Interplay between s-d exchange interaction and Rashba effect: Spin-polarized transport

The authors investigate the spin-polarized transport properties of a two-dimensional electron gas in a n-type diluted magnetic narrow gap semiconductor quantum well subjected to perpendicular magnetic and electric fields. Interesting beating patterns in the magnetoresistance are found which can be tuned significantly by varying the electric field. A resonant enhancement of spin-polarized current is found which is induced by the competition between the s-d exchange interaction and the Rashba effect [Y. A. Bychkov and E. I. Rashba, J. Phys. C 17, 6039 (1984)]. (c) 2006 American Institute of Physics.

西北干旱区多种植物地理分布与气候的相关性及其可能潜在分布预测

　　作为西部大开发的关键地区，西北干旱区由于地理位置和环境条件的独特性、生态系统的脆弱性以及人类活动的长期干扰，对其周边乃至全国的生态环境有较大的影响，在这一地区研究植物种分布与气候的关系，并模拟预测其可能的潜在分布范围，具有理论上和实践上的重要意义。 　　通过广泛收集了西北干旱区优势种和常见种的地理分布资料，共选择128个植物种，利用Holdridge的生命地带分类系统，计算各植物种的生物温度(BT)、可能蒸散(PE)、降水量(P)及可能蒸散率(PER)，分析植物种与气候的相互关系，并将所有植物种进行经验归纳分类。随后，对这砦植物种及其气候信息进行TWINSPAN定量分类，并与经验分类结果相比较，得出西北干旱区128种植物的生态气候分类，分属于以下几大类型：高寒草甸、森林一草原过渡带、草原（典型草原、荒漠草原）、荒漠（草原化荒漠、荒漠、高寒荒漠）。具体来说，包括以下17个生态气候类型： 1)高寒草甸：异针茅。 2)森林一草原过渡带：牛尾蒿、鬼箭锦鸡儿、沙棘。 3)草原a：沙蒿。 4)草原b：长芒草、百里香（变种）、多叶隐子草、贝加尔针茅、大针茅。 5)草原c：羊茅、小叶锦鸡儿、荒漠锦鸡儿、线叶菊、华北岩黄芪、廿青针茅、碱蒿、内蒙古沙蒿、裂叶蒿、狭叶锦鸡儿、山竹岩黄芪、女蒿、小蓬、两伯利亚杏、沙地柏、角果碱篷、霸王、糙隐子草。 6)草原d：紫狐茅、紫花针茅。 7)草原一荒漠草原a：包括沙竹、琵琶柴、吉尔吉斯针茅。 8)草原一荒漠草原b：华北米蒿、差巴嘎蒿、星星草、长芒针茅、铁竿蒿、柠条锦鸡儿。 9)荒漠草原：沙生冰草、蒙古冰草、羊草、冷蒿、中亚紫菀木、刺旋花、老瓜头、木贼麻黄、西伯利亚白刺、唐古特白刺、戈壁针茅、石生针茅、盐地碱蓬、冰草、蓍状亚菊、油蒿、木蓼、刺针枝蓼、长枝木蓼、中间锦鸡儿、尖叶盐爪爪、黄花琵琶柴、松叶猪毛菜、珍珠猪毛菜、东方针茅、囊果碱蓬、四合木、白滨藜、短脚锦鸡儿。 10)草原化荒漠，荒漠a：川青锦鸡儿、优若藜、苦艾蒿、无芒隐子草、沙冬青、籽蒿、地白蒿、菭草、齿叶白刺、绵刺、盐角草、多枝柽柳、盐生假木贼。 11)草原化荒漠．荒漠b：蒿叶猪毛菜、短花针茅、芨芨草、灌木亚菊、博乐蒿、小蒿、喀什蒿、南山短花菊、盐爪爪、木本猪毛菜、针茅、细枝盐爪爪。 12)草原化荒漠．荒漠c：白梭梭、白羊草、无叶假木贼。 13）干旱荒漠a：戈壁短花菊、荒漠细柄茅、刺蓬、沙生针茅、多花柽柳、细枝柽柳。 14)干旱荒漠b：梭梭柴、铃铛刺、天山猪毛菜、帕米尔麻黄、座花针茅、旱蒿、克氏狐茅、短叶假木贼、准格尔沙蒿、长穗柽柳、刚毛柽柳。 15)高寒荒漠植被：匍生优若藜。 16)干旱荒漠c：粉花蒿、白杆沙拐枣、膜果麻黄、花花柴、灌木紫菀木、裸果木、合头草、塔里木沙拐枣。 17)超干旱荒漠植被：沙拐枣、胡杨、盐穗木、灰杨、盐节木、圆叶盐爪爪。 　　综合分类结果表明：多数植物种的生态气候类型与实际生境相符，但也有少数植物种有明显偏差，主要原因有三点：首先，某些种的分布范围超出了西北干旱区，在东北、华北、甚至全国范围内分布，所计算的植物种的气候范围本身存在局限性;其次，西北干旱区的研究资料如植物种的分布范围、分布点的气象资料等有许多缺失：最后，由于文献中对某些植物种分布范围的描述比较笼统，无法确定其精确的地理分布界限，使得植物种所对应的分类结果与其真正所属的植 被类型有一些偏差。 　　本文还进一步在这128种植物中选取了10种分布明确、资料齐备的代表性植被类型的优势种，根据它们的降水和生物温度指标，模拟预测了它们的可能潜在分布区，包括其主要中心分布区和最大可能分布区，并与实际分布范围进行比较。结果表明．其潜在分布区的分布范围与实际调查所得资料所处范围基本一致，特别是中心分布区的预测图，而最大可能分布区与实际有一定误差。

