(6aR,11aR)-3-羟基-4,9-二甲氧基紫檀烷分子的晶体结构

从多刺锦鸡儿 (豆科 )中分离得到一个紫檀烷型化合物— (6aR ,11aR) 3 羟基 4,9 二甲氧基紫檀烷 ,通过红外光谱、质谱、核磁共振氢谱、核磁共振碳谱、氢核 氢核相关谱、异核多量子相干谱和异核多键相干谱进行结构鉴定 .其单晶经X射线衍射测试表明 ,该化合物晶体属单斜晶系 ,空间群为P2 1 ,化学式为C1 7H1 6 O5,Mr =3 0 0 .3 0 .晶胞参数为 :a =6.4778(13 ) ,b =12 .63 1(3 ) ,c=8.83 68(18) ,β =95 .80 (3 ) o,V =719.3 (3 ) 3,Z =2 ,Dc=1.3 86Mg/m3,F(0 0 0 ) =3 16,μ =0 .10 2mm- 1 .结构由直接法解出 ,用全矩阵最小二乘法修正 ,最终偏离因子R =0 .0 3 3 2 ,wR =0 .0 862 .该分子由一个苯并吡喃环和苯并呋喃环组成 ,X射线衍射测试表明其绝对构型为顺式紫檀烷型     

葛根素-7-磷酸二乙酯的NMR研究

葛根素是从常用中药野葛根中分离提取出来的一种具有很强生物活性的异黄酮碳苷类化合物,设计并合成了一种新的化合物葛根素-7-磷酸二乙酯. 在常温下,这种新的化合物在NMR谱上有两组相关的信号峰,即在溶液中以两种不同的构象存在. 本文利用HSQC和HMBC等多种二维核磁共振技术对这种化合物的NMR谱进行了全归属.     

2-甲基-6-(2-甲苯基)-2-庚烯的波谱学研究

采用色谱法从蒲儿根花部位中分离得到2-甲基-6-(2-甲苯基)-2-庚烯,该化合物第一次以单体的形式得到,通过测定氢-氢相关谱(1H-1H COSY)、DEPT谱、异核单量子相关谱(HSQC)及异核多键相关谱(HMBC)等二维谱确定了该化合物的结构,并对该化合物的1H NMR和13C NMR谱进行了归属.     

2D NMR技术在多季碳二萜结构确定中的应用

应用二维核磁共振技术（2D NMR：¹H-¹H COSY、HMQC、HMBC）, 尤其是HMBC谱准确归属了多季碳二萜伊丽莎白素B（Elisabatin B）的¹H,¹³C信号,并经与已报道的数据比较,进一步明确指定了11个季碳的化学位移. 以伊丽莎白素B为例,较系统阐明了几种二 维核磁共振技术在天然产物结构确定中的作用和方法.     

吡虫啉生产过程中吗啉精馏副产物的核磁共振分析

采用核磁共振(NMR)技术对吡虫啉生产过程中吗啉精馏后的副产物进行了定性定量分析.二维扩散排序谱(2D DOSY)表明该产物由两种化合物组成.对样品的核磁共振氢谱(1H NMR)、二维扩散排序谱(2D DOSY)、碳谱(13C NMR)、DEPT、氢-氢相关谱(1H-1H COSY)、碳氢相关谱(HSQC)与碳氢远程相关谱(HMBC)进行了解析,对其所有的NMR谱信号进行了归属,确定样品所含的两种主要组份为双吗啉和烯胺.最后采用定量13C NMR技术得到了该精馏副产物中双吗啉和烯胺组成的摩尔比例为1∶4.     

3-氧,11α-羟基、Δ12-齐墩果烯及其类似化合物的13C NMR分析

化合物1-8属于近似结构的齐墩果烷型三萜,它们分别为:β-amyrin(1);3-氧,Δ^11,13(18)-齐墩果二烯(2);3β-羟基,Δ^11,13(18)-齐墩果二烯(3);3β,24-二羟基,Δ11,13(18)-齐墩果二烯(4);3,11-二氧,Δ¹²-齐墩果烯(5);3-氧,Δ9^(11),12-齐墩果二烯(6);3-氧,11α-羟基,Δ¹²-齐墩果烯(7);3β,11α-二羟基,Δ¹²-齐墩果烯(8).它们的¹³C NMR化学位移归属已确定,并通过了DEPT谱的验证.按结构特点分为三组:2~4为第一组,1,5,7,8为第二组,6为第三组.本文重点讨论了它们的¹³C NMR化学位移由其结构特点引起的变化,得到了化学位移与结构相关的有意义的结果.     

对氯苯氧基氯苯乙酮异构体的NMR分析

2-氯-4-(4-氯苯氧基)苯乙酮和2-(4-氯苯氧基)-4-氯苯乙酮互为同分异构体,它们的核磁共振谱十分相似,只通过一维核磁共振谱对其结构确定有很大的困难. 本文借助2-(4-氯苯氧基)-4-氯苯乙酮的分子晶体结构信息,利用二维核磁共振方法,对两个化合物的¹H NMR和¹³C NMR进行了指认,为这两种化合物的结构鉴定提供了重要依据.     

