稀土催化四氢呋喃开环聚合

关于η~6-芳烃过渡金属有机络合物催化烯烃聚合的研究已早有报道.但对于η~6-芳烃稀土络合物催化烯烃聚合的研究至今未见报道.我们在研究了(η~6-C_6H_6)Nd-(AlCl_4)_3-AlR_3催化异成二烯聚合的基础上,又考察了不同芳烃烯土络合物和几种AlR_3组成的催化剂对丁二烯聚合的催化活性. 1.原料及试剂:丁二烯和烷基铝均为聚合级.汽油分别经浓硫酸,氢氧化钠水溶

(C_8H_8)Sm(C_8H_8)Na(THF)_3的晶体结构

(C_8H_8)Sm(C_8H_8)Na(THF)_3的晶体属单斜晶系,P2_1空间群.晶胞参数为α=12.140(3),b=13.794(3),c=8.944(3)(?),β=111.68(3)°,V=1391.8(7)(?)~3,Z=2,μ=21.93cm~(-1),D_c=1.43g/cm~3,F(000)=610,Mr=598.0。结构经Patterson函数和Fourier技术解出并经最小二乘修正,最终的偏离因子R为0.046.配合物具有双层夹心结构.其中Sm~(3+)和Na~+通过η~8-环辛四烯基连接。

SYNTHESIS OF ALKALI-METAL HYDRIDES USING LANTHANIDE TRICHLORIDE-NAPHTHALENE AS CATALYST UNDER MILD CONDITIONS

The hydrogenation of alkali metals using lanthanide trichloride and naphthalene as catalyst has been studied. LnCl3(Ln = La, Nd, Sm, Dy, Yb) and naphthalene can catalyze the hydrogenation of sodium under atmospheric pressure and 40-degrees-C to form sodium hydride. The activities of lanthanide trichlorides are in the following order: LaCl3 > NdCl3 > SmCl3 > DyCl3 > YbCl3. Although lithium proceeds in the same catalytic reaction, the kinetic curve of the lithium hydrogenation is different from that of sodium. Lanthanide trichlorides display no catalytic effect on the hydrogenation of potassium in presence of naphthalene. The mechanism of this reaction has been studied and it is suggested that the anion-radical of alkali metal naphthalene complexes may be the intermediate for the hydrogenation of alkali metals and the function of LnCl3 is to catalyze the hydrogenation of the intermediate. The products are porous solids with high specific surface area (83 m2/g for NaH) and pyrophoric in air. They are far more active than the commercial alkali metal hydrides. The combination of these hydrides with some transition metal complexes exhibits high catalytic activity for the hydrogenation of olefins.

温和条件下稀土氯化物-萘催化的碱金属氢化物的合成

本文研究了稀土氯化物对碱金属氢化反应的催化作用.金属钠在稀土氯化物LnCl_3(Ln=La,Nd,Sm,Dy,Yb)和萘的催化下,在常压、40℃下能与氢气反应,生成氢化钠;稀土氯化物的催化活性顺序为LaCl_3>NdCl_3>SmCl_3>DyCl_3>YbCl_3.金属锂可发生类似反应,生成LiH;但其反应动力学曲线与金属钠相比明显不同.稀土氯化物对金属钾的氢化反应不显示催化作用.对反应机理的初步探索表明:碱金属与萘反应生成的阴离子自由基型物种可能是氢化反应的中间体,稀土氯化物的作用是催化该中间体的氢化反应.该反应的产物是一类大比表面积(NaH的比表面积为83m~2/g)、多孔性固体粉末,在空气中可自燃.它们具有比一般市售碱金属氢化物高得多的反应活性,并能与过渡金属配合物组成高活性烯烃加氢催化剂.

不同配位基团稀土化合物在异戊二烯本体聚合中的催化活性

采用本体聚合法,以合成高顺式-1,4结构的稀土异戊橡胶为目的,对6种稀土催化体系的催化恬性进行了研究。结果表明,催化活性顺序为:对烷基铝,Al(i-Bu)_3>AIEts >AlMes,对氯化物,Al(i-Bu)_2Cl>AlEt_2Cl>Al_2Et_3Cl_3>Me_3CCl;对钕化物,Nd(naph)_3>NdCl_3·nD(D为给电子试剂)>Nd[R(RO)POO]_3>Nd[(RO)_2POO]_3>Nd(OCHMe_2)_3,式中R为Me(CH_2)_3CHEtCH_2—。

YBa_2Cu_3O_(7-Y)超导体激光熔凝处理的研究

利用CO_2激光对YBa_2Cu_3O_(7-Y)块材进行熔凝处理后,证明可逆反应式YBa_2Cu_3O_(7-Y)(?)Y_2Cu_2O_5+4BaCuO_2成立,在结构上消除了孔洞等缺陷,使晶粒细化均匀,有序化程度及致密度提高,有效地提高了材料的临界电流密度J_c,从而提出用CO_2激光制备高温超导体YBa_2Cu_3O_(7-y)超导体块材、带材及线材实用化的新工艺.