Bacillus pallidus sp nov., isolated from forest soil

A Gram-positive bacterium, designated strain CW 7(T), was isolated from forest soil in Anhui Province, south-east China. Cells were strictly aerobic, motile with peritrichous flagella and rod-shaped. The strain grew optimally at 30-37 degrees C and pH 7.0-8.0. The major fatty acids of strain CW 7(T) were anteiso-C-15:0, iso-C-15:0 and anteiso-C-17:0. The predominant menaquinone was MK-7. The cell-wall peptidoglycan contained meso-diaminopimelic acid. The G + C content of the genomic DNA was 42.3 mol%. Phylogenetic analysis indicated that strain CW 7(T) belonged to a monophyletic cluster within the genus Bacillus and showed 16S rRNA gene sequence similarities of less than 96.5% to recognized species of the genus Bacillus. The results of the polyphasic taxonomic study, including phenotypic, chemotaxonomic and phylogenetic analyses, showed that strain CW 7(T) represents a novel species of the genus Bacillus, for which the name Bacillus pallidus sp. nov. is proposed. The type strain is CW 7(T) (=KCTC 13200(T)=CCTCC AB 207188(T)=LMG 24451(T)).

三氟甲基修饰苯并呋喃的合成研究及天然产物discodermolide片段的合成与修饰

苯并呋喃类化合物和吲哚类化合物在自然界中广泛存在，具有重要生理活性，近年来得到广泛的研究。三氟甲基在药物设计中有非常重要的地位，一般来说，三氟甲基引入药物分子中能提高药物的生物活性和减少用药量。合成三氟甲基修饰的苯并呋喃和吲哚在药物设计上很有意义，目前这方面的研究有限。本论文发展了一条合成三氟甲基修饰的苯并呋喃类化合物的方法。此方法从取代的水杨醛出发合成了一类关键中间体2-(3,3,3-三氟-2-氯丙烯基)酚氧酸酯，此中间体在碱的作用下，选用不同溶剂得到了2位三氟甲基取代的苯并呋喃类化合物和2-(3,3,3-三氟丙炔基)苯酚类化合物；后者在单质碘作用下环化得到2位三氟甲基3位碘取代的苯并呋喃类化合物。将此方法应用于三氟甲基修饰的吲哚的合成，发现了一个新的反应，此反应中酰基氧进攻不饱和键成环，得到一个苯并六员杂环体系，此体系水解开环得到N-(2-(3,3,3-三氟丙酰基)苯基)乙酰胺。 天然海洋产物discodermolide具有优异的抗癌效果，对其以及其类似物的合成与研究是当前研究的热点。本论文合成了discodermolide的C(17)-C(22)骨架片段和环氧化的C(19)-C(24)片段类似物，并且进行了氟原子修饰的尝试。

