-¹H HSQC、¹³C-¹H HMBC等2D NMR技术对该化合物的¹H、¹³C NMR谱的信号进行了全归属,通过量子化学计算和NMR数据证实了化合物中亚甲基上2个氢的磁不等价性. 讨论了红外吸收光谱的特征峰,并对阿普唑仑的TOF MS的裂解途径进行了分析.      

含芳基噻唑糖基胍的NMR研究

通过对4种含芳基噻唑半乳吡喃糖基胍的¹H NMR谱的分析, 确证其糖苷键为β-构型, 对其一般特征进行了对比和讨论,并用¹H-¹H COSY, gHMQC, gHMBC, NOESY等2D NMR技术对它们的¹H和¹³C NMR谱峰进行了全归属.     

射干异黄酮的NMR波谱研究

为研究中药射干(Belamcanda chinensis)的化学成分,应用多种柱色谱方法对其乙醇提取物进行分离和纯化,并得到了11个异黄酮化合物,通过¹H NMR、¹³C NMR及HMBC、HSQC、¹H-¹H COSY、NOESY等波谱手段解析化学结构,发现一个新化合物,命名为异野鸢尾苷. 对这些化合物的¹H NMR和¹³C NMR进行了完全归属,并探讨了取代基对¹H、¹³C化学位移的影响.     

含全氟烷基香豆素衍生物的简易合成及结构表征

以含全氟烷基香豆素为原料合成了一系列含全氟烷基香豆素亚胺类化合物，通过对该类化合物的IR、MS、¹H NMR、¹³C NMR的分析，归属了各NMR谱线，对相关化合物进行了结构确证，同时对该类化合物的光物理行为进行了初步研究.     

克林霉素磷酸酯的波谱学研究

克林霉素磷酸酯是临床上广泛使用的一种抗菌类药物. 本文对克林霉素磷酸酯进行了¹H、¹³C、³¹P NMR检测,通过DEPT、¹H-¹H COSY、¹³C-¹H HSQC、¹³C-¹H HMBC等2D NMR技术对该化合物的¹H、¹³C谱的信号进行了全归属,并结合量子化学计算和NOESY谱证实了化合物的立体结构. 另外,对克林霉素磷酸酯的飞行时间质谱(TOF-MS)的裂解途径进行了分析.     

双分子缬氨酸氢膦烷构型的确定

以缬氨酸为原料,和三氯化磷反应合成了双分子缬氨酸氢膦烷．采用¹H NMR、¹³C NMR、¹H-¹H COSY、DEPT和HSQC等技术确证了目标化合物的结构;对其¹H NMR和¹³C NMR信号进行了归属,同时利用IR和ESI-MS验证了其结构．³¹P NMR显示所得产物为缬氨酸氢膦烷的一对非对映异构体,利用NOESY技术对分离得到的其中一种异构体绝对构型进行了确定,该结果得到了X-射线单晶衍射的验证．     

3，5-二甲基金刚胺盐酸盐的NMR研究

NMR核磁共振谱显示3，5-二甲基金刚胺盐酸盐是一个刚性结构，但其分子结构包含2个非对映体的立体构型形式. 我们通过利用DEPT，¹H-¹H COSY，HSQC和HMBC等技术所测得的二维谱图数据对NMR数据进行了完整的归属分析，其中¹³C NMR谱图显示在δ=29~54 ppm之间的十组峰表示所有碳的共振，而且由于不同的分子构象导致在¹³C NMR谱中有3个不同的季碳峰和¹H NMR中的2个不同的甲基峰. 由于H-5的叔碳H原子与邻近CH₂ 的平面二面夹角均约为600，致使耦合常数极其小，波谱仪难以分辨它们从而使¹H NMR峰为单重峰.     

4-[(E)-2-(3, 4-二甲氧基苯基)乙烯基]苯氧基乙酸乙酯的合成及其NMR研究

以对硝基甲苯、3, 4-二甲氧基苯甲醛为起始原料,经过缩合,还原,重氮化水解,亲核取代反应,最终合成了新的化合物4-[(E)-2-(3, 4-二甲氧基苯基)乙烯基]苯氧基乙酸乙酯,用¹H 和¹³C NMR及多种二维核磁共振谱确定了该化合物的结构,完成了¹H 和¹³C NMR的归属,给出了分子中各氢,碳原子的准确化学位移.     