天然紫杉烷类化合物的核磁共振氢谱特征

在系统分析天然紫杉烷类化合物核磁共振氢谱的基础上，对具有不同骨架类型的天然紫杉烷类二萜化合物的核磁共振氢谱的特征进行了总结, 提供了部分不同类型的紫杉烷类化合物的核磁共振氢谱图. 这些¹H NMR特征对于紫杉烷类化合物的结构确定非常有益.     

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.     

丁酸氯维地平的波谱学数据与结构确证

丁酸氯维地平是一种短效二氢吡啶类钙通道阻滞剂,对丁酸氯维地平的紫外吸收光谱（UV）、红外吸收光谱（IR）、核磁共振氢谱（¹H NMR）、氢-氢相关谱(¹H-¹H COSY)、核磁共振碳谱¹³C NMR、DEPT谱、碳氢相关谱(HMQC)、碳氢远程相关谱(HMBC)及质谱（MS）进行了解析,对其所有的NMR谱信号进行了归属;讨论了红外光谱特征吸收峰所对应的官能团的振动形式,确证了丁酸氯维地平的结构.     

Time-resolved study of intramolecular charge transfer fluorescence in 1,2,3,4-tetrachloro-11H-isoindolo-[2, 1-a]-benzimidazol-11-one

Fluorescent properties of 1,2,3,4-tetrachloro-11H-isoindolo-[2,1-a]-benzimidazol-11-one (TCIB) in various organic solutions are described. Detailed investigation of the fluorescence from the solutions revealed that it was ascribable to the electronic transition from the lowest singlet excited state of an isolated molecule to its ground state, though the fluorescence spectrum was broad and structureless and the Stokes’ shift was about 1 eV. The absorption peak of TCIB was relatively insensitive to change in solvent polarity, whereas its fluorescence peak shifted to the red with an increase in the polarity. This finding suggests that the dipole moment of the molecule in the ground state is almost zero, and that the excited state has a non-zero dipole moment, which coincides with the predicted semiempirical molecular orbital calculation. Fluorescence quantum efficiency decreased with increase of solvent polarity. The efficiency was reduced by a factor of 39 in going from n-hexane solution to acetonitrile solution. The radiative rate constant also decreased with increase of solvent polarity. However, its reduction was very moderate; the reduction factor was only 2.5 for acetonitrile solution as compared with n-hexane solution. This finding indicates that the emitting state of the title compound is influenced by a solvent-dependent non-radiative mechanism, for which solvent-sensitive intersystem-crossing deactivation is tentatively proposed.     

晶型转变对尼龙11分子链运动的影响

为进一步认识分子链运动与晶型之间的关系,用熔融、冰水淬火和退火等方法制备了α和δ′两种晶型的尼龙11薄膜试样.42Hz～5MHz的介电松弛谱显示了两种不同晶型试样的分子运动特征.不同频率下的介电温度谱显示α型结晶中代表分子链段运动的主松弛较δ′型结晶出现在更高温度,说明退火引起的δ′向α晶型转变使分子链段运动受到了限制.研究结果还显示,α和δ′型结晶中分子链局域松弛运动的活化能基本相同,但α型的松弛时间较δ′型的大,松弛强度则较δ′型的小,表明晶型转变使尼龙11的分子链局域松弛运动也受到了一定程度的抑制.     

微过氧化酶的共振拉曼和表面增强拉曼光谱研究

采用电化学、共振拉曼和表面增强共振拉曼光谱研究了溶液态和吸附态微过氧化酶－１１（ＭＰ－１１）的电子传递及溶液和界面结构特征。结果表明,ＭＰ－１１在溶液中中心血红素铁以六配位状态存在,吸附于粗糙银电极表面时,则因ＭＰ－１１分子的重新取向而部分转化为五配位状态,氧化还原反应进一步促进这种配位状态的转化,并且配位状态也直接影响ＭＰ－１１的氧化还原性质。     

圆波导TM_(01)-TE_(11)模式变换器

提出了一种在圆波导中添加金属分割片及半边金属管壳的结构以实现圆波导TM01-TE11模式转换。通过金属分割片将圆波导分成两个半圆区域:其中一个半圆区域为空波导,另一半圆区域为填充一定厚度金属管壳的空波导。在S波段对设计的中心频率为2.8GHz的物理模型进行数值模拟与实验研究,模拟结果表明:在中心频率2.8GHz转换效率为99.56%,反射率低于0.01;在2.716～2.946GHz频带内转换效率大于90%,S11小于-10dB。实验中测试到的S11参数与模拟结果基本一致,证明了该变换器技术方案的可行性和模拟结果的正确性。     

Electromagnetic Properties of S11 States in a Light Cone Quark Model

Using relativistic spin-flavor wave functions of a Lorentz-covariant light cone quark model, we calculate the electromagnetic form factors of two S11 resonances, N（1535） and N（1650）, and the helicity amplitudes A1/2 and S1/2 for electroexcitation of the S11 resonances from the nucleon. The electromagnetic form factors of these S11 resonances are found to be similar to those of the nucleon in shape, while the charge form factor of neutral N（1650） is nearly zero. The relative peak height of the S11 charge form factors is controlled by the mixing angle common to both resonance wave functions. As in most quark models, there is a systematic overestimate of A1/2 in both N（1535） and N（1650） cases at the photon point. A sizeable S1/2 for all cases is produced as suggested by experiments.     

