Pd(OAc)_2/FePc催化环己烯氧化合成环己酮的研究

考察了几种Ｆｅ大环配合物与Ｐｄ（ＯＡｃ）２组成的双组分催化体系，在乙腈酸性水溶液中环己烯氧化合成环己酮的催化活性．实验结果表明，其中以酞菁铁（ＦｅＰｃ）与Ｐｄ（ＯＡｃ）２组成的催化体系活性最高，而ＦｅＴＰＰＣｌ与Ｐｄ（ＯＡｃ）２催化体系，虽然催化活性较高，但催化剂的稳定性较低．各种因素对Ｐｄ（ＯＡｃ）２／ＦｅＰｃ催化活性影响的研究结果指出，在无水和酸存在的非水溶液中，Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对环己烯氧化未显现出任何催化活性．认为在乙腈酸性水溶液中，Ｐｄ（ＯＡｃ）２／ＦｅＰｃ催化环己烯氧化合成环己酮的作用机理与Ｗａｃｋｅｒ催化剂的作用机理相似，ＦｅＰｃ是起再生作用的催化剂.

Hydroxylation of phenol by iron(II)-phenanthroline(Phen)/MCM-41 zeolite

MCM-41 zeolite and Tron (II)-Phen/MCM-41 zeolite have been prepared and characterized by XRD, IR, NH3-TPD, HET and UV-Vis. The Iron( II)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of phenol.

镧和钙对人红细胞膜的作用

采用荧光偏振，自旋标记电子顺磁共振波谱和激光拉曼光谱等技术研究了镧和钙对人红细胞膜结构和功能的影响。结果表明，低浓度的Ｌａ￣（３＋）（０．５μｍｏｌ／Ｌ）对（Ｎａ￣＋＋Ｋ￣＋）－ＡＴＰ酶，Ｍｇ￣（２＋）－ＡＴＰ酶有轻微的激活作用，随着浓度的增大，则明显抑制酶的活性。Ｌａ￣（３＋）可降低红细胞的膜脂流动性，使膜蛋白酰胺Ｉ’－ａ螺旋振动强度减弱；Ｃａ￣（２＋）对膜脂流动性和膜蛋白酰胺Ｉ’－ａ螺旋的影响比Ｌａ￣（３＋）小。

π－烯丙基稀土配合物的合成、结构及其催化烯烃聚合反应机理的研究 Ⅲ．LiLn（π－C_3H_5）_4·nD催化异戊二烯和苯乙烯均聚合反应的研究

本文研究了ＬｉＬｎ（π－Ｃ_３Ｈ_５）_４·ｎＤ（Ｌｎ＝Ｌａ、Ｔｂ，ｎ＝３；Ｌｎ＝Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｒ，ｎ＝２；Ｌｎ＝Ｙ、Ｄｙ，ｎ＝２．５；Ｄ为二氧六环）催化异戊二烯和苯乙烯的均聚合反应．其中，钇配合物的催化活性为最高．聚异戊二烯顺式－１，４链节含量在４３－８１％．聚合体系内少量给电子体的加入使聚合物中３，４－链节含量高达８４％．所得聚苯乙烯为无规结构．

PREPARATION AND STRUCTURE OF HALF-OPEN VANADOCENE, V[2,4-(CH3)2C5H5](C5H5)CO

The half-open vanadocene, V[2,4-(CH3)2C5H5](C5H5)CO, was obtained by the reaction of V[2,4-(CH3)2C5H5](C5H5)PMe3 with CO in petroleum ether at room temperature. Its crystal structure was determined by X-ray diffraction technique. The crystal was monoclinic with space group P2(1)/n, a = 16.614(3), b = 7.636(1), c = 19.128(6) angstrom, beta = 99.92(2)-degrees, V = 2390.5(9) angstrom3, and Z = 8. The final R value was 0.043. The V(1)-CPD(1) (half) (PD = 2,4-(CH3)2C5H5) bonds were shorter (0.038 angstrom) than the V(1)-CCP(1) (half) (CP = C5H5) bonds, averaging 2.224(4) versus 2.262(4) angstrom, respectively. 4V[2,4-(CH3)2C5H5](C5H5)CO has been characterized by IR and EPR methods.

A WOUND-TYPE LITHIUM POLYANILINE SECONDARY CELL

A wound-type cell with a polyaniline (PAn) positive electrode, a LiClO4-propylene carbonate (PC) electrolyte, and a lithium foil negative electrode has been constructed. The two electrodes are separated by a polypropylene separator. The PAn is deposited on carbon felt from a HClO4 solution containing aniline by galvanostatic or potentiostatic electrolysis. Using cyclic voltammetry charge/discharge cycles and charge/retention tests, the following results have been obtained: (i) reversibility of the charge/discharge reaction of the PAn electrode is very good; (ii) more than 50 charge/discharge cycles at 80% charge/discharge efficiency and 260 W h kg-1 discharge energy density can be achieved at 50 mA between 2 and 4 V; (iii) the open-circuit voltage and the capacity retention of the battery after storage at open-circuit for 60 days are 3.4 V and 33%, respectively.

