Synthesis and polymerization of some macrocyclic (arylene ether sulfone) containing cardo groups and macrocyclic (arylene ether ketone sulfone) oligomers

Some novel macrocyclic (arylene ether sulfone) containing cardo groups and (arylene ether ketone sulfone) oligomers have been synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-difluorophenylsulfone with bisphenols in the presence of anhydrous potassium carbonate under a pseudo-high-dilution condition. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), fast atom bombardment mass spectrometry (f.a.b.-m.s.), nuclear magnetic resonance spectrometry (n.m.r.) and single-crystal X-ray structure analysis confirms their cyclic nature, and the composition of the oligomeric mixtures is provided by g.p.c. analysis. Ring polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 59.1 k was achieved by heating at 290 degrees C for 40 min in the presence of a nucleophilic initiator. (C) 1998 Elsevier Science Ltd. All rights reserved.

Macrocyclic oligomeric arylene ether ketones: Synthesis and polymerization

Some novel macrocylic(arylene ether ketone)oligomers were synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-dinitrobenzophenone with bisphenols in the presence of anhydrous potassium carbonate under pseudo-high-dilution conditions. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), H-1 NMR and FT-IR confirmed their cyclic nature and the compositions of the oligomeric mixtures was indicated by GPC analysis. Ring-opening polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 52.3 and M-n of 17.2 k was achieved by heating at 280 degrees C for 40 min in the presence of a nucleophilic initiator.

T-Muurolol Sesquiterpenes from the Marine Streptomyces sp M491 and Revision of the Configuration of Previously Reported Amorphanes

Two new sesquiterpenes, 15-hydroxy-T-muurolol (3d) and 11,15-dihydroxy-T-muurolol (3e), along with the plant cadinenes T-muurolol (3f) and 3 alpha-hydroxy-T-muurolol (3g), were isolated from the marine-derived Streptomyces sp. M491. Their absolute configuration was established via NMR spectroscopy and X-ray crystallography of 3-oxo-T-muurolol (3a), which was reisolated from this strain. In addition, the absolute configuration of further sesquiterpenes previously reported from this strain was revised. These products were tested for their cytotoxicity against 37 human tumor cell lines using the MTT method. Only 3d was cytotoxic against a range of human tumor cell lines with a mean IC50 of 6.7 mu g/mL.

Bifurcation of Pacific North Equatorial Current at the surface

The grid altimetry data between 1993 and 2006 near the Philippines were analyzed by the method of Empirical Orthogonal Function (EOF) to study the variation of bifurcation of the North Equatorial Current at the surface of the Pacific. The relatively short-term signals with periods of about 6 months, 4 months, 3 months and 2 months are found besides seasonal and interannual variations mentioned in previous studies. Local wind stress curl plays an important role in controlling variation of bifurcation latitude except in the interannual timescale. The bifurcation latitude is about 13.3A degrees N in annual mean state and it lies at the northernmost position (14.0A degrees N) in January, at the southernmost position (12.5A degrees N) in July. The amplitude of variation of bifurcation latitude in a year is 1.5A degrees, which can mainly be explained as the contributions of the signals with periods of about 1 year (1.2A degrees) and 0.5 year (0.3A degrees).

An N-shape thermal front in the western South Yellow Sea in winter

An N-shape thermal front in the western South Yellow Sea (YS) in winter was detected using Advanced Very High Resolution Radiation (AVHRR) Sea Surface Temperature data and in-situ observations with a merged front-detecting method. The front, which exists from late October through early March, consists of western and eastern wings extending roughly along the northeast-southwest isobaths with a southeastward middle segment across the 20-50 m isobaths. There are north and south inflexions connecting the middle segment with the western and eastern wings, respectively. The middle segment gradually moves southwestward from November through February with its length increasing from 62 km to 107 km and the southern inflexion moving from 36.2A degrees N to 35.3A degrees N. A cold tongue is found to coexist with the N-shape front, and is carried by the coastal jet penetrating southward from the tip of the Shandong Peninsula into the western South YS as revealed by a numerical simulation. After departing from the coast, the jet flows as an anti-cyclonic recirculation below 10 m depth, trapping warmer water originally carried by the compensating Yellow Sea Warm Current (YSWC). A northwestward flowing branch of the YSWC is also found on the lowest level south of the front. The N-shape front initially forms between the cold tongue and warm water involved in the subsurface anti-cyclonical recirculation and extends upwards to the surface through vertical advection and mixing. Correlation analyses reveal that northerly and easterly winds tend to be favorable to the formation and extension of the N-shape front probably through strengthening of the coastal jet and shifting the YSWC pathway eastward, respectively.