维库溴铵合成工艺中雄甾类中间体的NMR研究

维库溴胺合成中的6个中间体均为雄甾类化合物,我们以重要中间体2β,16β-二(1-哌啶基)-5α-雄甾烷-3α, 17β-二醇为例,使用质谱、红外光谱和核磁共振技术确定了它的结构,并结合¹H NMR, ¹³C NMR, DEPT, ¹H-¹H COSY, HSQC, HMBC多种核磁共振分析方法,详细归属了其所有的¹H NMR和¹³C NMR数据,利用ROESY确定了其相对构型. 根据相同方法,归属了其它5个中间体的¹³C NMR数据,为它们的结构鉴定提供了重要依据,为维库溴铵合成工艺的中间体质量控制提供了参考数据.     

Imaging of (13)C-labeled glucose and sorbitol in bovine lens by (1)H-detected (13)C nuclear magnetic resonance spectroscopy

Bovine lenses were incubated in a solution containing [1-(13)C]glucose (50 mM) for 1, 2 and 4 days. Spectroscopic images of [1-(13)C]glucose and [1-(13)C]sorbitol were constructed using (1)H-detected gradient-enhanced heteronuclear multiple-quantum coherence (GE-HMQC) in a 2.0-tesla magnetic field. Accumulations of [1-(13)C]glucose and [1-(13)C]sorbitol were mainly observed at the periphery of the lens. Their distributions corresponded to the cortex. (1)H-detected (13)C nuclear magnetic resonance (NMR) spectroscopic imaging by GE-HMQC successfully demonstrated the distribution of [1-(13)C]glucose and [1-(13)C]sorbitol at the periphery of bovine lenses.     

运用预饱和对HOESY实验灵敏度优化

二维异核NOESY(HOESY)内在的低灵敏度限制其在结构分析上的应用,利用¹H探测（反式探测）可以提高其灵敏度. 这里我们提出一种预饱和二维¹³C-¹H HOESY实验,利用异核之间的NOE增强效应,进一步提高实验的灵敏度. ¹H探测HOESY谱图中经常有严重的t₁噪声,可以通过脉冲梯度场相关选择和相位循环压制,得到改善的¹³C-¹H的NOE相关谱图.     

Experimental Study of High-Spin States in Deformed Odd-Odd 180 Ir

High spin states in deformed odd-odd ¹⁸⁰Ir have been investigated using the ¹⁵⁴Sm (³¹P, 5nγ)¹⁸⁰Ir reaction through the measurements of excitation functions at 150, 155, 160, 165 and 170 MeV beam energies, K X-γ and γ-γ coincidences at 160 MeV. A new level scheme composed of 5 rotational bands has been established. According to the band structure characteristics and the deduced in band B(M1)/B(E2) ratios, the quasiparticle configurations and spin and parity have been proposed to the observed bands. The neutron AB crossing is observed at hω_c≈0.26 MeV for the π1/2^－[541]⊙ν1/2^－[521] and π1/2^－[541]⊙ν5/2^－[512] bands. This AB crossing frequency is close to that in the ν5/2^－[512] band of ¹⁷⁹Os indicating the loss of intruder nature of the π1/2 - orbit. Gradual alignment gain in both the π9/2^－[514]⊙ν7/2⁺[633] and π9/2^－ν5/2^－[512] bands is observed which is similar to the low spin anomaly in alignment in the πh_11/2,πd_5/2 and πi_13/2 bands of neighboring Ir and Re isotopes. Different alignment properties have been discussed in the framework of cranked shell model, and a larger quadrupole deformation is suggested for the bands with π9/2^－[514] orbit involved.     

