红光皂甙元及其两个甾体皂甙的NMR研究

从番麻(Agave americana L.)发酵的叶汁中分离得到红光皂甙元(hongguanggenin)、Cantalasaponin-1及一个新的甾体皂苷Agameroside-1. 运用2D NMR技术,包括DQF ¹H-¹H COS Y,HSQC,HMBC,HSQC-TOCSY,ROESY等技术,首次全归属了3个甾体化合物的氢和碳的化学位移,并总结了红光皂甙元的甙化位移效应,从而修正了文献中部分碳信号归属以及甙元的甙化位移效应.     

一系列薯蓣皂甙元-α-L鼠李糖基-(1→2)和(1→4)-β-D葡萄糖甙的1H和13C NMR归属

用同核和异核二维核磁共振方法全归属了一系列合成的薯蓣皂甙元-α-鼠李糖基-β-D葡萄糖甙的¹H和¹³C核磁共振谱线.这些薯蓣葡萄糖甙是薯蓣皂甙元-β-D葡萄糖甙(1),薯蓣皂甙元-α-L鼠李糖基(1→2)-β-D葡萄糖甙(2),薯蓣皂甙元-α-L鼠李糖基(1→4)-β-D葡萄糖甙(3),薯蓣皂甙元[-α-鼠李糖基-(→2)]-α-L鼠李糖基→-(1→4)-β-D葡萄糖甙(4)以及薯蓣皂甙元[-α-L鼠李糖基-(1→2)]-β-D阿拉伯糖基-(1→4)-β-D葡萄糖甙(5).     

一系列薯蓣皂甙元-β-D葡萄糖基-(1→2)和(1→3)-β-D葡萄糖甙的1H和13C NMR归属

用同核和异核二维核磁共振方法全归属了一系列合成的薯蓣皂甙元-β-D葡萄糖甙的¹H和¹³C核磁共振谱线.这些薯蓣葡萄糖甙是薯蓣皂甙元-β-D葡萄糖甙(1),薯蓣皂甙元-β-D葡萄糖基-(1→2)-β-D葡萄糖甙(2),薯蓣皂甙元,-β-D葡萄糖基-(1→3)-β-D葡萄糖甙(3),薯蓣皂甙元[-β-D葡萄糖基-(1→2)-β-D葡萄糖基(1→3)-β-D葡萄糖甙(4)以及薯蓣皂甙无[-α-L鼠李糖基-(1→2)]-β-D葡萄糖基-(1→3)-β-D葡萄糖甙(5).     

二维核磁共振波谱归属人参二醇的NMR谱线

人参二醇是构成人参皂甙的三种甙元之一,具有较高的生物活性,对它的生理活性和药理作用研究证明:人参二醇具有一定的抗肿瘤作用,本文报道用异核COSY、COLOC-S等2D NMR方法归属人参二醇的¹³C和¹H化学位移.     

一系列薯蓣皂甙元-β-D葡萄糖基-(1→2)和(1→3)-β-D葡萄糖甙的1H和13C NMR归属

用同核和异核二维核磁共振方法全归属了一系列合成的薯蓣皂甙元-β-D葡萄糖甙的1H和13C核磁共振谱线．这些薯蓣葡萄糖甙是薯蓣皂甙元-β-D葡萄糖甙（1）,薯蓣皂甙元-β-D葡萄糖基-（1→2）-β-D葡萄糖甙（2）,薯蓣皂甙元,-β-D葡萄糖基-（1→3）-β-D葡萄糖甙（3）,薯蓣皂甙元[-β-D葡萄糖基-（1→2）-β-D葡萄糖基（1→3）-β-D葡萄糖甙（4）以及薯蓣皂甙无[-α-L鼠李糖基-（1→2）]-β-D葡萄糖基-（1→3）-β-D葡萄糖甙（5）．     

20(R)和20(S)-人参皂甙Rg2碳氢NMR信号全指定

20(R)和20(S)人参皂甙Rg₂属于达玛烷型四环三萜类化合物.应用2DNMR技术:¹H-¹H COSY、HMQC和HMBC全归属20(R)和20(S)人参皂甙Rg₂碳和氢质子信号,为该类型化合物的结构鉴定提供波谱学依据.     

二维接力-HOHAHA和NOE差谱法测定甙类化合物的结构

该文提出一种新的二维接力-HOHAHA实验方法.研究结果表明,该方法可用于从高度重迭的谱图中分离出各个糖体的¹H NMR信号,并且与NOE差谱实验相结合可以用于测定甙类化合物中糖体间和糖体与甙元间的连接位置.本方法以¹H NMR为基础,故其灵敏度比以¹³C NMR为基础的甙化位移方法高得多.     