An approach to prediction of the South China Sea summer monsoon onset

In the present paper, correlation between the South China Sea summer monsoon (SCSSM) onset and heat content in the upper layer of the warm pool in the western Pacific Ocean is examined using the Scripps Institution of Oceanography dataset for the period of 1955-1998 and an approach to prediction the SCSSM onset is proposed. Correlation showes that there exists interdecadal variability of the SCSSM onset demarcated by 1970 with the largest correlation coefficient in the area west of the center of the warm pool rather than near its centers, implying certain effect from other factors involved besides ENSO. As the correlation is poor for the period before 1970, the heat content anomaly of the warm pool after 1970 is used to indicate early or late onset of the SCSSM beforehand. An ideal representative area (1A degrees x1A degrees) for the warm pool heat content was determined with its center at 3A degrees N/138A degrees E. The nearest TAO (TAO-Tropical Atmosphere Ocean-array) mooring to the center is at 2A degrees N/137A degrees E, and chosen to calculate the heat content for prediction. It is suggested that the TAO mooring at 2A degrees N/137A degrees E could be used to predict the SCSSM onset with the heat content in the upper layer, if the correlation between the SCSSM onset and the heat content of the warm pool runs like that of after 1970. On the other hand, if the situation does like the one before 1970, the representative station is determined at 13A degrees S/74A degrees E with relatively poor correlation, meaning that the warm pool in the western Pacific Ocean plays more important role in the SCSSM onset than the Indian Ocean.

渤海近代沉积物的古地磁与古环境研究

本论文的主要实验测量工作可分为古地磁学与地球化学二大部分。在古地磁学方面。对JX91-2A（168），JX91-2B（80），JX91-3A（66）和JX91-3B（137）共451个样品进行了天然剩磁（NRM）及交变退磁测量，还进行了磁化率及磁化率各向异性的测量。对JX91-2A，JX91-2B和JX91-3A开展了岩石磁学研究，测量了非粘滞性剩磁（ARM），等温剩磁（ARM），饱和等温剩磁（FIRM）以及个别样品的FIRM衰减曲线，对JX91-3B求出了中间破坏强度（MDF）。在地球化学方面，对JX91-2A（79），JX91-3B（67），JX91-3m(50)和JX91-4G（27）共223个样品进行了X光萤光（XRF）分析。包括10种主要元素及21种向量元素，以及X光衍射（XRD）分析。还对JX91-2A进行了有机碳、微体古生物学及稳定碳氧同位素分析；对JX-91-3B进行了~（210）Pb 测量。另外还对此四岩芯测定了含水量及粒度分布等。所有实验数据都用计算机进行了分析处理，并做了广泛的多学科综合对比研究。在充分借鉴前人成果的基础上，本论文就以下四个方面的问题得到了一点新的认识。一、渤海黄河口外的浊流系统及浅水浊流沉积。这一浊流系统的存在具有多方面的证据。二、渤海沉积物的高精度年代学。对于渤海中央盆地沉积物主要采用了全新世以来的海平面变化曲线及古地磁场强度曲线确定年代，定出JX91-2A底部年代为距今8，500年。三、古地磁记录改正方法及渤海地区古地磁长期变样本曲线的建立。四、渤海古环境综合分析及黄河全新世以来的河道变迁。

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。

Phylogenetic position and morphology of thecae and cysts of Scrippsiella (Dinophyceae) species in the East China Sea

Resting cysts of the marine phytoplanktonic dinoflagellate Scrippsiella spp. are encountered in coastal habitats and shallow seas all over the world. Identification of Scrippsiella species requires information on cyst morphology because the plate pattern of the flagellated cell is conserved. Cysts from sediments of the East China Sea were identified based on traits from both the cysts and the thecal patterns of germinated cells. Calcareous cysts belonged predominantly to S. trochoidea (F. Stein) A. R. Loebl., S. rotunda J. Lewis, and S. precaria Montresor et Zingone. The former two species also produced smooth and noncalcified cysts in the field. A new species, S. donghaienis H. Gu sp. nov, was obtained from six noncalcified cysts with organic spines. These cysts are spherical, full of pale white and greenish granules with a mesoepicystal archeopyle. The vegetative cells consist of a conical epitheca and a round hypotheca with a plate formula of po, x, 4', 3a, 7 '', 6c (5c + t), 6 s, 5''', 2'''' and are morphologically indistinguishable from S. trochoidea. Results of internal transcribed spacer (ITS) sequence comparisons revealed that S. donghaienis was distinct from the S. trochoidea complex and appeared nested within the Calciodinellum/Calcigonellum clade. Culture experiments showed that the presence of a red body in the cyst and the shape of the archeopyle were constant within cell lines from one generation to the next, while the morphological features of the cyst wall, such as calcification and spine shape, appeared to be phenotypically plastic.