Development of SSR primers from EST sequences and their application in germplasm identification of Porphyra lines (Rhodophyta)

This paper reports the development of SSR markers from EST data and their utilization in germplasm identification of Porphyra. The publicly available EST (expressed sequence tag) sequences of Porphyra were searched from the Internet (www.kazura.or.jp/en/plant/porphyra/EST/). From a total of 20,779 obtained EST sequences, 391 SSRs (simple sequence repeats) were analysed with SSRIT software (www.gramene.org/db/searches/ssrtool). From those, 48 SSR primer-pairs were designed and tested by commonly used SSR reaction conditions using 22 Porphyra DNA samples as templates. Results showed that 41 SSR primer-pairs gave good amplification patterns. These were used to conduct SSR analyses of genetic diversity and variety identification of the 22 Porphyra lines. A dendrogram and the DNA fingerprints of the Porphyra lines were developed based on the obtained SSR data.

Cultivation of the brown alga Hizikia fusiformis (Harvey) Okamura: enhanced seedling production in tumbled culture

The reuse of holdfasts for regeneration of young seedlings or using wild juvenile plants as the seedling source has played the major role in commercial cultivation of the brown alga Hizikia fusiformis in East Asia over the past 20 years. The possibility of employing zygote-derived germlings for producing seedlings has been discussed in the literature, but has not yet become a reality. Three main obstacles have limited the use of zygotes as a main source of seedlings, (1) the dioecious nature of the algal life cycle which may lead to asynchronous male and female receptacle development and thus different timing of egg and spermatozoa expulsion, (2) the low attachment rate when using zygote-derived germlings with developed rhizoids from wild parental plants for seeding production, and (3) the problem of culturing young germlings in regions where water temperature is high in summer. In this investigation, shifting the timing of receptacle formation earlier than in nature was performed by tumbling the algae in a long-day tank (16-h light per day). Synchronization of egg and spermatozoa expulsion and thereafter fertilization were conducted in indoor tanks. Receptacle formation in constant long days could be shifted by 20 days earlier than in plants cultured on long lines in the open sea, or I month earlier than in plants growing on intertidal rocks. Synchronized expulsion of eggs and spermatozoon led to a high rate of fertilization. This was achieved by tumbling the male and female receptacle-bearing branchlets in the same tank at low density in high irradiance. In two independent trials, a total of 1,400,000 zygote-derived germlings were obtained from 620 g (fresh weight) female sporophytes. The germlings shed from the receptacles were at an identical developmental stage indicating high synchronization of expulsion of eggs and spermatozoon followed by fertilization. Approximately 63% ( +/-9.6%) of the germlings were shed from the receptacle between 16 and 24 It after fertilization and 20% ( +/-11.9%) remained on the receptacle for 3 days after fertilization. Germlings were seeded on string collectors before rhizoids started to elongate and the attachment efficiency was enhanced. Young seedlings reached 800 ( +/-50) mum in length in 25 days at 25 degreesC before they were transferred to open sea cultivation. These results provide the basis of a practical way of seedling production by use of zygote-derived germlings in the commercial cultivation of Hizikia fusiformis. (C) 2004 Elsevier B.V All rights reserved.

Molecular cloning and response to laminarin stimulation of arginine kinase in haemolymph in Chinese shrimp, Fenneropenaeus chinensis

Arginine kinase (AK) was previously reported as a phosphagen-ATP phosphotransferase found in invertebrates. In this study, an 1184 bp cDNA was cloned and sequenced. It contained an open reading frame of 1068 bp that coded for 356 deduced amino acids of AK in Fenneropenaeus chinensis. The calculated molecular mass of AK is 40129.73 Da and pI is 5.92. The predicted protein showed a high level of identity to known AK in invertebrates and creatine kinase from vertebrates, which belong to a conserved family of ATP:guanidino phospho-transferases. In addition, AK protein in plasma of F. chinensis was identified using two-dimensional electrophoresis (2DE) and electrospray ionization mass spectrometry (ESI-MS) according to the calculated molecular mass and pI. AK was significantly decreased in the plasma of F. chinensis at 45 min and recovered at 3 It after laminarin injection as confirmed by 2DE and ESI-MS. The results showed that AK was one of the most significantly changed proteins on two-dimensional gel in the plasma proteins of F. chinensis at 45 min and 3 It after simulation. (c) 2005 Elsevier Ltd. All rights reserved.

Mean sea surface heights of the South and East China Seas from ocean circulation model and geodetic leveling

The mean sea surface heights (sea surface topography) of the South China, East China, Yellow and Bohai Seas are derived from an ocean general circulation model and surface air pressure. The circulation model covers the global oceans, with fine grid (1/6degrees) covering the East Asian marginal seas and coarse grid (31) covering the rest part of the global oceans. The result shows that the China 1985 National Altitude Datum is 24.7 cm above the me-an sea surface height of the world oceans. The mean sea surface in the coastal ocean adjacent to China is higher in the south than in the north. Intercomparison of the model results with the geodetic leveling measurements at 28 coastal tidal stations shows a standard deviation of 4.8 cm and a fitting coefficient of 95.3%. After correction through linear regression, the standard deviation is reduced to 4.5 cm. This indicates that the accuracy of model results is sufficient for practical application. Based on the model results, the mean sea surface heights for the study area with a resolution of 1/6 degree are given. This result also links the mean sea levels at islands with those on the mainland coast and gives the mean sea surface heights at tidal stations in the Taiwan Island, the Dongsha Islands, the Yisha Islands and the Nansha Islands relative to the China 1985 National Altitude Datum.

