苯甲醛缩4-氨基安替比林希夫碱的合成、晶体结构和量子化学研究

用4-氨基安替比林与苯甲醛在质量分数为0.1的醋酸钠水溶液中反应合成了化合物C18H17N3O,并培养出了单晶,其晶体结构通过单晶X-射线衍射法测定.化合物(C18H17N3O,Mr=291.35)属单斜晶系,空间群P21/c,晶胞参数:a=13.046(3),b=6.935 0(14),c=17.266(3)(A),α=89.91(3)(A),γ=90.08(3)(°),V=1 561.8(5)(A)3,Z=4,Dc=1.239 g·cm-3,F(000)=616,R=0.053 0,wR =0.153 8,μ0.079mm-1.采用密度泛函理论(DFT)B3LYP方法,运用Gaussian 03量子化学程序包,对该化合物的分子轨道成分及能级、原子自然电荷分布、自然键轨道及稳定化能等进行了量子化学计算.     

8-羟基喹啉锰配合物结构和电子性质的密度泛函研究

用密度泛函理论(DFT)B3LYP方法,对8-羟基喹啉锰配合物进行理论研究,探讨配合物的结构,分子轨道成份和能级、电荷分布、自然键轨道等。Mn与8-羟基喹啉中的N原子和O原子形成不对称六配位的稳定配合物,其中Mn与N的平均配位键长为0.207 2 nm,Mn与O的平均配位键长为0.188 7 nm。金属Mn对前线轨道的贡献很大,在HOMO轨道中占29.39%,在LUMO轨道中占58.62%。     

3-溴-2-(2′,3′-二溴-4′,5′-二甲氧基苯甲基)-4,5-二甲氧基苯甲酸甲酯的合成及其PTP1B 酶抑制活性研究

为了研究海洋溴系列化合物的生物活性,以香兰素(1)为起始原料,经过溴代、还原、氧化、傅克酰基化及酯化等反应,成功的合成了新化合物3-溴-2-(2′,3′-二溴-4′,5′-二甲氧基苯甲基)-4,5-二甲氧基苯甲酸甲酯(9),总收率为19.6%。通过1H-NMR,13C-NMR等方法对目标产物进行了结构表征。通过比色法对目标化合物进行了PTP1B酶抑制活性测定,结果显示化合物浓度为20 mg/L时,PTP1B酶抑制率为55.84%,表明该化合物有一定的PTP1B酶抑制活性。     

2种新型18β-甘草次酸修饰物对四氯化碳致小鼠肝损伤的保护作用

本文研究了顺式-3β-O-[4-(R)-(3-氯苯基)-2-氧代-1,3,2-二氧磷杂环己基]-18β-甘草次酸(GA16R)和顺式-3β-O-[4-(S)-(3-氯苯基)-2-氧代-1,3,2-二氧磷杂环已基]-18β-甘草次酸(GA16S)2种修饰物对四氯化碳致小鼠急性肝损伤的保护作用.结果表明,GA16R和GA16S均能减轻CCl4致小鼠急性肝损伤程度,明显降低血清中丙氨酸氨基转移酶(ALT)、天门冬氨酸氨基转移酶(AST)、乳酸脱氰酶(LDH)的升高,明显降低肝组织中丙二醛(MDA)的含量,明显增加肝组织中超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GSH-PX)的活力.证明2种新型甘草次酸化合物对四氯化碳致小鼠急性肝损伤均有明显的保护作用.     