稀土铁双核配合物的合成

本文通过LnCl_3·nTHF和[C_5H_4(SiMe_3)]Na反应得到了两类配合物[C_5H_4(SiMe_3)] LnCl_2·nTHF (Ln = Nd，Sm，Gd；n = 0，1，2)、[C_5H_4(SiMe_3)] LnCl_2·HCl·nTHF (Ln = Nd，Sm，Gd；n = 1，2)。通过元素分析、红外分析、质谱、核磁共振和热重分析确定了配合物的分子组成，特别是带氯化氢的产品在红外光谱中有1250 cm~(-1)，835 cm~(-1)，748 cm~(-1)自的三甲基硅基特征吸收峰。对氯化稀上进行了结构分析，结果发现LnCl_3·4THF (Ln = Sm，Gd)是与NdCl_3·4THF之间存在着变态关系。GdCl_3·4THF。晶体属单斜晶系，空间群为P21/C，晶胞参数为a = 30.765(7)，b = 8.219(3)，C = 17.534(3)A~·，β = 93.71(2)°；SmCl_3·4THF。晶体属单斜晶系，空间群为P21/C，晶胞参数为a = 30.921(13)，b = 8.287(7)，C = 17.665(8)，β = 94.17(4)°。LnCl_3·4THF的单位晶胞中存在着八个分子，每对分子互相等同，但每对分子内部两个分子之间互不等同。SmCl_3·2THF·DME晶体属单斜晶系，空间群为P21/a，晶胞参数为a = 13.547(8)，b = 8.607(4)，C = 16.029(9)A°，β = 90.53(5)°。铲原子与三个氯原子。两个四氢呋喃中的氧原子以及DME中的两个氧原子键合，形成七配位的配合物，但是配位多面体不是理想的五角双锥，而是形成了比五角双锥(D_(5h))对称性更低的多面体(C_(3v))。它能看作是在正八面体的一个面的中心加上第七个原子的结果，而且这八面体主要受到决定上述那个面的三个原子伸展开的畸变。在制备C_5H_5SiMe_3时，如果不用减压蒸馏，而在常压下直接蒸馏，则得到的不是C_5H_5SiMe_3而是它的二聚体(C_5H_5SiMe_3)_2。用红外光谱和核磁共振确定了它的组成和结构，特别是在1650 cm~(-1)处出现(C_5H_5SiMe_3)_2的孤立双键吸收峰。用C_5H_5SiMe_3和Ee(CO)_5回流反应制得了[C_5H_4(SiMe_3) Ee(CO)_2]_2。经过元素分析，红外光谱，质谱，顺磁共振确定了配合物的组成，红外光谱中有桥羰基的吸收峰，质谱图中498的离子峰的出现标志着上述二聚体的存在。用[C_5H_5Fe(CO)_2]_2作为制备双金属配合物的原料，用Na/Hg并还原[C_5H_5Fe(CO)_2]_2。反应时间为6-7小时得到中间体[C_5H_5Fe(CO)_2]_2Na·4THF的深紫红色晶体。反应时间加长，中间体被破坏，反应到15小时时生成了[C_5H_5Fe(CO)_2]Na·TMEDA的黄色晶体，特别是中间体的获得及晶体结构的测定对我们解释反应的机理非常重要。[C_5H_5Fe(CO)_2]_2Na·4THF为单斜晶系，空间群为P21/n，晶胞参数为a = 10.155(5)，b = 17.121(4)，C = 18.667(6)A°，β = 97.61(3)°，V = 3216.9A°~3， 2 = 4。铁的配位数为七，钠的配位数为六，钠离子和桥连羰基氧以配位键结合，每个钠离子连结着两个[C_5H_5Fe(CO)_2]_2~-，而每个[C_5H_5Fe(CO)_2]_2~-又连结着两个钠离子，组成一个无限链状分子，键状分子间以Van de W力结合。[C_5H_5Fe(CO)_2]Na·TMEDA正交晶系，空间群为P_(2,2,2,)。晶胞参数为a = 6.001(4)，b = 10.644(6)，C = 24.214(11)A~·。α = β = r = 90°。z = 4 V = 1546·7A°~3，铁的配位数为五。钠的配位数为四，钠离子和羰基氧以配位键结合，每个钠离子连结着两个[C_5H_5Fe(CO)_2]~-，每个[C_5H_5Fe(CO)_2]~-又连结着两个钠离子，体系就是以这种连结方式或正负电荷交替的形式无限螺旋分子，每个链节存在着两个[C_5H_5Fe(CO)_2]Na·TMEDA分子，链节的长度为a轴的轴长，说明螺旋分子以a轴轴长向上平移。用LnCl_3·nTHF和[C_5H_5Fe(CO)_2]Na反应制得了[C_5H_5Fe(CO)_2] LnCl_2·nTHF (Ln = Nd, Sm, Gd; n = 1, 2)，用[C_5H_5Fe(CO)_2] LnCl_2和[C_5H_4(SiMe_3)]Na或用[C_5H-4(SiMe_3)] LnCl_2和[C_5H_5Fe(CO)_2]Na得到[C_5H_5Fe(CO)_2] [C_5H_4(SiMe_3)] LnCl·nTHF (Ln = Nd, Sm, Gd; n = 0, 1, 3)，配合物[C_5H_5Fe(CO)_2] LnCl_2·nTHF及[C_5H_5Fe(CO)_2] [C_5H_4(SiMe_3)] LnCl·nTHF中存在着2000 cm~(-1)左右的终端羰基吸收峰及1766 cm~(-1)左右的桥连羰基吸收峰。说明稀土和铁之间是以羰基相连的。在TOTOE质谱仪上，配合物[C_5H_5Fe(CO)_2]Gd~·Cl·THF出现[C_5H_5Fe(CO)]GdCl_2、[Fe(CO)_2] Gd~+Cl_2的离子峰，配合物[C_5H_5Fe(CO)_2]-[C_5H_4(SiMe_3)] GdCl·THF出现[C_5H_5Fe(CO)_2] [C_5H_4]Gd~+Cl、[C_5H_5Fe(CO)_2]Gd~+Cl·[C_5H_4C(SiMe_3)] Gd~+Cl等离子峰。所有稀土有机配合物都溶于四氢呋喃、苯，对空气和水敏感。