黄酮类化合物-O-甙的13C NMR谱

概述了黄酮类化合物-O-甙(包括双糖甙及寡糖甙)的¹³C NMR谱鉴定中涉及的溶剂选择,糖的数目与鉴定,糖的端基信号与甙化位移,甙元的鉴定,双糖及寡糖甙中各单糖的连接次序,以及糖链上的酰基取代等.     

三七皂苷NMR研究Ⅱ——3个原人参二醇型双糖链配糖体的NMR信号全归属

运用2D NMR技术，如DQF ¹H-¹H COSY，HMQC，HMBC，TOCSY等，对3 个原人参二醇型双糖链配糖体人参皂甙-Rd,三七皂甙-E和七叶胆皂甙XVII的氢和碳的化学位移首次进行了全归属.     

脱水淫羊藿素-3-O-甙类化合物的核磁共振谱研究

用远程¹H-¹³C COSY (HMBC)技术研究了从朝鲜淫羊藿中分离出的二个脱水淫羊藿素-3-O-甙类化合物,朝藿甙A和箭藿甙B,确定了其骨架碳的化学位移.并重新评估了前期文献对该类化合物C-5、C-7和C-4'信号的归属.     

蒜氨酸和甲基蒜氨酸的红外及拉曼光谱研究

利用傅里叶红外光谱和共聚焦显微拉曼光谱技术,比较分析了大蒜主要功能活性成分前体蒜氨酸和甲基蒜氨酸粉末纯品的红外和拉曼谱。在3 200～2 800 cm-1和1 700～200 cm-1波段检测到显著的红外和拉曼吸收峰,其中蒜氨酸在3 080,1 617,1 582,1 496,1 418,1 342,1 301,919 cm-1处有8个较强的红外吸收峰,以及在3 088,1 636,1 404,1 290,1 051,790,745,693,588 cm-1处有9个较强的拉曼振动峰,可作为蒜氨酸的特征峰;甲基蒜氨酸在1 644,1 481,1 395,1 370,1 233,1 068,1 004,892 cm-1处有8个较强的红外吸收峰,以及在1 644,1 310,1 073,1 011,998,893,846,702,676 cm-1处有9个较强的拉曼振动峰,可作为甲基蒜氨酸的特征峰。蒜氨酸和同系物甲基蒜氨酸的红外及拉曼光谱具有明显差异,红外及拉曼光谱技术为蒜氨酸及其同系物的快速、 简便的分析提供了方法。     

Computation of the electric and magnetic fields induced in a plasmacreated by ionization lasting a finite interval of time

S.C. Wilks et al. (1988) showed that when an infinite expanse of gas, carrying a linearly polarized electromagnetic wave, is instantly ionized, the initial wave is frequency upshifted. This phenomenon of frequency upconversion through flash ionization gives rise to steady-state transmitted and reflected electromagnetic waves and to a time-independent magnetic field. The case in which the final state of ionization is achieved not instantly but in a finite turn-on time, 0⩽t⩽t 0, which is followed by the steady state, is studied. It is shown that the electric field is obtained from the one-dimensional Helmholtz equation, d²F(t)/dt² +ω₀²g(t)F( t)=0, if electrons are born at rest when they are created during ionization. As a result, the instantaneous frequency of the upshifted radiation is ω(t)=√g(t). The electric field can be solved exactly for specific choices of g(t). It is solved using WKB approximations for arbitrary g(t). The magnetic field is then found by integrating Faraday's law. It is found that the steady-state electric field amplitude depends on the steady-state value o f g(t) but does not depend on the ionization time t₀. Conversely, the static magnetic field amplitude decreases with increasing turn-on time     

Some interruption criteria for short high-frequency vacuum arcs

If the contacts of a vacuum interrupter open shortly before a current zero, the transient recovery voltage (TRV) can cause a reignition and reestablish the arc. When the current in a diffuse vacuum arc passes through zero, there is a distinct pause before the TRV builds up (approximately 40 ns for copper). During this pause the gap carries conduction current only with an ion component which depends on dI /dt, varying between 3 A for dI/dt=60 A/μs and 60 A for dI/dt=1235 A/μs. The ion current subsequently decays in tens or hundreds of nanoseconds. It can be distinguished from the displacement current at this time by varying dV/dt, keeping the other parameters constant. Among the interruption criteria for short high-frequency vacuum arcs, dI /dt prior to current zero and initial dV/dt are the most important. High values of dI/dt are more likely to precipitate reignitions, but breakdowns can occur after lower dI/dt's if the gap has been subjected to a high current for a relatively long time (>100 μs)     