激发态质子转移分子2-(2''-羟基苯基)苯并噻唑溶液的全光开关效应

研究了激发态质子转移(ESPT)分子2-(2'-羟基苯基)苯并噻唑(HBT)在不同极性溶剂中的光开关行为,探讨了溶剂极性对HBT分子光开光效应的影响.揭示了光开关脉冲信号的形成原因,建立了基于光诱导HBT分子激发态非线性折射效应的皮秒全光开关的理论模型.根据对时间响应函数的理论计算和实验结果分析,确定了光开关脉冲信号下降前沿和上升后沿的形成机理以及影响因素,并提出了增强光开关信号下降前沿的关断深度,提升上升后沿的恢复速度的有效途径和方法.本文工作为制成皮秒量级关断,微秒甚至纳秒量级重新打开的快速全光开关器     

2种新型18β-甘草次酸修饰物对四氯化碳致小鼠肝损伤的保护作用

本文研究了顺式-3-βO-[4-(R)-(3-氯苯基)-2-氧代-1,3,2-二氧磷杂环己基]-18β-甘草次酸(GA16R)和顺式-3β-O-[4-(S)-(3-氯苯基)-2-氧代-1,3,2-二氧磷杂环己基]-18β-甘草次酸(GA16S)2种修饰物对四氯化碳致小鼠急性肝损伤的保护作用。结果表明,GA16R和GA16S均能减轻CCl4致小鼠急性肝损伤程度,明显降低血清中丙氨酸氨基转移酶(ALT)、天门冬氨酸氨基转移酶(AST)、乳酸脱氢酶(LDH)的升高,明显降低肝组织中丙二醛(MDA)的含量,明显增加肝组织中超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GSH-PX)的活力。证明2种新型甘草次酸化合物对四氯化碳致小鼠急性肝损伤均有明显的保护作用。     

多环芳烃对2种海洋微藻的联合毒性效应研究

本文以青岛大扁藻 (Platymonassubcordiformis) ,球等鞭金藻 870 1 (Isochrysis galbana870 1 )为试验材料 ,采用水生毒理联合效应指数法 ,比较了 3种多环芳烃 ,蒽 (anthracene) ,并 [a]芘 (benzo[a] pyrene)及 1 ,2 -苯并蒽 (1 ,2 - benzonthracene)单剂和混剂对青岛大扁藻和球等鞭金藻 870 1的急性毒性和联合毒性。实验结果表明 :对青岛大扁藻 ,胁迫 72 h,蒽与苯并 [a]芘的联合及苯并 [a]芘与 1 ,2 -苯并蒽的联合为协同作用 ,蒽与 1 ,2 -苯并蒽的联合及蒽 ,苯并 [a]芘与 1 ,2 -苯并蒽的联合为拮抗作用。对球等鞭金藻 870 1胁迫 72 h,苯并 [a]芘与 1 ,2 -苯并蒽的联合为协同作用 ,其它联合均为拮抗作用。     

大黄鱼β2-微球蛋白基因的克隆及其在大肠杆菌中的重组表达

主要组织相容性复合体（major histocompatibility complex，MHC）是一类高度多态的基因群，它广泛分布于各种脊椎动物体内，在启动特异性免疫应答中起关键作用．MHC根据结构分为Ⅰ型和Ⅱ型两种．β2-微球蛋白（β2mcroglobulin，β2m）是MHCI型分子的轻链．本文根据大黄鱼β2m的表达序列标签（expressed sequence tags，EST）序列设计合成了特异性引物，利用RT—PCR技术从大黄鱼脾脏组织中克隆了β2m基因（Pscr-β2m）；构建了合β2m因的原核表达载体（pGEX4T-2-β2m，在0．1mmol／dm^3IPTG诱导下重组β2m得到了表达；采用Sepharose 4B亲合层析纯化目的蛋白并制备了抗体；Western—blotting分析证实了该抗体具有与天然大黄鱼脾脏组织中β2m蛋白反应的特性．这些结果为进一步研究鱼类β2m构与功能的关系，以及制备MHCI类分子四聚体奠定基础．     

