Study of electrochemical behavior of ergosterol by in situ thin layer circular dichroic spectroelectrochemistry

The electroxidation of ergosterol was studied by in situ circular dichroic (CD) spectroelectrochemistry with a long optical path length thin layer cell. It was confirmed that the oxidation of ergosterol in ethanol solution is a two-electron irreversible electrochemical process with strong adsorption of an electroinactive product at the glassy carbon electrode, which blocks the electrochemical reaction. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential, E-0 = 1.00 V, alpha n(alpha) = 0.302, the standard electrochemical rate constant, k(0) = 6.1(+/-0.4) x 10(-4) cm s(-1) and the adsorption constant, beta = 19 +/- 1, were obtained. The number of electrons transferred (n = 1.86) was estimated by cyclic voltammetry.

聚电解质中阳离子对铁氰化钾还原过程影响的原位显微红外光谱电化学

采用原位显微红外光谱电化学方法研究了聚电解质中不同阳离子(Li+,Na+,K+和TBA+)存在下铁氰化钾的电化学还原过程．观察到支持电解质阳离子对Fe(CN)3-/4-6动频率的影响，探讨了还原反应机理

Oxygen permeating properties of the mixed conducting membranes without cobalt

A new series of mixed conducting oxides, Sr10-n/2BinFe20Om (n = 4, 6, 8, 10), were synthesized by a solid state reaction method, and they have high oxygen permeability. The oxygen permeation rate at 1150 K is 0.41 ml(STD)/ cm(2).min for n = 6 and 0.90 ml(STD)/cm(2).min for n = 10, which is two times higher than that for Sr1-xBixFeO3 (x = 0.5). For the Sr1-xBixFeO3 (x = 0.1, 0.3, 0.5) series, the oxygen flux increases with increasing Bi content. (C) 1998 Elsevier Science Ltd.

Magnetic and magnetotransport properties of intermetallic SmMn2Si2

The magnetic properties of naturally layered intermetallic compound SmMn2Si2 with textured structure have been studied. There exist a ferromagnetic transition at 35 K and two antiferromagnetic transitions at 120 and 230 K. The antiferromagnetic state below 230 K exhibits different magnetoresistance, with a negative magnetoresistance of 3%-4% for current I applied perpendicular to the c axis and with a positive magnetoresistance effect of about 4%-6% for current I parallel to the c axis. The observed magnetoresistance is likely to be related to magnetovolume effects. In the ferromagnetic state, a positive magnetoresistance with a maximum increase of 22% under an applied field of 5 T is observed at 4 K, and both H perpendicular to I and H parallel to I configurations show positive magnetoresistance. (C) 1997 American Institute of Physics.

1,4-二丙氧基-2,3二氰基萘的晶体结构

用 Siemens P4四圆衍射仪,测得了1,4-二丙氧基-2,3-二氰基萘的晶体结构。晶体属单斜晶系,空间群为 C2/C。晶格参数 a=14.987(3)A,b=10.527(2),c=11.755(2),β=118.98°(3),晶胞体积 V=1622.4(6)3,Z=4,Dc=1.205Kg/m~3,μ(MoK_α)=0.079mm~(-1),F(000)=624,T=293(2)K_o晶体结构应用直接法,解出最后的偏离因子 R=0.0554[1425个Ⅰ≥2σ(Ⅰ)衍射点]。结构分析表明,萘环的1,4和2,3位碳原子上的氢原子分别被丙氧基和氰基所取代,由于取代基的引入使萘环的结构有所改变。