Adsorption of hydrogen and carbon monoxide on Rh(1 1 1)/V surface alloys

A detailed study of the interaction of hydrogen and carbon monoxide with two different Rh(1 1 1)/V surface alloys (1/3 monolayer of V in the second atomic layer or 1/3 monolayer of V in form of islands on the surface) is presented in comparison to the clean Rh(1 1 1) surface. For hydrogen a decrease in the sticking coefficient is found for both alloy surfaces. The sticking coefficient of H₂ as a function of the translational energy is similar to the Rh(1 1 1) surface, showing a direct activated adsorption mechanism. For low translational energies hydrogen adsorption is dominated by dynamical steering on Rh(1 1 1) and by a precursor mechanism on the Rh(1 1 1)/V subsurface alloy. The H₂ TPD desorption peaks are shifted to lower temperatures on the alloy surfaces, caused by the downshift of the metal d-band due to V alloying. On all three surfaces the saturation coverage of hydrogen was measured, giving 1.2, 1.0 and 0.8 monolayer for Rh(1 1 1), the Rh(1 1 1)/V subsurface alloy and for the Rh(1 1 1)/V islands, respectively. For CO the sticking coefficients and the saturation coverages are basically the same on the Rh(1 1 1) and the alloy surfaces. There is an extrinsic precursor on the ordered CO (√3×√3) phase on the Rh(1 1 1) surface, but there is no evidence for such a precursor on the Rh(1 1 1)/V subsurface alloy. On the Rh(1 1 1)/V islands surface, the extrinsic precursor exists on the Rh(1 1 1) surface between the V islands. Apparently this precursor is only stable on the ordered CO layer on Rh(1 1 1).     

傅里叶红外光谱研究血清白蛋白构象

用傅里叶红外光谱法研究了ＢＳＡ及其水溶液的红外光谱。通过对其酰胺Ｉ带傅里叶自转积谱分析,为其及部分水溶液中的二级结构构象进行了指认。结果表明,ＢＳＡ水溶液状态与固态时的二级结构是不同的。随着溶液浓度的降低,酰胺Ｉ带二级结构峰存在明显的位移现象,即１６０９．８６ｃｍ＾－１位移到１６０８．２４ｃｍ＾－１,１６３３．８５位移到１６３８．３６ｃｍ＾－１,１６５３．６９ｃｍ＾－１位移到１６５６．１０ｃｍ＾－     

Structural, electronic properties and stability of the (1 × 1) PbTiO3 (1 1 1) polar surfaces by first-principles calculations

Under GGA, the structural, electronic properties and stabilities of four different (1 × 1) terminations of cubic PbTiO₃ (1 1 1) surface, the directly cleaved (1 1 1)-Ti and (1 1 1)-PbO₃ terminations and the constructed (1 1 1)-TiO and (1 1 1)-PbO₂ ones, have been systematically studied by using projector-augmented wave method implemented in VASP. For (1 1 1)-Ti and (1 1 1)-PbO₃ terminations, Ti-O bonds between the outermost two layers are enhanced after relaxation, while those between the second and the third layers are weakened. In addition, a contraction of O-O distance in surface PbO₃ layer is also found for (1 1 1)-PbO₃ termination. Moreover, electronic structures of both (1 1 1)-Ti and (1 1 1)-PbO₂ terminations are significantly influenced by structure relaxations, and the effects of the surface on the DOS are dominantly on the Ti layers, especially the CB. For a constructed (1 1 1)-TiO termination, the relaxation results show both Ti-O bonds between the outermost two layers and those between the second PbO₃ layer and the third Ti layers are enhanced. For a constructed (1 1 1)-PbO₂ termination, Ti-O bonds between the outermost two layers are also enhanced as in the (1 1 1)-TiO termination, however, inequivalent Ti-O bonds between the second layer Ti atom and the third layer O atoms are found, with two bonds expanding and the other one contracting. Results of electronic structure calculations show these two constructed terminations are all insulating and changes of DOS originate dominantly from modifications of surface compositions. Furthermore, it is found that for all four different (1 1 1) terminations, the movements of the cation and/or anion on the outermost layer along the surface normal direction after relaxation all result in a reduction of the space electric field. In O and Pb external environments, it is predicted that (1 1 1)-PbO₂ termination is the most stable one in O- and Pb-rich environments, however, the (1 1 1)-Ti termination is stable one in O- and Pb-poor conditions. The (1 1 1)-TiO termination also shows a stability domain in moderate O and Pb environments.     