Relationship between the ennoblement of passive metals and microbe adsorption kinetics in seawater

The relationship between microbial colonization of two kinds of passive metals and ennobling of their corrosion potentials (E-corr) were studied. Two types of passive metal coupons were exposed to natural seawater for about ten days. Under laboratory conditions, all corrosion potentials of the samples ennobled for about 200 mV. Epifluorescence microscopy showed that bacteria adsorption was the main process during about the first day immersion and bacteria reproduced in the following days. The bacteria number increased on the metal surface according to an exponential law and the kinetics of bacteria adsorption at the metal surface during this period was proposed. The ennoblement of E-corr was similar to the increasing bacteria number: E-corr increased quickly during the bacteria adsorption process and increased slowly after biofilms had formed.

紫花冷蒿挥发油成分的研究

采用水蒸气蒸馏法提取, 运用气相色谱-质谱联用法对香叶蒿挥发油化学成分进行了分析, 用气相色谱面积归一化法测定了各成分的质量分数. 结果鉴定出72个化合物, 主要成分为樟脑(33.136%), 桉树脑(23.419%), 6-甲基-2-乙烯基-1,3-庚二烯醛(8.414%), 孟烯醇(3.819%), 桥环萜烯酮(3.276%), 莰烯(2.454%), 1R-α-蒎烯(1.917%), 去甲基丁香酚(1.550%), α-松油醇(1.449%), 冰片(1.674%), β-香叶烯(1.165%), 百里香酚(0.329%)等. 研究表明紫花冷蒿挥发油主要为单萜及其氧化衍生物. 其挥发油成分的研究为挖掘其药用及食品香料工业的应用价值提供了科学依据.

不同放牧强度对鹅绒委陵菜克隆生长特征的影响

在中国科学院海北高寒草甸生态系统定位站,对通过17 a不同放牧强度干扰后金露梅灌丛草甸内鹅绒委陵菜克隆生长特征进行实地调查统计研究.结果显示：长期放牧并增加放牧强度后,植物群落的高度、盖度和草场质量指数下降.随着放牧强度增大,鹅绒委陵菜无性系匍匐茎数目增加,分枝强度加大;基株变矮,逐渐由直立、半直立型变为匍匐状,形态可塑性明显;根长有逐渐增加的趋势;放牧强度对鹅绒委陵菜无性系分株高度、根长和分株叶数影响不显著;间隔子有变短、变粗的趋势,间隔子数目和分株数目有增加的趋势,但影响不显著;轻牧和不牧样地中用于鹅绒委陵菜克隆生长的平均能量投资（分株和匍匐茎的干重及其所占比例）小于重牧样地.表明随放牧强度增大,鹅绒委陵菜无性繁殖能力增强,呈现出典型的生态适应策略.

隆务河流域植物区系研究

隆务河流域共有种子植物65科、329属、970种。区系特征如下：（1）本区系是在高寒类型和寒温、干旱类型兼具的生态环境下形成的。（2）以多年生草要为主、木本植物和一年生植物为辅的植物种类比较丰富。（3）以北温带成分为主的温带性质明显。（4）区系具有年轻性和衍生性质。（5）本区的中国特有种是以我国西南、西北和华北地区为集中分布区或分别为分布中心的种为基础组成的。（6）本区系具有促使物种分化的“过渡生境”的性质和作用，或可称之为“过渡区效应”。区系分析表明，本区系应属与横断山和甘肃南部区系联系密切的青藏高原区系范围，并且在以高原、高山区系成分为主的基础上兼有我国西北寒旱区的荒漠旱生成分。建议是否可在其周围区系更进一步研究的基础上重新确定唐古特地区的界线。

青藏高原东部生态系统土壤碳排放

在青藏高原探讨不同生态系统碳平衡规律及其影响因子并揭示其对全球含碳温室气体变化的影响与响应 ,有重要的现实意义和理论价值。分别在海北高寒草甸生态站、贡嘎山森林生态站和拉萨农业生态站用静态箱法进行了土壤CO2 排放的试验研究。土壤CO2 排放速率日平均值为草甸215.87～329.68mgCO2m -2h -1 ,森林713.72～2102.56mgCO2m -2h -1 ,农田913.05～1135.83mgCO2m -2h-1。土壤碳排放速率日变化 ,在农田和高寒草甸区表现为单峰型 ,均以地方时8∶00～16∶00最高 ,0∶00～8∶00最低。草甸、农田土壤碳排放随着牧草、作物生长发育的加速而逐渐增加 ,越接近成熟 (或枯黄期 )其值越低 ,林区以6～9月的生长旺季为最高。土壤碳排放与温度之间有较好的相关性 ,温度是影响土壤碳排放的重要因子，全球变暖有可能引起高原土壤碳排放的增加。