LUMINESCENCE AND ENERGY-TRANSFER OF RARE-EARTH-METAL IONS IN MG2Y8(SIO4)(6)O-2

The photoluminescence of Ce3+, Tb3+ and Sm3+, and energy transfer from Ce3+ to Tb3+, Dy3+ and Sm3+ in Mg2Y8(SiOd(4))(6)O-2 are reported and discussed. The Ce3+ ion shows blue luminescence under UV excitation, and occupies simultaneously the 4f site and 6h site in the host lattice. The optimum concentrations for the D-5(3) and D-5(4) emissions of Tb3+ and the (4)G(5/2) emission of Sm3+ are determined to be 0.04, 0.20 and 0.10 mol in every mol of Mg2Y8(SiO4)(6)O-2, respectively. The critical distances responsible for the cross-relaxation between the D-5(3)-D-5(4) and F-7(6)-F-7(0) transitions of Tb3+ and between the (4)G(5/2)-F-4(9/2) and H-6(5/2)-F-4(9/2) transitions of Sm3+ are estimated to be 1.43 and 1.06 nm, respectively. Both Tb3+ and Dy3+ can be sensitized by Ce3+, but Ce3+ and Sm3+ quench each other.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF SOME NITRO-CONTAINING BIFUNCTIONAL AROMATIC-COMPOUNDS - LOCATION OF PROTONATION SITE

It is found that the nitro substituent of some aromatic bifunctional compounds shows unusual reactivity towards protonation. In the chemical ionization mass spectra of nitrobenzoic acids and their esters and amides, and of nitrophenols and their ethers, protonations on the carboxyl, ester, amide, hydroxyl or alkoxyl groups are highly suppressed by that on the nitro group. As a result, fragmentations based on protonation on these groups unexpectedly become negligible. Ortho effects were observed for all the ortho isomers where the initial protonation on the nitro group is followed by an intramolecular proton transfer reaction, which leads to the expected 'normal' fragmentations. Protonation on the nitro substituent is much more favourable in energy than on any of the other substituents. The interaction of the two substituents through the conjugating benzene ring is found to be responsible for this 'unfair' competitive protonation. The electron-attracting nitro group strongly destabilizes the MH+ ions formed through protonation on the other substituent; although the COR (R = OH, OMe, OEt, NH2) groups are also electron-withdrawing, their effects are weaker than that of NO2; thus protonation on the latter group produces more-stable MH+ ions. On the other hand, an electron-releasing group OR (R = H, Me, Et) stabilizes the nitro-protonated species; the stronger the electron-donating effect of this group the more stable the nitro-protonated ions.

ISOPOLYMOLYBDIC ACID-POLY(4-VINYL)PYRIDINE FILM MODIFIED ELECTRODE

Electrochemical polymerization of 4-vinylpyridine produced a uniform poly(4-vinyl)pyridine(PVP) film on the glassy carbon (GC) electrode surface. The isopolymolybdic acid-PVP film-modified electrode was prepared by soaking the PVP/GC electrode in the 0.05 M H2SO4 aqueous solution containing 0.005 M isopolymolybdic acid (H4Mo8O26). The latter (catalyst) is incorporated and held in the PVP film electrostatically. The electrochemical behavior and electrocatalytic properties of this H4Mo8O26-PVP/GC electrode was described. The results indicate that this modified electrode has good stability and electrocatalytic activity on the reduction of chlorate and bromate ions in aqueous solution. The catalytic process is regarded as an EC mechanism.

ANALYSIS OF A NEW SUPERCONDUCTING PHASE IN THE BISRCACUO SYSTEM

By doping Sb, Ba and In to the Bi-system and with the variation of nominal atomic ratio of Cu, Sr and Ca, a new possible phase is found with T(c) almost-equal-to 105 K, but with a structure of 2212 phase. Effects of post-sintering treatment from air-quenched to O2-annealed were investigated for the approximately 105 K new phase.

