967 resultados para 3-R-concept


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合成了新化合物K_5H[Co_4(VW_9O_(33))·5H_2O,并运用IR,UV-ViS,DTA和单晶X射线衍射对其结构进行了表征.测定结果证实标题化合物具有α-B-Keggin型结构,两个(VW_9O_(33)~(7-)结构单元由四个Co(Ⅱ)O_6 八面体连接.杂多化合物属单斜晶系P2_(1/n),a=1.2307(3)nm,b=2.1250(4)nm,c=1.5817(3)nm,β=91.86(3)°,V=4.1343(14)nm~3,R=0.0895,R_w=0.2180.

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The crystal structure and mechanism of the title molecule are described. This crystal is orthorhombic, belonging to space group PC21/B with a=1,002 1(2) nm, b=1.483 0(3) nm, c=2.173 6(4) nm, V=3.230 39(2) nm(3), Z=2, D-c=1.80 g/cm(3), R=0.069 3. The structure was solved by direct method. The tin atom of the title compound exists in two distorted-trigonal-bipyramidal geometry, defined by two carbon, one bromide, one chloride and one oxygen atoms leading to a five-membered chelate ring. In the structure, the five-membered ring containing the intermolecular O-->Sn has a half chair conformation.

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[(C6H5CH2C5H4)(2)GdCl . THF](2) (1) and (C6H5CH2C5H4)(2)ErCl . THF (2) were prepared by the reaction of LnCl(3) (Ln=Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P2(1)/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, beta=108.75(2), V=2.4732(9) nm(3), Z=2(four monomers), D-c=1.54 g . cm(-3). R=0.0342 and R(w)=0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P2(1)2(1)2(1) space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm(3), Z=4, D-c=1.56 g . cm(-3). R=0.0514, R(w)=0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd3+ are located in the opposite direction (139 degrees); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er3+ are located in the same direction (6.5 degrees).

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The electrochemical transfer behaviour of vanadium-containing heteropolytungstate anions [PW12-xVxO40]((3+r)-) (x = 1-4) across the water \nitrobenzene interface has been investigated by cyclic voltammetry and chronopotentiometry with cyclic linear current scanning. The transfer of PW11V1O404-, HPW10V2O404-, H2PW10V2O403-, H3PW9V3O403- and H4PW8V4O(40)(3-) across the water \nitrobenzene interface can be observed within the potential window. The effects were observed of pH in the water phase on the transfer behaviour and the formation of vanadium-containing heteropolytungstate anions in solution. Heteropolytungstate anions become more stable due to their involving the vanadium atom. The degree of protonation and the dissociation constant of the trivalent vanadium-containing heteropolytungstate anion of protonation increase with increasing vanadium content. The transfer processes are diffusion-controlled The standard transfer potential, the standard Gibbs energy and the dissociation constant for vanadium-containing heteropolytungstate anions have been obtained and the transfer mechanisms are discussed.

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The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usual F conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C12H17N4OS+.I- . 1.5 H2O, monoclinic, P2(1)/c, a = 12.585(2), b = 25.303(5), c = 12.030(2) angstrom, beta = 115.15(1)degrees, V = 3468(1) angtrom3, Z = 8, D(c) = 1.606 g cm-3, R = 0.045 for 3328 observed reflections.

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Rare earth trifluoroacetates, Ln(CF3CO2)(3) (Ln = thirteen rare earth elements), combined with R(n)AlH(3-n) (R = methyl, octyl, n = 3; R = ethyl, i-Butyl, n = 2, 3) were used as catalysts for the polymerization of tetrahydrofuran (THF). The activity increased by adding propylene oxide (PO), as a promoter, to the polymerization system, producing high molecular weight polytetrahydrofuran (PTHF). The effects of Ln, PO/Ln, and Al/Ln, and others on the polymerization of THF were also studied. (C) 1993 John Wiley & Sons, Inc.