取代环戊二烯基稀土有机氯化物的合成及其反应

本文通过无水LnCl_3(Ln = Pr.Nd.Gd)与两倍摩尔的叔丁基环戊二烯基碱金属盐在THF中60－80℃反应，分离到一类新的二（叔丁基环戊二烯基）稀土氯化物（T-DuCp）_2 2net.nTHF (Ln = Pr,Nd,n = 2 Ln = Gd,n = 1)，对它们进行了元素分析。红外光谱及水鲜色质谱的表征。对于配合物（t-BuCp）_2PrCl·2THF的单晶，测定了它的晶体结构，晶体层单斜晶系P21/C空间群，晶胞参数为：a = 15.080 b = 8.855 c = 21.196A, β = 110.34°V = 2653.9A~3 δ = 4，结构分析表明此配合物是一中性的单分子配合物。最后的R = Rw = 0.058平均Pr-C.2.81 Pr-Cent 2.53A, Pr-Cl及Rr-O键长分别为2.72与2.62A。本文通过Lnel_3(Ln = Nd.Pr.Ga)与等摩尔的叔丁基环戊二烯基碱金属盐在THF中60－80℃反应，分离到一类中性的单(叔丁基环戊二烯基)稀土二氯化物，并对它们进行了元素分析，红外光谱及水鲜色质谱的表征。本文通过轻稀土元素La,Pr的三氯化物与带基钠以1:2摩尔比在THF中70－80℃反应，分离到了二带基轻稀土氯化物（CaH_7）_2LaCl.2THF及[(CqH_7)_2PrCl.THF]_2。并且对此二配合物进行了元素分析。红外光谱及水鲜色质谱的表征。对于[(CuH_7)_2PrCl.TH]_2配合物，测定了它的晶体结构，这是第一个得到结构表征的茚基稀土氯化物，晶体层于单斜晶系，P_(21)/C空间群，晶胞参数为a = 7.808 b = 17.796 c = 14.070A β = 93.97°v = 1950.31A. E = 2最后的R = 0.045. Rw = 0.039结构分析表明此配合物以中性的二聚体形式存在。平均的Pr-C.2.81 Pr-Cent 2.53. Pr-Cl.2.84H Pr-O钻长2.54A。为了进一步研究不同配体对配合物结构的影响，我们还研究了Gael_3与Nae_5Mes以1:1摩尔比在THF中的反应，分离到了两种配合物[(NaTHF)(C_5MesGd.THF)_2Cl_5]_2.6THF(I)及L_5Me_5GdCl2.3THF(II)并且对配合物（I），测定了它的晶体结构，晶体层于三斜晶系。Pi空间群。晶胞参数a = 12.183 b = 13.638 c = 17.883A, α = 110.38 β = 94.04 γ = 99.44°, V = 2721.20A, E = 1。结构分析表明，此配合物是一种以两个Na原子通过THF中的O原子而桥联的金层有机配合物，在结构上有十分新颖的特点。在此配合物分子中含有四个Gd原子及二个Na原子，Na及Gd间以Cl桥键相联结，Gd-Gd_2 = 4.033 Gdll-Na = 2.818A。最后的R = 0.04M Rw = 0.042。本文还对（t-BuCp）_2P_2Cl.2THF与NaH及LiAlH4的反应进行了初步的研究，分离到（t-Bucp）_2PrH.2THF及(t-Bucp)_2P_2RIH_4.3THF两种新的氢化物，并且对它们进行了元素分析，红外光谱的表征，对于它们水鲜产物的气相分中的H_2，用气相色谱法进行了定性表征。