不同放牧强度草原休牧后土壤养分和植物群落变化特征

在内蒙古典型草原，对不同放牧率草地休牧3a后的土壤养分空间异质性和植物群落的数量变化特征进行了研究，结果表明：不同放牧率草地休牧3a后，由于维持土壤养分或植被空间格局的匀质化条件消失，土壤养分的空间异质性呈不同程度的增大趋势，随机性因素所占比例增加，其中土壤有机碳、全氮、无机氮、有效磷和有效硫的空间异质性均以0．00羊/hm^2区最大，4．00羊／hm^2区（中牧区）最小，其它样地不同土壤养分指标表现不同的变化特征；群落生物量和群落盖度均表现增加趋势，但群落盖度增加不显著（P〉0．05），与1998年相比，群落生物量除对照区外均达到了显著性差异（P〈0．05），与1．33羊／hm^2、4．00羊／hm^2和6．67羊／hm^2相比，O．00羊／hm^2优势植物出现多样化特征；群落的灌丛化与牧压和恢复演替的时间序列高度相关，牧压越小，恢复演替的时间序列越大，群落灌丛化的趋势越明显；1年生植物、羊草、克氏针茅、木地肤、冷蒿（除6．67羊／hm^2）和扁蓿豆（除O．00羊／hm^2）均表现增加趋势，星毛委陵菜则均表现降低趋势；植物群落的生物量、群落高度、群落盖度和群落物种多样性与土壤养分分布均表现一致的正相关关系，但只有植物群落生物量和群落高度与土壤有机碳、全氮、无机氮、土壤有效磷和有效硫相关显著（P〈0．05）。

青藏高原高山植物麻花艽的传粉生态学研究

对青藏高原东部麻花艽(Gentiana straminea)海北居群的传粉生态学进行了3a连续的观察和实验。试验表明自然去雄、人工自交和杂交处理均结实，而人工去雄套袋和自然套袋不结实。麻花艽自交亲合，但必须依赖传粉媒介才能完成授粉过程，不存在无融合生殖。野外捕捉到14种访花昆虫，它们分别属于2个纲，7个目，8个科。观察和分析了各种昆虫的访花行为后，认为苏氏熊蜂(Bombus sushikini)是麻花艽有效而稳定的传粉者。测量表明麻花艽花蜜通道的深度和苏氏熊蜂的舌长基本吻合。苏氏熊蜂的访花频率在lO：00～12：00，13：00～15：00和16：00～18：OO时间段没有差别，单花的访花频率为0．005次／(花·rain)。和其它高山植物相比，青藏高原高山植物麻花艽的访花频率较高。熊蜂传粉和高频率的访花维持了麻花艽在极端寒旱的青藏高原环境下的有性生殖。此外，高频率的访花对于维持该地区高山植物的生殖保障具有重要的现实意义，但是否具有普遍性，还有待研究更多的高山代表类群。

巨穗小麦种质主要特异性状的遗传和相关性研究

本文分析了来源相同的14种巨穗小麦种质的主要特异性状间的相关性，回归分析了性状对间的数量关系，并结合基因定位的结果探讨了性状间的相关性与基因连锁程度的关系，结果表明：小穗数与穗数的正相关程度最高（r=0.9625)；千粒重与多数性状间呈负相关；株高与多数性状间的正相关程度较高(r>0.8)；控制相关性的基因多位于同一染色体或染色体的同一臂上，且正相关程度越高的性状对，其控制基因连锁程度越高；3A染色体上控制千粒重基因的作用效应，以及该基因与3A染色体上控制其它性状的基因间的连锁关系是造成千粒重与其他性状呈负相关的主要遗传因素。

巨穗小麦种质株高的基因定位

巨穗小麦新种质材料是一种有茎杆粗壮、叶片短宽直立、大穗、大粒 、高结实率等特点的种质资源。本研究应用单体分析和双端体分析方法对“241”材料进行了遗传学研究。结果表明，小麦新种质材料“241”的1A、3A、5A和4B染色体上具有控制株高的隐性基因，6B染色体上具有控制株高的显性基因，其中3A、5A和6B染色体上的基因表现为强效，1A和4B染色体上的基因表现为弱效。通过双端体分析进一步将控制株高的基因定位到1AS、3AS、5AL和4BL上。

巨穗小麦种质株高的基因定位

巨穗小麦新种质材料是一具有茎杆粗壮、叶片短宽直立、大穗、大粒、高结实率等特点的种质资源。本研究应用单体分析和双端体分析方法对241材料进行了遗传学研究。结果表明，小麦新种质材料241的1A，3A，5A和4B染色体上具有控制株高的隐性基因，6B染色体上具有控制株高的显性基因，其中3A，5A和6B染色体上的基因表现为强效，1A和4B染色体上的基因表现为弱效。通过双端体分析进一步将控制株高的基因定位到1AS，3AS，5AL和4BL上。

巨穗小麦种质小穗数的染色体定位研究

巨穗小麦新种质材料是一具有茎秆粗壮、叶片短宽直立、穗大、粒大、结实率高等特点的种质资源。应用单体分析和双端体分析方法对“241”材料进行遗传学研究，结果表明，小麦新种质材料“241”的3A、1B、2B和6B染色体上具有控制小穗数的隐性基因，其中3A、1B和2B染色体上的基因表现为强效，6B染色体上的基因表现为弱效。通过双端体分析进一步将控制小穗数的基因定位到3AS、1BL和6BS上，其中3AS、6BS上可能具有控制“241”小穗数的新基因。控制“241”穗粒数和控制小穗数的基因可能存在一定的连锁关系。