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New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

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合成了三茚基稀土配合物(η~5-C_9H_7)_3Ln·OC_4H_8(Ln=Nd、Gd、Er),经元素分析、红外光谱、水解产物核磁共振谱及质谱表征,并测得了(η~5-C_9H_7)_3Nd·OC_4H_8(1)及(η~5-C_9H_7)_3Gd·OC_4H_8(2)的晶体结构。(1)、(2)均属六方晶系,P6_3空间群,Z=2。(1)的晶体学参数为a=b=1.1843(3)nm,c=1.0304(4)nm,V=1.25165(87)nm~3,D_c=1.49g·cm~(-3),最后一致性因子R=0.049;(2)的晶体学参数a=b=1.1805(2)nm,c=1.0236(2)nm,V=1.23536(56)nm~3,D_c=1.54 g·cm~(-3),R=0.023。平均Nd-C=0.2812nm,Gd-C=0.2795nm;Nd-O=0.2557(21)nm,Gd—O=0.2459(13)nm。配合物中四氢呋喃的四个碳原子处于完全无序状态。

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LaCl_3和LiCl在THF中于室温反应,以已烷为沉淀剂,在-78℃得到晶体,经色谱、元素分析及X射线晶体结构测定,得到了组成为(LaCl)(THF)_2(μ-Cl)_4[Li(THF)_2]_2的配合物.在约-80℃收集该配合物晶体的衍射强度数据,计算结果表明属于单斜晶系,P2_1/c空间群,其晶胞常数a=10.542(4)(?),b=32.236(14)(?),c=11.182(6)(?);β=113.50(3)°,最后R值为0.0477.四个氯桥键构成了分子的基本骨架,表明桥键在小配体轻希土双金属配合物结构中具有稳定作用.

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在害赤潮作为一种全球性的海洋灾害,给海洋环境、水产养殖业和人类健康造成巨大危害,研究赤潮的发生规律,探索新的、经济有效的赤潮的防治方法具有重要的科学意义和应用前景。本文针对中国沿海常见赤潮生物种,研究了粘土矿物双赤潮生物基本生理指标的影响,进一步探讨了粘土矿物的控制赤潮机制;并针对粘土矿物去除效率不高的特点,制备出具有较高絮凝胶效率的改性粘土;此外,本文还首次将无机高分子絮凝效率的改性粘土;此外,本文还首次将无机高分子絮凝剂MMH(混合金属氢氧化物正电胶体)和PSMS(聚硅酸金属盐)用于赤潮治理研究中,并探索了上述赤潮防治剂的环境生态效应,主要成果与内容有:1、粘土矿物的筛选 采集国内外近30种粘土矿物,分别考察了它们对中国沿海常见赤潮生物种赤潮异弯藻(Heterosigma akashiwo)和塔玛亚历山大藻(Alexandrium tamarense)的去除效果。结果表明,不同粘土矿物对赤潮生物的絮凝能力有显著差别,实验筛选出去除效果较好的几种粘土,分别为来自美国的Chemically treated kaolin、WHOI土、江苏吴县高岭土及苏州特号土等。通过絮凝实验得到上述几种粘土矿物对两种赤潮生物的絮凝曲线,发现不同粘土矿物对赤潮生物的最大去除率及达到最大去除率所需的粘土浓度有较大差别,同一粘土矿物对不同赤潮生物的去除效果也不相同。塔玛亚历山大藻较赤潮异变藻更易被粘土矿物去除。2、粘土矿物对赤潮生物的生理效应 研究了高岭土对赤潮异弯藻和塔玛来历山大藻生长繁殖、叶绿素a含量、光合作用以及呼吸作用的影响。结果表明,高岭土对赤潮生物生长、叶绿素a含量及光合作用均有抑制作用,表现为随粘土浓度的增加及作用时间的延长,抑制作用增强,并认为这可能与粘土的加入导致光照效应降低及藻类生长的营养环境改变有关。实验同时发现高岭土对不同赤潮生物的抑制程度不同,塔玛亚历山大藻上述各项生理指标比赤潮异弯藻更易受粘土影响。3、无机絮凝剂的制备及絮凝作用研究 主要考察了无机高分子絮凝剂MMH及PSMS(聚硅酸金属盐),包括聚硅酸氯化铝(PSAC)和聚硅酸硫酸铝(PSAS)的合成及对赤潮生物的絮凝作用。在MMH的合成过程中,考察了镁铝摩尔比及制备温度对MMH絮凝赤潮异弯藻的影响,认为镁铝摩尔比为2的条件下制备的MMH具有较好的絮凝和沉降性能,其絮凝赤潮异弯藻的最佳用量为1.5mmolAl/L。在PSAS的合成中采用三因子三水平的正交试验设计,得到PSAS的最佳制备条件为:SiO_2浓度 = 2%, Al~(3+)/SiO_2 = 1, pH = 4。絮凝实验结果表明,PSAS对赤潮生物的絮凝效果优于传统絮凝剂AS(硫酸铝),同时PSAS对不同赤潮生物的絮凝效果也不同,认为这主要与不同赤潮生物的形态结构、运动性及胞外分泌物有关。4、粘土矿物表面改性及机理研究 为提高粘土矿物去除赤潮生物的效率,分别用插入法和表面吸附法制备改性粘土。实验得出插入法的最佳制备条件为:制备温度70 ℃,镁离子浓度2mol/L;表面吸附法中粘土和MMH(混合金属氢氧化物胶体)的适宜配比为:粘土/MMH=10。改性后粘土去除赤潮异弯藻的效率较改性前提高2-3倍。相关分析表明,改性粘土去除赤潮生物的效率与改性后表面电位呈正相关,两种情况下R~2均大于0.8,说明表面电位是影响粘土矿物去除赤潮生物的一个重要因素。5、赤潮治理的现场模拟实验及环境生态效应 在1999年夏季胶州湾中肋骨条藻(Skeletonema costatum)赤潮的发生现场进行了改性粘土及PSAS对藻类去除率、悬浮物、DO、COD、pH等指标的影响研究。结果表明,改性粘土及PSAS对现场中肋骨条藻有较高的去除率,1g/L的改性高岭土和改性蒙脱土对中肋骨条藻的去除率分别可达77%和93%,1ml/L的PSAS去除率达90%以上。DO的含量轻微下降,不致影响其他生物的生长,COD下降幅度较大,达50-80%。6、赤潮防治剂对中国对虾的毒性研究 进行了粘土、次氯酸钙、氯化铝和氯化铁对中国对虾的毒性试验,结果表明,1g/L的高岭土对虾基本无毒性;次氯酸钙在低浓度下对对虾无毒,在高浓度下对对虾有急性毒性效应,安全使用浓度为0.5ml/L游离氯;氯化铝和氯化铁在对虾体内有一定的积累,其长期的毒性效应有待于进一步的分析。上述几种试剂均可用于粘土矿物的改性处理中,是比较安全的赤潮防治剂。