两种海藻提取物的化学成分和生物活性的研究及其应用

本论文的研究工作由两部分组成，第一部分研究了海带（Laminaria japonica）水提取物中的活性物质，并研究了提取物对蔬菜促生长的影响及其作用机制。第二部分对三列凹顶藻(Laurencia tristicha)乙醇提取物的乙酸乙酯相进行了活性筛选和化学成分研究，并对其中分离得到的单体化合物进行了生物活性筛选。 第一部分主要以中国人工养殖的海带为原料，使用与海藻多糖生产相结合的提取技术并浓缩其中的有效成分。对浓缩提取物进行了蔬菜的农田效果实验，并对作物抗旱性能的增加、作物硝酸盐积累的减少、作物品质的改善、以及作物抵抗病毒病的能力等影响进行了作用机制方面的研究。海藻浓缩提取物进行的农田效果实验表明：作物抗旱型相对含水量RWC值在92%~94%之间；病毒病的防治效果最高可达到91%；作物的品质有明显的改善，最重要的是首次发现海藻提取物有降低蔬菜中硝酸盐的含量（硝酸盐的含量是与有机蔬菜区别的重要指标之一）的作用。该部分研究工作的创新性主要体现在：（1）首次在国内外提出和采用与海藻多糖生产相结合的提取技术。该技术的应用不但减少了提取成本，使工业化生产成为可能,更重要的是使我国的海藻工业生产可能实现高值化和开辟综合利用的新途径。（2）首次发现海藻中的小分子海藻多糖具有和细胞激动素、甜菜碱、植物生长素等活性物质同样的生物活性。 第二部分的研究是在查阅了大量的近20年来国内外有关红藻凹顶藻中化学成分研究的相关文献的基础上，对凹顶藻中的次生代谢产物进行了综述。该论文主要是通过对红藻三列凹顶藻的95%乙醇提取物的乙酸乙酯相进行化学成分分析和生物活性筛选以期能够发现具有药用前景的活性先导化合物。 为了寻找具有生物活性的化合物，我们对采自我国南海硇洲岛海域的红藻三列凹顶藻的95%乙醇提取物的乙酸乙酯相进行了活性筛选。采用MTT法对其在KB细胞株、Bel-7402细胞株、PC-3M细胞株、MCF-7细胞株、Ketr-3细胞株模型上进行了细胞毒活性测试；采用酶模型对其进行了Na+,K+-ATPase的抑制活性测试；采用MTT法对其在犬主动脉血管模型上进行了血管平滑肌细胞增殖抑制活性测试；结果表明，三列凹顶藻的95%乙醇提取物的乙酸乙酯相对Na+,K+-ATPase和犬血管平滑肌细胞增殖具有一定的抑制活性。 利用正相和反相色谱、Sephadex LH-20色谱以及反相HPLC等手段进行分离纯化，从我国南海海域的红藻三列凹顶藻中分离得到33种化学成分，通过波谱学方法（IR、MS、NMR）以及X-ray单晶衍射试验对其化学结构进行了确证，其中化合物L1~L8为新结构化合物，化合物L5为具有新骨架的全新结构化合物，化合物L9~L13为新天然产物，化合物L18和L22系首次从海洋生物中获得，所有化合物均为首次从该属海藻中得到。新化合物L1~L8均为倍半萜类化合物，命名分别为：(1R,3R)-(-)-3-(3-hydroxy-4-methylphenyl)- 1,3-dimethyl–2-methylidene cyclopentanol (L1), (1R,3R)-(-)-3-(4-methylphenyl)-1,3-dimethyl-2-methylidenecyclopentanol (L2)， (1R, 3R)-(-)-3-(2-hydroxy-4-methylphenyl)-1,3-dimethyl–2–methylidenecyclopentanol (L3)，(+)-(1S,2R)–2-(3–hydroxy–4–methylphenyl)-1,2-[3.1.0]bicy-clohexane (L4)，()-(1S,2R) -5-hydroxy–6–methyl-spiro-dihydrobenzofuran-2(3H),2-{1-methyl-[3.1.0]bicyclohexane} (L5), (+)-6-methyl-2-(p-tolyl)hept-4-en-2,6-diol (L6)，(3R,3aS,8bS)-(-)-2,3,3a,8b–tetrahydro–7-bromo – 3 a– hydroxymethyl - 3, 6, 8b - trimethyl-1H- cyclopenta[b] benzofuran (L7 )，(3R, 3aS, 8bS) - (-) - 2,3,3a,8b–tetrahydro–3 a–hydroxymethyl-3,6,8b -trimethyl -1H – cyclopenta [b] benzofuran (L8)。25个已知结构化合物确定为：(+)-(1R,2R)-4-bromo-1,5, 9–trimethyl–12– methylidene–8–oxa-tricyclo[7.2.1.02]dodeca-2,4,6-triene (L9)，(3S,3aR,8bS)-(-)-2,3,3a, 8b– tetra -hydro–7-bromo–3–hydroxy-3,3a,6,8b-tetramethyl-1H-cyclopenta[b]benzofu- ran (L10 )，(3R, 3aR, 8bS) - (-) - 2, 3, 3a, 8b – tetrahydro – 7 - bromo – 3 – hydroxy - 3,3a,6,8b - tetramethyl - 1H - cyclopenta [b] benzofuran (L11 )，(3S,3aR,8bS) - (-) - 2, 3, 3a, 8b – tetrahydro –3–hydroxy -3, 3a, 6, 8b - tetramethyl-1H-cyclopenta[b]benzofuran (L12 )， ( 3aR, 8bS) - (-) - 3a,8b –dihydro–7 - bromo – 3, 3a, 6, 8b - tetramethyl - 1H - cyclopenta[b]benzofuran (L13 )，aplysinol (L14 ) ，aplysin (L15)，laurebiphenyl (L16)，johnstonol (L17)，gossonorol (L18)，7,10-epoxy-ar- bisabol-11-ol (L19)，10-epi-7,10-epoxyarbisabol-11-ol (L20) 3β-hydroxy- 5α, 6α-epoxy- β- ionone (L21 )，3β-hydroxy-5β,6β-epoxy-β-ionone (L22 )，胆甾醇 (L23 )，胆甾-5-烯-3β,7α二醇胆甾-5-烯-3β,7α二醇 (L24)，β-谷甾醇 (L25)，叶绿醇 (L26 )，玉米黄素 (L27 )，对羟基苯甲醛 (L28 )，3-吲哚甲醛 (L29 )，1-O-十六烷酰基-3-O-β-D-吡喃半乳糖基-丙三醇(L30 )，1-O-十八烷酰基-3-O-β-D-吡喃半乳糖基-丙三醇 (L31 )，丙三醇-1-软脂酸单酯 (L32 )，正十六碳酸 (L33 )。 采用MTT法对其中23个单体化合物在Bel-7402细胞株、BGC-823细胞株、A549细胞株、A2780细胞株、HCT-8细胞株和HELL细胞株模型上进行了细胞毒活性测试；采用MTT法对其中13个单体化合物在犬主动脉血管模型上进行了血管平滑肌细胞增殖抑制活性测试；结果表明，部分单体化合物显示出一定的生物活性。