Configuration-Dependent Bands in 169Re

High-spin states in ¹⁶⁹Re were studied and resulted in the identification of a strongly coupled band based on the 9/2^－[514] Nilsson state and a decoupled band built on the h_9/2 intruder proton orbital (nominally 1/2^－[541]). The cranked shell nodel calculations present configuration-dependent deformations that can explain the different band crossing frecpiencies. The experimental 9/2^－[514] band in Re shows the largest signature splitting at low spin among the known odd mass Re isotopes. After the alignment of a pair of the i_13/2 neutrons, the phase of the splitting is inverted with a significantly reduced amplitude. Additionally, a three-quasipariticle band was observed and assigned to be built likely on the π9/2^－[514]⊙AE configuration.     

Fine-Structure Splittings of Nitrogen Isoelectronic Sequence： Competitions among Spin-Orbit Interactions, Breit Interactions and Electron Correlations

Using the multi-configuration Dirac-Fock self-consistent field method and the relativistic configuration interaction method with quantum-electrodynamics corrections performed by the GRASP code, we calculate the fine-structure energy levels of the ground-state configuration （1s^22s^22p^3） of the nitrogen isoelectronic sequence, according to the L-S coupling scheme with atomic number Z up to 22. Based on the calculated results, we elucidate the mechanism of the orderings of fine-structure energy levels of 2^ D3/2,5/2 and 2^P1/2,3/2 respectively, i.e. for 2^D3/2,5/2 orderings, the competition between the spin-orbit interactions and the Breit interactions; for 2^P1/2,3/2 orderings, the electron correlations, especially the electron correlations owing to the 2p^5 configuration interactions.     

高压下Gd3Ga5O12晶体的弹性性能

 利用超声“脉冲回波重合法”技术,测定了立方晶体镱镓石榴石（GGG）各对称方向的超声波声速,及它们在流体静压力和单轴应力条件下,随压力的变化,计算了GGG的二阶和三阶弹性常数。它们分别是：c₁₁=3.04,c₁₂=1.31,c₄₄=0.94和c₁₁₁=-17.97,c₁₁₂=-12.86,c₁₂₃=-1.06,c₁₄₄=-2.11,c₁₆₆=-3.29,c₄₅₆=-0.94,单位是10¹¹ N/m²。根据这些数据,我们还计算了GGG晶体的德拜温度以及沿它的[001]→[111]→[110]→[100]传播的三个声学波分支（一个纵波,两个横波）的Gruneisen参数γ(p,N)的分布。     

ANALYSIS OF THE E2 TRANSITIONS BETWEEN THE d+a CLUSTER STATES OF 6Li WITH THE RGM

The E2 reduced transition probabilities between the d-a cluster states of ⁶Li were calculated by the RGM in this paper.The resulting B(E2;E₁→E₀)=21.06fm⁴ consistented with the experimental value 25.1±2.0fm⁴ more than the calculated values of the double-well cluster model including p-state exciting and LCCO.Also,the B(E2;E₃→E₀)=9.67fm⁴ coincided with the exprimental value 6.483±3.360fm⁴ within the error range.     

ZrN-ZrB2纳米复合材料的高压制备及性能表征

 以金属锆粉（Zr）和六方氮化硼粉（h-BN）为原料,结合高能球磨和高温高压合成技术,制备出了ZrN-ZrB₂纳米复合材料。利用X射线衍射、透射电镜和拉曼光谱等测试手段,对材料的结构和合成规律进行了研究。结果表明,高能球磨过程中只合成出了ZrN_x,没有出现ZrB₂,从N、B原子与Zr进行固态反应的热力学和动力学方面分析了原因。利用Zr与BN粉球磨10 h后的混料,在压力为5 GPa、温度为1 300 ℃的条件下,制备出了具有高致密度的ZrN-ZrB₂纳米复合材料。其维氏显微硬度（17 GPa）、热膨胀系数（7.57×10^-6 ℃^-1）和电阻率-温度系数（8.846×10^-4 ℃^-1）等材料参数的测量结果表明,ZrN-ZrB₂复合材料是一种集优良的力学、热学和电学性能于一体的纳米复合材料。     

THE ι-E PUZZLE AND THE GENERALIZED MOMENT ANALYSIS

We have introduced the photon angular distribution for moments of the process e⁺e^－→J/ψ→γB,B→P₁P₂P₃ to discuss the ι-E puzzle and got an effective criterion to distinguish whether there exist E(1⁺⁺) component in the peak for the process e⁺e^－→J/ψ→γKKπ.