环戊二烯基轻稀土烷基配合物的合成、表征和反应性能的研究

本文通过LnCl_3·2LiCl (Ln=La, Nd)和等摩尔的CH_3C_5H_4Na在四氢呋喃中于室温反应，得到了一种新的阴离子型配合物[Li(THF)_2]_2 (M-Cl)_4[(η~5-CH_3C_5H_4)Ln·THF] (Ln=La, Nd)，对其进行了元素分析，红外光谱和核磁谱的鉴定，并测得了[Li(THF)_2]_2 (M-Cl)_4[(η~5-CH_3C_5H_4)Nd·THF]的X-光晶体结构。晶体属单斜晶系，空间群为P_(21/n)，晶脆参数为a=12.130(5)，b=17.343(5)，c=17.016(5)A，β=108.54(3)°，V=3393.87A~3，E=4，R=0.0505，中心钕原子分别与CH_3Cp~-。THF和四个桥氯配位，形成稳定的八配位的八面体结构。通过[Li(THF)_2]_2(M-Cl)_4[(η~5-CH_3C_5H_4)Nd·THF]与2摩尔的t-BuLi在四氢呋喃和戊烷的混和溶液中反应，分离得到一种新的阴离子型配合物晶体，经元素分析，红外光谱，核磁和水解色质谱的鉴定，证明为[Li(DME)_3][(η~5-CH_3C_5H_4)Nd(t-Bu)_3]，此配合物不仅对空气和水汽极为敏感，而且对温度也很敏感，即使在-5 ℃下放置也会逐渐分解，发生β-H消除。我们进一步研究了LnCl_3·2LiCl与2摩尔的C_5H_5Na的四氢呋喃反应液在低温下与等摩尔的CH_3Li乙醚溶液反应，从中分离得到一种新的阴离子型烷基配合物晶体[Li(DME)_3][(η~5-C_5H_5)_3LnCH_3] (Ln=La, Nd)对其进行了元素分析，红外光谱，核磁和水解色质谱的鉴定。此外，从这一反应中还得到另一种副产物，经X-光结构鉴定为[Li(DME)_3]~+{[(η~5-C_5H_5)Nd(M-Cl)_2Nd(η~5-C_5H_5)](M-Cl)_4(M_4-D)[(η~5-C_5H_5)Nd(M-CH_3)_2Nd(η~5-C_5H_5)]}~(2-)[Li(DME)_3]~+。本文还研究了NdCl_3·2LiCl与2倍摩尔的CH_3C_5H_4Na的四氢呋喃反应液和等摩CH_3Li乙醚溶液于-78 ℃下反应，从中分离得到另一种新的阴离子型配合物[Li(DME)_3][(η~5-CH_3C_5H_4)_3NdCH_3]并对其进行了元素分析，红外光谱的鉴定。我们还研究了配合物[Li(DME)_3][(η~5-CH_3C_5H_4)Nd(t-Bu)_3]对苯乙烯的催化聚合活性，发现它可以单独引发苯乙烯聚合，得无规聚苯乙烯。

野桂花的化学成分研究

首次从野桂花（Osmanthus yunnanensis Fr. P. S. Green）地上部分95%乙醇提取物中通过色谱分离得到20个化合物, 其中化合物20为新化合物。基于波谱数据它们被鉴定为(E)-阿魏酸二十烷基酯(1)、β-谷甾醇(2)、羽扇豆醇(3)、齐墩果酸(4)、7-oxo-β-sitosterol(5)、乙酰齐墩果酸(6)、(6′-O-palmitoyl)-sitosterol 3-O-β-D-glucoside(7)、rotundioic acid(8)、地榆糖甙Ⅱ(9)、27-O-(E)-对羟基肉桂酰-28-齐墩果酸(10)、27-O-(Z)-对羟基肉桂酰-28-齐墩果酸(11)、hycandinic acid ester(12)、绿原酸丁酯(13)、4,5-二咖啡酰奎尼酸丁酯(14)、4,5-dihydroxyprenyl caffeate(15)、28-O-β-D-glucopyranosyl rotundioic acid (16)、4-(6-O-caffeoyl-β-D-glucopyranosyloxy)-5-hydroxyprenyl caffeate (aohada-glycoside C, 17)、 4-β-D-glucopyranosyloxy-5-hydroxy-prenyl caffeate (aohada-glycoside A, 18)、β-胡萝卜甙(19)以及3-[O-β-D-(6-O-咖啡酰吡喃葡萄糖)]-甲基-2-烯-γ-内酯 (20)。化合物13、14、15和17有较强的α-葡萄糖甙酶抑制活性。当浓度为1 mg/ml时，它们对α-葡萄糖甙酶的抑制分别为61.5%、95.5%、72.1%、62.6%，活性高于阿卡波糖。 综述了木犀属植物化学成分及1993年以来苯丙素甙类化合物活性研究进展。 Twenty compounds were isolated from the 95% ethanol extract of the aerial parts of Osmanthus yunnanensis Fr. P. S. Green by chromatography for the first time. On the basis of spectral data, they were identified as (E)-ferulic acid eicosyl ester (1), β-sitosterol (2), lupenol (3), oleanolic acid (4), 7-oxo-β-sitosterol (5), acetyloleanolic acid (6), (6′-O-palmitoyl)-sitosterol 3-O-β-D-glucoside (7), rotundioic acid (8), ziyu glycosideⅡ (9), 3β-hydroxy-27-p-(E)-coumaroyloxy-olean-12-en-28-oic acid (10), 3β-hydroxy-27-p-(Z)-coumaroyloxyolean-12-en-28-oic acid (11), hycandinic acid ester (12), chlorogenic acid butyl ester (13), 4,5-di-O-caffeoylquinic acid butyl ester (14), 4,5-dihydroxyprenyl caffeate (15), 28-O-β-D-glucopyranosyl rotundioic acid (16), 4-(6-O-caffeoyl-β-D-glucopyranosyloxy)-5-hydroxyprenyl caffeate (aohada- glycoside C, 17), 4-β-D-glucopyranosyloxy-5-hydroxyprenyl caffeate (aohada- glycoside A, 18), β-daucosterol(19) and 3-[O-β-D-(6-O-caffeoylglucopyranosyl)]- methyl-2-en-γ-lactone (20). Compound 20 is a new one. Compounds 13, 14, 15 and 17 inhibit α-glucosidase with corresponding inhibitory rate of 61.5%, 95.5%, 72.1% and 62.6% at a concentration of 1 mg/ml, higher than acarbose. The chemical studies on Osmanthus genus and bioactivities of phenylpropanoid glycosides were summarized.