一种具有“浮萍”结构的单分子膜与Langmuir-Blodgett多层膜

本文以St-DVB微凝胶/甲基丙烯酸两性接枝共聚物制成了一种新型“浮萍”结构的单分子膜,并转移制备了LB多层膜,对其单分子膜的性质、LB多层膜的二维有序结构及膜的热稳定性进行了较深入的研究。

镧系元素混价配合物的电子结构 Ⅰ.三价铈和四价铈的成键研究

不久以前,本文的作者之一在试图合成C_9H_7CeCl_3时,得到了非预期产物[Ce(THF)_5Cl_2]~+[Ce(THF)Cl_5]~-(THF=四氢呋喃)的单晶,并测定了其晶体结构,该混价配合物的分子由合Ce(Ⅲ)的配阳离子和含Ce(Ⅳ)的配阴离子组成,它的培养成功为研究铜系元素4f轨道的成键作用及对比镧系离子价态变化对其成键的影响提供了一个极好的机会。本文用INDO方法研究了铈离子混价配合物的电子结构和成键性质。

钙钛石型复合氧化物La_(1-x)Sr_xFeO_(3-λ)催化性能的研究——Ⅲ.Fe离子的状态及其对催化活性的影响

用Mossbauer,IR等技术及对样品磁化率与电导率的测量,研究了钙钛石型复合氧化物La_(1-x)Sr_xFeO_(3-λ)体系中,活性金属铁离子在改变x时的价态和配位环境的变化及其对催化活性的影响。发现催化剂在0≤x<0.5～0.7范围内,其Fe—O键的相互作用较强,催化活性主要由催化剂的表面化学所控制;在0.7≤x≤1.0范围内,催化剂中Fe-O键相互作用减弱,氧空位出现有序化,在这一范围内,催化活性主要由催化剂的体相化学控制。

激光引发Cl_2和CH_2Cl_2对Cu的化学刻蚀

本文利用氩离子激光引发的化学反应,对铜片进行刻蚀研究,给出了刻蚀速率与激光能量和工作气体压强的关系曲线,得到 Cu—Cl_2体系的光刻能量阀值低于 Cu—CH_2Cl_2体系的结果并讨论了这一差别的原因。

Population genetic structure of crimson snapper Lutjanus erythropterus in East Asia, revealed by analysis of the mitochondrial control region

The population genetic structure of the crimson snapper Lutjanus erythropterus in East Asia was examined with a 427-bp hypervariable portion of the mtDNA control region. A total of 262 samples were collected and 75 haplotypes were obtained. Neutrality tests (Tajima's and Fu's) suggested that Lutjanus erythropterus in East Asia had experienced a bottleneck followed by population expansion since the late Pleistocene. Despite the low phylogeographic structures in mtDNA haplotypes, a hierarchical examination of populations in 11 localities from four geographical regions using analysis of molecular variance (AMOVA) indicated significant genetic differentiation among regions (Phi(CT) = 0.08564, p < 0.01). Limited gene flow between the eastern region (including a locality in the western Pacific Ocean and two localities in the East Sea) and three geographic regions of the South China Sea largely contributed to the genetic subdivision. However, comparisons among three geographic regions of the South China Sea showed little to no genetic difference. Populations of Lutjanus erythropterus in East Asia are inferred to be divided into two major groups: an eastern group, including populations of the western Pacific Ocean and the East Sea, and a South China Sea group, consisting of populations from northern Malaysia to South China. The results suggest that fishery management should reflect the genetic differentiation and diversity in East Asia. (c) 2006 International Council for the Exploration of the Sea. Published by Elsevier Ltd. All rights reserved.