Electromagnetic Properties of S11 States in a Light Cone Quark Model

Using relativistic spin-flavor wave functions of a Lorentz-covariant light cone quark model, we calculate the electromagnetic form factors of two S11 resonances, N(1535) and N(1650), and the helicity amplitudes A1/2 and S1/2 for electroexcitation of the S11 resonances from the nucleon. The electromagnetic form factors of these S11 resonances are found to be similar to those of the nucleon in shape, while the charge form factor of neutral N(1650) is nearly zero. The relative peak height of the S11 charge form factors is controlled by the mixing angle common to both resonance wave functions. As in most quark models, there is a systematic overestimate of A1/2p in both N(1535) and N(1650) cases at the photon point. A sizeable S1/2 for all cases is produced as suggested by experiments.     

Radiation patterns of the HE11 mode and Gaussian approximations

The problem of the approximation of the HE₁₁ radiation pattern by a Gaussian distribution is discussed. A numerical comparison between the HE₁₁ far-field theoretical pattern, and the Gaussian approximations derived by Abrams and by Crenn, permits and evaluation of the precision of these approximations. A new optimized HE₁₁ Gaussian approximation is calculated: the value of r_o=0.421a (or w_o=0.596a) for the beam radius at the waist is demonstrated to give the best HE₁₁ Gaussian approximation in the far-field and is very close to the result given by Crenn, while the Abrams value is less precise. The calculations are extended to the near-field. Universal curves for intensity, amplitude and power distribution are given for the HE₁₁ radiated mode. These results are of interest for laser waveguide applications and for plasma ECRH transmission systems.     

An Improved Time-Saving Synthesis for [11CMethyl] Iodide

[¹¹]CMethyliodide is a key to a large scale of ¹¹C-PET-radiopharmaceuticals. A method was devised for its efficient production in a yield between 85 and 90% within 7 minutes only. The use of tetrahydrofuran (THF) opens the possibility to absorb the starting [¹¹C]CO₂ at room temperature. The methyl iodide generation from its precursor can be achieved in THF directly or in aqueous solution.

Es wird die Mögliclikeit gezeigt, [¹¹C]Mthyliodid, einer Schlüssclverbindung der ¹¹C-Chemie, innerhalb von nur 7 Minuten in Ausbeuten zwischen 85 und 90% herzustellen. Die Verwendung von Tetrahydrofuran als Lösungsmittel anstelle von Diethylether ermöglicht die vollständige Absorption des Ausgangs- [¹¹C]C0₂ bei Raumtemperatur. Die Umsetzung des Vorproduktes zum Alelhyliodid kann wahlweise direkt in Tetrahydrofuran oder in wäβriger Lösung vorgenommen werden.     

Effect of pressure and interstitial atoms on magnetic properties of LuFe11Ti Intermetallics

Magnetisation and magnetocrystalline anisotropy of the LuFe₁₁Ti intermetallics have been studied under pressure up to 1.2 GPa in temperatures from 5 K to 350 K using a miniature CuBe pressure cell and a SQUID magnetometer. A decrease of Fe-moment under pressure is compatible with the increase of Fe-moment in hydride and nitride of LuFe₁₁Ti. A complex dependence of magnetocrystalline anisotropy on volume of the elementary crystal cell of LuFe₁₁Ti and its hydride and nitride has been observed.     

退火与极化温度对尼龙11薄膜驻极体内陷阱能级分布的影响

用热释电技术研究了尼龙11薄膜驻极体制备过程中热处理与极化温度对驻极体陷阱能级分布的影响.结果显示，淬火驻极体的热释电流谱上存在四个空间电荷退陷阱电流峰，而在退火处理后则显示两个退陷阱电流峰.采用多点法对热释电流谱进行理论拟合可以将各个退陷阱电流峰分离并得到它们的陷阱深度参数.这些参数进一步表明，淬火尼龙11薄膜驻极体内存在四个空间电荷的陷阱能级，极化温度升高对它们的分布情况影响不大；退火处理后，陷阱能级减少为两个，且随着极化温度的升高，较浅的陷阱能级有明显向较深陷阱能级接近的趋势. 关键词： 尼龙11 薄膜驻极体 热释电 热处理