红笛鲷(Lutjanus sanguineus)CD4和CD4-2基因克隆与诱导表达

应用RT-PCR和RACE-PCR技术克隆了红笛鲷(Lutjanus sanguineus)CD4和CD4-2基因,并分析了它们在健康鱼不同组织的表达分布及免疫刺激物诱导后的表达变化。CD4基因c DNA序列全长2216bp,包含180bp的5′UTR(untranslated regions)、605bp的3′UTR和1431bp的开放阅读框(open reading frame,ORF),编码476个氨基酸;红笛鲷CD4-2基因c DNA序列全长为1520bp,包含62bp的5′UTR、525bp的3′UTR和933bp的ORF,编码310个氨基酸。CD4分子由信号肽、4个免疫球蛋白样结构域(D1—D4)构成的胞外区、跨膜区和胞浆区组成,CD4-2分子由信号肽、2个免疫球蛋白样结构域(D1—D2)构成的胞外区、跨膜区和胞浆区组成。荧光定量PCR(Real Time Quantitative PCR,q PCR)分析显示红笛鲷CD4和CD4-2基因在健康鱼的胸腺中表达量最高,其次是中肾、鳃、皮肤、脾、头肾和肠。红笛鲷头肾淋巴细胞体外经脂多糖(Lipopolysaccharide,LPS)和刀豆蛋白A(Concanavalin A,Con A)刺激12h后,CD4和CD4-2表达量显著上调(P0.05)。哈维氏弧菌疫苗免疫24h后鳃、头肾、脾脏和肠的表达量显著上升(P0.05)。研究结果为进一步研究鱼类CD4和CD4-2在抗菌免疫反应中的作用提供了基础资料。     

Ln(Ⅲ)与2-羟基-1-萘醛缩4-氨基安替吡啉配合物的合成、表征及热分解动力学

合成了稀土硝酸盐与希夫碱 2 -羟基 - 1 -萘醛缩 4-氨基安替吡啉 (以 HL表示 )的 3种配合物。通过元素分析、IR、UV和摩尔电导分析等方法 ,确定配合物的组成为 [Ln(HL) (C2 H5OH)(H2 O) 2 ] (NO3 ) 3 (Ln=La,Nd,Eu) ,并用非等温热重法研究了 Eu( )配合物的热分解反应动力学 ,推断出第 3步热分解动力学方程为 :dα/dt=A· e-E /RT· 1 /2 (1 -α) [- ln(1 -α) ] -1 。     

2-(N-芳基氨甲基)苯并异噻唑啉酮类化合物对海洋浮游生物的生长抑制活性研究

本文研究了13个2-(N-芳基氨甲基)苯并异噻唑啉-3-酮类化合物对球等鞭金藻Isochrysis galbana、亚心形扁藻Platymonas subcordiformis及舟形藻Navicula的生长抑制性能,并测试了其对藤壶二期无节幼虫的生物活性。结果表明:2-(N-芳基氨甲基)苯并异噻唑啉-3-酮类化合物对球等鞭金藻、亚心形扁藻和舟形藻都有良好的生长抑制活性,其中对球等鞭金藻和亚心形扁藻的抑制作用较强;对藤壶幼虫的生物活性测试表明,化合物最低质量浓度为2.0 mg/L时,除化合物g和l,都具有良好的生长抑制活性。化合物的结构与浮游生物的生长抑制活性关系表现为间位取代优于对位取代。     