滇金足草、凋缨菊和长喙吴萸的化学成分研究

本论文对滇金足草（Goldfussia yunnanensis）、凋缨菊（Camchaya loloana）和长喙吴萸（Evodia vestia）的化学成分进行了研究，通过色谱分离得到40个化合物。主要基于波谱数据鉴定了它们的结构，其中10个为新化合物。 1．从滇金足草地上枝叶的95%乙醇提取物中共分离鉴定了16个化合物：泽漆内酯A（1）、18-羟基泽漆内酯A（2）、18-氧代泽漆内酯A（3）、18-羟基-3-O-β-D-吡喃葡萄糖-泽漆内酯A（4）、3-O-β-D-吡喃葡萄糖-泽漆内酯A（5）、3-O-β-D-吡喃半乳糖-泽漆内酯A（6）、6-E-肉桂酰哈巴俄苷（7）、E-哈巴俄苷（8）、5，6-异亚丙二氧基哈巴俄苷（9）、β-谷甾醇（10）、β-胡萝卜苷（11）、齐墩果酸（12）、肉桂酸（13）、麦角固醇（14）、硬脂酸（15）和丁二酸（16）。其中2-7为新化合物。5，6-异亚丙二氧基哈巴俄苷（9）以人工产物形式得到。 2．从凋缨菊地上枝叶的95%乙醇提取物中分离并鉴定了13个化合物：凋缨菊内酯A~C (17-19)、1β-乙酰基凋缨菊内酯C(20)、b-谷甾醇（10）、β-胡萝卜苷（11）、羽扇豆醇（21）、桦木醇（22）、桦木酸（23）、芥子醇（24）、紫丁香苷（25）、咖啡酸（26）和熊果酸（27）。其中化合物17-20为桉叶烷内酯类新化合物。化合物17、18、20对细胞株HepG2的GI50依次为7.80、7.08、4.99 µg/mL。 3．从长喙吴萸（E. vestia）地上枝叶的95%乙醇提取物中分离并鉴定了13个化合物：佛手内酯（28）、花椒毒素（29）、异茴芹内酯（30）、七叶内酯（31）、东莨宕素（32）、瑞香素（33）、异紫花前胡内酯(34)、茵芋碱（35）、山刈碱（36）、白鲜碱（37）、黄柏酮（38）、柠檬苦素（39）和对羟基苯甲醛（40）。 4．综述了1990—2007年期间从菊科植物中发现的桉叶烷-12，6内酯的化学结构、生物活性、生物转化及化学合成方面的研究进展。 Phytochemical investigation on Goldfussia yunnanensis, Camchaya loloana, and Evodia vestia, led to the isolation of 40 compounds, 10 of which were new ones. 1. Six new compounds were isolation from 95% ethanolic extract of the aerial parts of G. yunnanensis, and identified as 18-hydroxyhelioscopinolide A (2), 18-oxohelioscopinolide A (3), 18-hydroxy-3-O-β-D-glucopyranosylhelioscopinolide A (4), 3-O-β-D-glucopyranosylhelioscopinolide A (5),3-O-β-D-Galactopyranosyl helioscopinolide A (6), 6-O-trans-cinnamoyl E-harpagoside (7). The known compounds isolated were helioscopinolide A (1), E-harpagoside A (8), 5,6-isopropylidene E-harpagoside A (9), β-sitosterol (10), β-daucosterol (11), oleanolic acid (12), cinnamic acid (13), ergosterol (14), stearic acid (15) and succinic acid (16). Compound 9 was an artifact. 2. Four new compounds, loloanolides A – C (17 - 19) and 1β-acetoxy-loloanolide C (20), were isolation from 95% ethanolic extract of the aerial parts of C. loloana. The known ones were β-sitosterol (10), β-daucosterol (11), lupeol (21), betulin (22), betulinic acid (23), sinapyl (24), syringin (25), caffeic acid (26) and ursolic acid (27). The GI50 values of compounds 17, 18 and 20 to HepG2 cell line were 7.80, 7.08 and 4.99 µg/mL, respectively. 3. Thirteen were isolated from 95% ethanolic extract of the aerial parts of E. vestia for the first time. They were determined to be bergapten (28), xanthotoxin (29), isopimpinellin (30), esculetin (31), scopoletin (32), daphnetin (33), marmesin (34), skimmianine (35), confusameline (36), dictamine (37), obacunone (38), limonin (39) and p-hydroxy phenyl aldehyde (40). 4. The structures, biological activities, biotransformation and chemical syntheses of eudesmane-12, 6-olides from the Asteraceae during 1990-2007 were reviewed.