杨木和桉木的二维相关红外光谱

采用红外光谱结合二维相关分析技术,对两种速生阔叶树杨木和桉木进行了快速鉴别研究。结果表明,二者在一维红外光谱图上差别不明显,而二维相关红外谱图具有较大的差别。在800～1 500 cm-1波段范围内,二者的同步二维相关光谱图还比较类似,都在1 221,954,879 cm-1处出现较强的自动峰,在1 470, 1 150,1 1 05, 1 008 cm-1处出现微弱的自动峰。在1 500～1 800 cm-1波段范围内,杨木在1 655 cm-1处有一个非常强的自动峰,在1 600 cm-1附近有一个很弱的自动峰,二者形成了一对正的交叉峰;桉木在1 725,1 650和1 600 cm-1处均出现较强的自动峰,并形成一个较强的3×3峰组。除此之外,桉木还在1 580和1 510 cm-1出现2个弱的自动峰,其中1 580 cm-1和其余4个自动峰形成了较弱的负交叉峰,1 510 cm-1和其他3个自动峰形成正的交叉峰。这说明,桉木在1 500～1 800 cm-1波段对应的官能团比杨木相应的官能团对热微扰更为敏感,杨木和桉木的二维相关红外光谱差别,快速鉴别这两种木材的。     

GeS分子基态和低激发态的势能曲线与光谱性质

本文以aug-cc-pv5Z为基组, 采用考虑Davidson修正的多参考组态相互作用方法(MRCI+Q)得到了GeS分子基态(X¹Σ⁺)和5个低激发态(1¹Σ, 1¹Δ, A¹Π, 1⁵Σ⁺, 2⁵Σ⁺)的势能曲线. 计算结果表明: 2⁵Σ⁺态为排斥态, 其余5个态为束缚态; 6个态有着共同的离解通道, 离解极限均为Ge(³P)+S(³P). 利用计算得到的势能曲线得了X¹Σ⁺, 1¹Σ^-, 1¹Δ, A¹Π和1⁵Σ⁺态的垂直跃迁能T_e, 平衡键长R_e, 离解能D_e, 谐振频率ω_e, 非谐性常数ω_ex_e及平衡位置的电偶极矩. X¹Σ⁺态的R_e 为2.034 Å, D_e 为5.728 eV, ω_e为571.73 cm^-1, ω_ex_e为1.6816 cm^-1, 平衡位置的电偶极矩为1.9593 Debye. 激发态1¹Σ, 1¹Δ, A¹Π, 1⁵Σ⁺的T_e 依次为25904.81, 26209.22, 32601.19, 43770.26 cm^-1; R_e依次为2.313, 2.322, 2.188, 2.8790 Å; D_e依次为2.524, 2.487, 1.694, 0.3036 eV, ω_e依次为358.90, 353.08, 376.32, 134.96 cm^-1; ω_ex_e依次为1.2421, 1.2151, 1.6608, 1.9095 cm^-1; 平衡位置的电偶极矩依次为1.3178, 1.4719, 1.5917, -1.9785 Debye. 通过求解核运动的薛定谔方程得到了J=0时X¹Σ⁺, 1¹Σ^-, 1¹Δ, A¹Π和1⁵Σ⁺态前30个振动态的振动能级G_v和分子常数B_v, 得到的结果和已有的实验值及其他理论值符合较好.     

应用红外光谱法鉴别肉苁蓉及其混淆品草苁蓉和锁阳

采用傅里叶变换红外光谱法结合二维相关分析技术分别对药用植物肉苁蓉及其混淆品草苁蓉、锁阳进行了鉴别研究.结果表明,三者的红外光谱图表现出了一定的差异性:肉苁蓉在1 730和931 cm-1有吸收峰,草苁蓉在1 510,1 375,1 266 cm-1处存在吸收峰,锁阳的最高峰位于1 614cm-1处.在二阶导数谱图上三者差异更加明显:肉苁蓉在1 453,1 336,931,892 cm-1处都有较强的吸收峰.其中931 cm-1处的吸收峰较尖锐,强度也最强;草从蓉的最强峰位于1 509 cm-1,并且1 633和1 161 cm-1处的吸收峰明显变宽,强度也变大;锁阳在1 682cm-1处有较尖锐的吸收峰,1 605 cm-1附近的吸收峰强度也较大.二维红外谱图不但差别明显,而且直观.三者提取物的红外光谱同样存在显著差异.应用该方法能够实现肉苁蓉药材与混淆品的快速、准确鉴别.