Catena-Poly[[[tetra-mu(2)-aqua-heptaaqua-(mu(2)-benzene-1,3,5-tricarboxylato)-mu(3)-hydroxido-trinickel(II)sodium]-mu(4)-benzene-1,3,5-tricarboxylato]sesqui-hydrate]

The title coordination polymer, {[Ni3Na(OH)(C9H3O6)(2)( H2O)(11)] center dot 1.5H(2)O}(n), is built up from three independent Ni-II ions and one Na-I cation bridged by benzene-2,4,6-tricarboxylate ( BTC) ligands and water molecules. Three Ni-II ions are bridged by three bidentate carboxylate groups of three BTC ligands, two aqua ligands and one OH- unit, to form a trinuclear metal cluster. The Na-I cation is bonded to the Ni-II cluster by two bridging water molecules. One of the three BTC ligands bridges neighbouring clusters into one-dimensional chains, which are further connected through a complex hydrogen-bonding scheme, forming a three-dimensional suprastructure. The title complex is isomorphous with the previously reported Co-II complex.

HPLC测定四川及青海地区獐牙菜植物中6种主要成分的含量

目的:建立反相高效液相色谱法同时测定四川及青海地区部分獐牙菜中獐牙菜苦苷、龙胆苦苷、芒果苷、当药醇苷、异荭草苷、1,8-二羟基-3-甲氧基(口山)酮的含量.方法:采用RP-HPLC,使用Kromasil C_(18)(4.6 mm×250mm,5 μm)柱;流动相甲醇-水(含0.02%磷酸);梯度洗脱程序为0～50 min,甲醇的体积分数(下同)由20%上升至80%;50～55 min由80%增至100%,55～60 min为100%,流速1 mL•min~(-1),检测波长254 nm;柱温35 ℃.结果:6种成分均达到基线分离,线性良好.结论:该方法快速、准确、重复性好,为该类药材的入药提供了理论依据.