南海软珊瑚共附生真菌Aspergillus sp. EGF15-0-3苯甲醛类化合物研究*

本文研究了具有克服肿瘤耐药活性的软珊瑚共附生真菌Aspergillus sp. EGF 15-0-3苯甲醛类化学成分。采用硅胶柱层析、十八烷基硅烷键合硅胶层析、Sephadex LH-20层析、高效液相色谱(high performance liquid chromatography, HPLC)等多种方法进行分离纯化; 通过核磁共振波谱(nuclear magnetic resonance, NMR)、质谱(mass spectrometry, MS)等现代波谱分析及物理常数对照等方法进行结构鉴定; 采用MTT法对苯甲醛部位和单体化合物进行克服肿瘤耐药活性研究。从EGF15-0-3的苯甲醛部位共得到9个苯甲醛类化合物, 结构依次为flavoglaucin (1)、tetrahydroauroglaucin (2)、isoaspergin (3)、 isotetrahydroauro-glaucin (4)、dihydroauroglaucin (5)、isodihydroauroglaucin (6)、2-(1',5'-heptadienyl)-3, 6-dihydroxy-5-(3'-methyl-2'-butenyl) benzaldehyde (7)、auro-glaucin (8)和2-(2',3-epoxy-1'-heptenyl)-6-hydroxy-5- (3'methyl-2'-butenyl) benzaldehyde (9)。体外克服肿瘤耐药活性研究表明, 苯甲醛类化合物9具有较强的克服肿瘤耐药活性, 可能是由于其结构2位烷基侧链与3羟基形成吡喃环所致。     

Effect of exposure to benzo[a]pyrene on SODs, CYP1A1/1A2- and CYP2E1 immunopositive proteins in the blood clam Scapharca inaequivalvis

The effects of water-borne exposure to benzo[a]pyrene (36 h; celite-bound 0.44 mg L(-1) B[a]P) on cytochrome P450 (CYP) and superoxide dismutases (SODs) were examined in digestive gland of the blood clam, Scapharca inaequivalvis. B[a]P accumulation and elimination were rapid, with maximum whole-body concentrations of 1.78 ng g(-1) wet wt after 12 h of treatment, followed by a progressive decline to 0.89 ng g(-1) at 36 h. The presence of B[a]P resulted in an increase in total CYP of digestive gland microsomes from 54+/-14 to 108+/-21 pmol/mg protein (mean+/-SD; p<0.05, 24 h). Increases were also seen in microsomal CYP1A1/1A2-immunopositive protein (50.5 kDa app. mol. wt; p<0.05), but not CYP2E1-immunopositive protein (49 kDa app. mol. wt.), indicating a specific response of the former isoform. Exposure to B[a]P produced a steady increase in Mn-SOD digestive gland activity (p<0.01; p<0.05) but no significant change in Cu/Zn-SOD activity. The respective proteins, measured by western blotting, were not significant induced after B[a]P exposure. Cu/Zn-SOD and Mn-SOD activities were correlated with total CYP levels (r=0.96 and 0.63, respectively), indicating a role for CYP in reactive oxygen species (ROS) production during exposure. Both 'NADPH-independent' and NADPH-dependent metabolism of B[a]P by digestive gland microsomes was seen, producing mainly 1,6-, 3,6- and 6,12-diones, with some phenols and 7,8-dihydrodiol; putative protein adducts were also formed. Redox cycling of the diones may also have contributed to ROS production, leading to the increased SOD activities.     

围隔生态系中叶绿素a浓度、化学耗氧量及透明度之间统计关系的研究

通过对水库中12个围隔两次取样的叶绿素a浓度(单位:μg/L)、化学耗氧量(单位:mg·O_2/L)和塞克透明度(单位:m)的实验数据分析,求得如下回归方程: (1)[Chla]=17.60·[SD]~(-1·86) r=-0.87 (2)[Chla]=-28.85+7.32·[COD] r=0.89 (3)[COD]=6.88·[SD]~(-0·68) r=0.91本文还对这些结果进行了讨论。     

B[a]P-DNA binding in early life-stages of Atlantic tomcod: population differences and chromium modulation

Atlantic tomcod (Microgadus tomcod) from the Hudson River (HR) are resistant at the molecular and organismic levels to the effects of exposure to dioxin-like aromatic hydrocarbon (AH) compounds, but much less so to benzo[a]pyrene (B[a]P). The aims of this study were to determine in early life-stages of tomcod exposed to B[a]P: (1) if DNA binding levels differed between fish from the HR and Miramichi River (MR), and (2) if co-exposure to chromium could modulate this genotoxic effect. After exposure to [(3)H]B[a]P alone, DNA-bound radioactivity was 5-10-fold higher in embryos and larvae of MR than HR descent. Co-exposure to chromium modulated DNA binding levels in offspring of both populations. In MR embryos, co-exposure to chromium inhibited B[a]P uptake. These results demonstrated resistance to the genotoxic effects of B[a]P in early life stages of HR tomcod at an ecologically important endpoint and suggest the ability of chromium to modulate AH-induced genotoxicity.     