Infrared spectroscopic study on thermal behavior of Langmuir-Blodgett films of octadecyl ammonium octadecanoate and octadecylammonium octadecanoate-d(35)

Langmuir-Blodgett (LB) films of octadecylammonium octadecanoate (C(18)H(37)j7NH(3)(+)C(17)H(35)COO(-),ODASA) and octadecylammonium octadecanoate-d(35) (C18H37+NH3+C17D35COO-, ODASA-d(53)) were prepared and their thermal behaviors were investigated by variable-temperature Fourier transform infrared transmission spectroscopy. It was found that the two hydrocarbon chains of ODASA molecule in LB films are highly ordered while that protonated (H) chain in ODASA-d(35) is partially disordered with some gauche conformers introduced at room temperature.

Crystal structures of EtEDTB center dot 1.4C(2)H(5)OH center dot 5H(2)O and H4EtEDTB(ClO4)(4)center dot C2H5OH (EtEDTB=N, N, N ', N '-tetrakis[2-(1-ethylbenzimidazolyl)methyl]-1,2-ethanediamine)

The crystal structures of EtEDTB.1.4C(2)H(5)OH.5H(2)O 1 and H4EtEDTB(ClO4)(4).C2H5OH 2 (EtEDTB = N, N,N',N'-tetrakis[2-(1-ethylbenzimidazolyl)methyl]-1,2-ethanediamine) have been determined by single-crystal X-ray diffraction method. Compound 1 crystallizes in the space group P(1) over bar with a = 11.489(2), b = 11.866(3), c = 12.002(3) Angstrom, alpha = 97.47(2), beta = 114.564(13), gamma = 114.11(2)degrees, V = 1266.6(5) Angstrom(3), Z = 1, M-r = 847.48, D-c = 1.111 g/cm(3), F(000) = 456 and mu(MoKalpha) = 0.076 mm(-1). A total of 5207 reflections were measured for 1, of which 4323 were independent. The structure of 1 was solved by direct methods and refined by full-matrix least-squares technique to the final R = 0.0706 and wR = 0.1802 for 1318 observed reflections with I > 2sigma(I). In the structure of 1, centrosymmetric EtEDTB molecules are linked by hydrogen bonds through water and ethanol to form 2-dimensional network. Compound 2 crystallizes in the space group C2/c with a = 24.260(5), b = 13.040(3), c = 17.680(4) Angstrom, beta = 97.50(3)degrees, V = 5545.2(2) Angstrom(3), Z = 4, M-r = 1140.80, D-c = 1.366 g/cm(3), F(000) = 2384 and mu(MoKalpha) = 0.289 mm(-1).

Synthesis and crystal structure of (1,3-(Bu2C5H3)-Bu-t)(2)Sm(mu-Cl)(2)Li(THF)(2)

Anhydrous SmCl3 reacts with two equal of Li(1-3-(Bu2C5H3)-Bu-t) to give a complex (1,3-(Bu2C5H3)-Bu-t)(2) Sm(mu -Cl)(2)Li(THF)(2) (C34H58Cl2LiO2Sm, M-r = 726.99), monoclinic, space group P2(1)/n, a = 10.615(2), b = 21.037(4), c = 17.166(3) Angstrom, beta = 93.60(3)degrees, V = 3825.7 (13) Angstrom (3), Z = 4, D-c = 1.262 Mg/m(3), mu = 1.699 mm(-1) and F(000) = 1508, final R = 0.0387 and wR = 0.0741 for 5320 observed[I greater than or equal to2 sigma (I)] reflections. The average Sm - C distance is 2.73 Angstrom. Sm - Cl1 and Sm - Cl2 distances are 2.719 (2) and 2. 697 (2) Angstrom, respectively. Two 1, 3-(Bu2C5H3)-Bu-t-ring centroids and two mu (2)-bridging chloride atoms around Sm atom form a distorted tetrahedron.