HPLC法测定野生与栽培藏药麻花艽中4种环烯醚萜苷类成分的含量

目的：对野生和栽培藏药麻花艽中龙胆苦苷、落干酸、獐牙菜苦苷和獐牙菜苷4种苦苷类成分进行高效液相色谱的含量测定，并比较分析它们之间的差异。方法：采用Eelipse XDB-C_8色潜柱(4.6 mm*150 mm，5 μm)，流动相A为95％乙腈水溶液，B为5％乙腈(含10 mmol•L~(-1)的甲酸)水溶液，A在0-20min内比例由0-100％进行线性洗脱，流速1.0 mL•min~(-1)，检测波长240 nm，柱温30℃。结果：4种成分均达到基线分离，龙胆菁苷、落干酸、獐牙菜苦苷、獐牙菜苷的线性范围分别为0.60～19•20μg(r=0.9999)，0.24～7.68μg(r=O.9999)，0.38-12.02μg(r=O.9999)，0.05～1.66μg(r=0.9999)；回收率分别为99.73％，98.13％，98.45％，96.22％。结论：栽培藏药麻花艽中苦苷类成分的含量已经接近或超过野生种的水平，可初步代替野生药材人药。

青藏高原东北部植物染色体数目和多倍性研究

对青藏高原东北部高山冰缘地区和相邻低海拔地区５９种多年生草本被子植物进行了染色体计数。其中，４５个种的染色体记数为首次报道，并确定其信性．对分布于高山冰缘地区和冰缘以下不同海拔地区植物染色体的多倍性进行分析研究，结果如下：（１）多年生草本被子植物多倍体频率随海拔高度上升而增加：海拔2000－3000ｍ，多倍体频率为29.4％－47.1％．3000－3800（4000）m（高寒灌丛－草甸区），多倍体频率为33.3％－53.3％；4000－5200ｍ以上的高山冰缘地区，多倍体频率达55.6％－70.4％．（２）高山冰缘地区新多倍体较多，并且与青藏高原上特有的植物类群（特有属、亚属或特有种）相关联。（３）分布在冰缘地区的多倍体广布种，通常都是较原始类群的古多倍体，它们可能在青藏高原强烈隆升以前就已经形成，并分化出许多生态型，在高原强烈隆升并出现高山冰缘环境以后，某些生态型突出繁殖适应机制（r型选择机制），能开拓新生境而在新出现的严酷而不稳定的冰缘地区繁衍，其它一些生态型则依靠营养生长优势（K型选择机制）广泛分布在其稳定、成熟的生境中。（4）冰缘以下地区的多倍体特有种多数属于古多倍体或次生多倍体。它们多数可能是由西南山地或秦岭、华北森林区系产生，然后扩散至青藏高原边缘。

Comparative analysis of allantoin quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid in Nitraria tangutorum Bobr. Seed by HPLC-APCI-MS and CE

This paper describes the simultaneous determination of allantoin, quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid (MTCCA) in Nitraria tangutorum Bobr seed by HPLC-APCI-MS and CE (capillary electrophoresis) methods. The final optimized chromatographic conditions were investigated in a reversed-phase Eclipse XDB-C8 column (150 x 4.6 mm, 5 mu m). A seventeen-minute gradient elution, (A: aqueous acetonitrile 20% (v/v); B: aqueous acetonitrile 60% (v/v); C: pure acetonitrile 100%) at a flow rate of 1.0 mL/min was selected for the separation of three natural products with diode array detection (DAD) at 220 nm. A CE experiment was carried out in a fused silica capillary with 32 mmol/L boric acid (pH 10), 32 mmol/L SDS and acetonitrile (10.0%, v/v). The applied potential and temperature was, respectively, set at 19 kV and 25 degrees C. After development, the validation was performed in parallel for HPLC and CE, with the same standards and sample to avoid differences due to the manipulation. The validation parameters of both techniques were adequate for the intended purpose.