南沙地块OBS2019-2测线数据处理与震相识别*

为揭示南海南部陆缘的地壳结构, 研究其张裂-破裂机制, 开展共轭陆缘对比, 我们在南沙地块礼乐西海槽附近的洋陆转换带上完成了OBS2019-2测线的探测工作。相较于北部陆缘, 南部陆缘已有的海底地震仪(ocean bottom seismometer, OBS)测线较少, 对深部地壳结构的研究也较少, 因此OBS2019-2测线就尤为重要。文章重点阐述了OBS2019-2测线的数据处理工作, 包括UKOOA文件制作、数据格式转换、位置校正、单个台站综合地震记录剖面的生成等, 然后在剖面图中对各类深部震相(Pg、PcP、PmP、Pn)进行识别追踪, 并建立初步的模型; 使用Rayinvr软件进行走时试算工作, 验证了震相识别的准确性。处理结果显示OBS2019-2测线的深部震相清晰, 最远震相可以连续追踪到120km以外, 数据整体质量良好, 能为后续速度建模和构造解释等工作提供坚实基础。     

Evidence for resistance to benzo[a]pyrene and 3,4,3'4'-tetrachlorobiphenyl in a chronically polluted Fundulus heteroclitus population

Halogenated aromatic hydrocarbons (HAHs) and polynuclear aromatic hydrocarbons (PAHs) are major environmental contaminants. Fish species that are chronically exposed to these compounds can develop resistance to their toxic effects. In all fish species studied to date, toxicant resistance has been accompanied by decreased inducibility of the xenobiotic metabolizing enzyme, cytochrome P450 1A (CYPIA). CYP1A induction is mediated through the Aryl Hydrocarbon Receptor (AHR). Although these compounds mediate their effects through this pathway, there have been resistant populations in which one chemical class cannot induce CYPIA expression (HAHs) while the other (PAHs) can. Resistance to PAHs was examined in a HAH-resistant population of Fundulus heteroclitus collected from a site contaminated with both compound classes (Newark Bay, NJ). Fish were injected intraperitoneally with the HAH 3,4,3',4'-tetrachlorobiphenyl (PCB77), benzo[a]pyrene (B[a]P, a PAH) or vehicle and sacrificed after 2 (B[a]P) or 5 days (PCB77, vehicle). We found no significant increase in CYP1A mRNA levels in resistant Newark Bay F. heteroclitus treated with either B[a]P or PCB77, while there was a 3.9 fold (PCB77) and 4.2 fold (B[a]P) increase in CYP1A mRNA in Flax fish relative to controls. AHR labeling studies revealed significantly (P < 0.05) lower levels of hepatic AHR in Newark fish (1,770 +/- 1,693.2 DPM) relative to Flax fish (6,082.5 +/- 1,709.9 DPM). Overall, these data suggest Newark F. heteroclitus are resistant to both PAHs and HAHs at the level of CYP1A mRNA, which might be mediated, in part, though lower expression of AHR. We are currently studying the promoter sequence to determine its role in chemical resistance.     