Synthesis, electrochemistry, and fluorescence of two Ru(phen)(3)(2+)-based surfactants

Two new Ru(phen)(3)(2+)-based surfactants, Ru(phen)(2)(phenNHCO-C-11)(PF6)(2) and Ru(phen)(2)(phenNHCO-C-17)(PF6)(2), have been designed and synthesized, whose chemical structures were characterized by means of IR, H-1 NMR and MS. Also, electrochemistry and fluorescence of them are reported.

Synthesis of lanthanide-alkylaluminium bimetallic complexes and studies on their catalytic activities for polymerization of some polar monomers

Three new lanthanide (Ln)-alkylaluminium (Al) bimetallic complexes with the formula [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AIR(2) . 2THF](2) (Ln = Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF,CO,), (Ln=Nd, Y) with HAI (i-Bu)(2) and of Eu(CF3CO2)(3) with AlEt(3), respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(mu-CF3CO2)(2)Nd (mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Nd-Al) and [(mu-CF3CO2)(2)Y(mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Y-Al) are isomorphous and crystallize in space group with a=12.441(3) Angstrom [12.347(5) Angstrom for Y-Al], b=12.832(3) Angstrom [12.832(4) Angstrom], c=11.334(3) Angstrom [11.292(8) Angstrom], alpha=104.93 (2)degrees [104.45(4)degrees], beta=98.47(2)degrees [98.81(4)degrees], gamma=64.60(2)degrees [64.30(3)degrees], R=0.519 [0.113], R(w)=0.0532 [0.110], Z=1 and [(mu-CF3CO2)(2)Eu(CF3CHO2)AlEt(2) . 2THF](2)(Eu-Al) in space group P2(1)/n with a=11.913(6) Angstrom, b=14.051(9) Angstrom, c=17.920(9) Angstrom, alpha=101.88(11)degrees, beta=gamma=90 degrees, R=0.0509, R(w)=0.0471 and Z=2. The six CF3CO2- (including CF3CHO2-) of each complex, among which pairs are equivalent, coordinated to Ln and Al in three patterns: (A) the two oxygen atoms in one of the three CF3CO2- type coordinated to two different Ln; (B) the two oxygen atoms in the second of CF3CO2- type coordinated to Ln and Al, respectively; (C) one of the two oxygen atoms in the third CF3CO2- type bidentately coordinated to two Ln and another oxygen coordinated to Al and one of the two Ln, respectively. Unlike types A and B, in type C the carboxyl carbon with a hydrogen atom bonded to it was found to appear as an sp(3)-hybridized configuration rather than an sp(2)-one. 1D and 2D NMR results further confirmed the existence of such a disproportionated CF3CHO2- ligand. Methyl methacrylate (MMA) and epichlorohydrin (ECH) could be polymerized by Y-Al or Eu-Al as a single-component catalyst and highly syndiotactic poly(MMA) was obtained. THF could also be polymerized by Y-Al in the presence of a small amount of ECH.

SYNTHESES OF METHYLCYCLOPENTADIENYL DERIVATIVES OF LANTHANIDES (LN = LA-ND) AND CRYSTAL-STRUCTURES OF [(THF)2LI(MU-CL)2]2[MECPND(THF)] AND [LI(DME)3][MECPLA(NPH2)3]

The reaction of LnCl3.2LiCl with 1 equiv of MeCpNa in THF gives the complexes [(THF)2Li(mu-Cl)2]2[MeCpLn(THF)] (Ln = Nd (1), La (2)) in good yield. These precursors react further with 2 equiv of LiNPh2 to produce the new complexes [Li(DME)3][MeCpLn(NPh2)3] (Ln = La (3), Pr (4), Nd (5)). They have been characterized by elemental analyses and IR and NMR spectra, as well as by structural analyses of 1 and 3. The chloride 1 crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 12.130 (5) angstrom, b = 17.343 (5) angstrom, c = 17.016 (5) angstrom, beta = 108.54 (3)-degrees, V = 3393.87 angstrom3, Z = 4, and D(c) = 1.45 g/cm3. Least-squares refinement led to a final R value of 0.051 (I greater-than-or-equal-to 3-sigma(I(o))) for 2004 independent reflections. Complex 3 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 18.335 (6) angstrom, b = 16.576 (5) angstrom, c = 17.461 (6) angstrom, beta = 96.04 (3)-degrees, V = 5277.17 angstrom3, D(c) = 1.26 g/cm3, Z = 4, and R = 0.057 (I greater-than-or-equal-to 2.5-sigma(I(o))) for 3378 reflections. The structure of 3 consists of discrete ion pairs [Li(DME)3]+ and [MeCpLa(NPh2)3]- with average La-N and La-C(ring) distances of 2.459 (8) and 2.84 (1) angstrom, respectively.