Identification of Porphyra lines (Rhodophyta) by AFLP DNA fingerprinting and molecular markers

Twenty-seven Porphyra lines from 5 classes, including lines widely used in China, wild lines, and lines introduced to China from abroad in recent years, were screened by means of amplified fragment length polymorphism (AFLP) with 24 primer pairs. From the generated AFLP products, 13 bands that showed stable and repeatable AFLP patterns amplified by primer pairs M-CGA/E-AA and M-CGA/E-TA were scored and used to develop the DNA fingerprints of the 27 Porphyra lines. Moreover, the DNA fingerprinting patterns were converted into computer language expressed with digitals 1 and 0, which represented the presence (numbered as 1) or absence (numbered as 0) of the corresponding band. On the basis of these results, computerized AFLP DNA fingerprints were constructed in which each of the 27 Porphyra lines has its unique AFLP,fingerprinting pattern and can be easily distinguished from others. Software called PGI-AFLP (Porphyra germplasm identification-AFLP) was designed for identification of the 27 Porphyra lines. In addition, 21 specific AFLP markers from 15 Porphyra lines were identified; 6 AFLP markers from 4 Porphyra lines were sequenced, and 2 of them were successfully converted into SCAR (sequence characterized amplification region) markers. The developed AFLP DNA fingerprinting and specific molecular markers provide useful ways for the identification, classification, and resource protection of the Porphyra lines.

Temperature tolerance of young sporophytes from two populations of Laminaria japonica revealed by chlorophyll fluorescence measurements and short-term growth and survival performances in tank culture

The cold-water subtidal brown alga Laminaria japonica has been commercially fanned in the Far East and has been on top of all marine-fanned species in terms of farming area and annual output worldwide. The successful trials of transplantation of young sporophytes from the north to the south in winter along the Chinese coast in the 1950s led to the spreading of cultivation activities down to a latitude of 25-26 degrees N. Up to today, nearly 50% of the annual output of this farmed alga, as a cold-water species, comes from the sub-tropical south in China. The demand to have high-temperature-tolerant strains/ecotypes in farming area calls for a practical method to judge and select the desired parental plants for breeding programs and for seedling production. In this paper, we report our results on using chlorophyll fluorescence measurement and short-term growth performance in tank culture to estimate the temperature tolerance of offspring from two populations, Fujian Farmed Population (FFP) sampled from Fujian province (latitude: 25-26 degrees N) in subtropical area and Qingdao Wild Population (QWP) sampled from Qingdao (latitude: 36 degrees N). Contrary to what has been usually thought, the results revealed that offspring from Qingdao wild population in the north showed better performance both in short-term growth and survival rates and in optimal quantum efficiency (F-v/F-m) when exposed to higher temperature (20-25 degrees C). This result was further confirmed by fluorescence quenching analysis. QWP distributed along the southern distribution limit at a latitude of 36 degrees N in the Pacific west coast is thus taken as a more ideal one than the fanned population in subtropical region as a source of parental plants for breeding high-temperature-tolerant varieties. (c) 2006 Elsevier B.V. All rights reserved.

Geochemical properties of the variolitic andesite from Susong in the Dabie orogenic belt, China

The variolitic andesite from the Susong County in the Dabie Mountains implies that it was erupted in water. The mineralogy of the varioles is primarily radiate plagioclase (albite sind oligoclase), with little pyroxene, hornblende and quartz (derived from alteration). The pyroxene, hornblende and quartz are in the interstices between plagiocalse. The matrix consists of glass, hornblende, chlorite, epidote and zoisite. It is clearly subjected an extensive alteration. The andesite has an uncommon chemical composition. The SiO2 content is about 56.8%, TiO2 = 0.9%, MgO = 6.4%, Fe2O3 (tot) = 6.7%similar to 7.6%, 100Mg/(Mg + Fe) = 64.1 similar to 66.2. Mg-# is significantly high. The andesite has high abundances of large-lithophile trace elements (e.g. K, Ba. Sr, LREE), e.g. La/Nb = 5.56 similar to 6.07, low abundances of high-strength-field elements (HFSE e.g. Ta, Nb, P, Ti), particularly Ta and Nb strongly depleted. These are consistent with the characteristics of subduction-related magmas. In the spider diagram of trace elements, from Ce to right hand, the abundances of elements decrease quickly, showing a character of the continental margins. There has a strong punishment of light-rare-earth elements, with a significant diffraction of REEs (the mean value of (La/Yb)(N) is 32.84). No Eu anomaly, but there are anomaly high (La/Yb)(N) = 28.63 similar to 36.74, (La/Y)(N) = 70.33 similar to 82.4. The elements Y and Yb are depleted greatly, Y<20 g/g, Y-N = 2.74 similar to 2.84, Yb-N = 2.18 similar to 2.35. From the La-(La/Sm) diagram, the andesite is derived from partial melting. But the epsilone value of Nd is - 18.7 similar to -19.2, so that the material source may be the mantle materials affected by the crustal materials. The Nd model age is 1.9 Ga indicating that the variolitic basaltic andesite was resulted from the mantle wedge of North China block, which had the Nd model age of 2.5Ga, when the Yangze block which had the Nd model age of 1.7Ga subducted beneath it. So the variolitic andesite has characteristics of the island-are volconic rocks oil a continental basement in the vicinity of the destructive continental margin.