Complex accumulation and leakage of YC21-1 gas bearing structure in Yanan sag,Qiongdongnan basin,South China Sea

YC21-1 is a gas-bearing structure found within the Yanan sag in the Qiongdongnan Basin, South China Sea. While the structure bears many geological similarities to the nearby YC13-1 gas field, it nevertheless does not contain commercially viable gas volumes. The main reservoirs of the YC21-1 structure contain high overpressures, which is greatly different from those of the YC13-1 structure. The pressure coefficients from drillstem tests, wireline formation tests and mud weights are above 2.1. Based on well-log analysis, illite content and vitrinite reflectance data of mudstones in well YC21-1-2, combining with tectonic and sedimentation characteristics, the timing and causes of overpressure generation are here interpreted. The results indicate the existence of two overpressure segments in the YC21-1 structure. The first overpressure segment resides mainly within the lower and the middle intervals of the Yinggehai Formation, and is interpreted to have been mainly caused by clay diagenesis, while disequilibrium compaction and hydrocarbon generation may also have contributed to overpressure generation. The second overpressure segment comprising the Sanya Formation (Pressure transition zone) and the Lingshui and Yacheng Formations (Hard overpressure zone) is interpreted to owe its presence to kerogen-to-gas cracking. According to petrography, homogenization temperature and salinity of fluid inclusions, two stages of oil-gas charge occurred within the main reservoirs. On the basis of overpressure causes and oil-gas charge history, combining with restored tectonic evolution and fluid inclusion characteristics, a complex accumulation and leakage process in the YC21-1 gas bearing structure has been interpreted. Collective evidence suggests that the first oil charge occurred in the Middle Miocene (circa 16.3–11.2 Ma). Small amount of oil generation and absence of caprocks led to the failure of oil accumulation. Rapid subsidence in the Pliocene and Quaternary gave rise to a sharp increase in geotemperature over a short period of time, leading to prolific gas-generation through pyrolysis and, consequently, overpressure within the main reservoirs (the second overpressure segment). During this period, the second gas charge occurred in the Pliocene and Quaternary (circa 4.5–0.4 Ma). The natural gas migrated in several phases, consisting of free and water soluble phases in a high-pressure environment. Large amounts of free gas are considered to have been consumed due to dissolution within formation water in highly pressured conditions. Water soluble gas could not accumulate in high point of structure. When the pore-fluid pressures in main reservoirs reached the fracture pressure of formation, free gas could leak via opened fractures within cracked caprocks. A repeated fracturing of caprocks may have consumed natural gas stored in formation water and have made water-soluble gas unsaturated. Therefore, the two factors including caprocks fracturing and dissolution of formation water are interpreted to be mainly responsible for the failure of natural gas accumulation in the YC21-1 structure.     

阻挫三角反铁磁AgCrO2螺旋自旋序的第一性原理研究

基于密度泛函理论的广义梯度近似(GGA)和投影缀加波(PAW)方法,分别从共线和非共线磁性结构出发,研究了自旋阻挫三角反铁磁AgCrO₂的基态、磁性以及电子结构,从理论计算的角度给出了基态磁性结构.计算结果表明:AgCrO₂具有120°螺旋自旋序反铁磁基态,其自旋螺旋面平行于(110)面或(11 0)面;由于Cr离子间的自旋几何阻挫,导致沿晶体的a,b和a+b方向上均形成了螺旋自旋转动角为120°的相互平行的螺旋自旋链;     

STUDY OF MARINE MICROFOULING ORGANISMSSOME CHARACTERISTICS OF THE MICROFOULING TO FIVEMATERIAL SURFACES OBSERVED BY THE SCANINGELECTRON MICROSCOPE

In the last few years, scanning electron microscope (SEM) has been widely used to observeand study community structure and succession of the microfouling organisms on various solid surfaces immersed in the sea, polysaccharide components of bacterial slime layer, two-tier microfouling layer structure , metal corrosion products in the attached process and character-istics of attached microorganisms on the coating surfaces. The SEM observations indicated that substrate components exposed to natural seawater are one of the important factors affecting microbial adhesion. The present paper examined the influences of several metal materials, from which ship is usually made on microbial adhesion during the exposure to seawater by the SEM and discussed the material selecting problems from the anti-microfouling point of view.