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海洋是一个巨大的天然产物宝库,约占地球表面积70%的海洋蕴藏着80%的生物资源。由于海洋生态环境的特殊性,导致海洋生物能够产生大量结构独特多变和活性特殊多样的代谢产物。我国海域辽阔,海洋资源丰富,为寻找结构新颖、生理活性独特的先导化合物,加强对海洋资源的开发利用,本论文对中国沿海的三种海洋红藻和两株放线菌次生代谢产物以及生物活性进行研究,为新药研究与开发提供模式结构和药物前体。 对红藻似瘤凹顶藻Laurencia similis乙酸乙酯萃取物进行分离纯化,从中得到单体化合物35个,通过波谱学方法(IR、MS、NMR等)鉴定了他们的结构。分别为:2, 2, 5, 5, 6, 6-sixibromo-3, 3-bi-1H-indole (1),3,5-dibromo- 1-methyl-indole (2),3',5',6,6'-tetrabromo-2,4-dimmethyldiphenyl ether (3),1,2,5- tribromo-3-bromoamino-7-bromomethylnaphthalene (4),2,5,8-tribromo-3-bromo- amino-7-bromomethylnaphthalene (5),2,5,6-tribromo-3-bromoamino-7-bromo- methylnaphthalene (6), 2,5,6,5',6'-pentabromo-3,4,3',4'-tetramethoxybenzophenone (7), (4E)-1-bromo-5-[(1'S*,3'R*)-3'-bromo-2',2'-dimethyl-6'-methylenecyclohexyl] -3-methylpent-4-ene-2,3-diol (8),4-hydroxy-Palisadin C (9),Isopalisol (10),Luzonensol (11),Palisadin B (12),Aplysistatin (13),Palisadin A (14),5-Acetoxypalisadin B (15),Aristolan-1(10)- en-9-ol (16),Aristol-8-en-1-one (17),Aristolan-9-en-1-one (18),Aristolan-1(10)-en- 9-one (19),Aristofone (20),Aristolan-1(10)-8-diene (21),Aristolan-1,9-diene (22),10-Hydroxyaristolan-9-one (23),7,11,15-trimethyl-3-methylene-hexadecan-1,2-diol (24),3β-Hydroxyergosta- 5,24(28)-dien-7-one (25),Isofucosterol (26),β-sitosterol (27),豆甾-4-烯-3α,6β-二醇 (28),Cholesta-5-en-3β-ol (29),Stigmasterol (30),2,3,5,6-四溴-吲哚 (31),2,3,6-tribromo-1H-indole (32),3,5,6-tribromo-1-methylindole (33),3,5,6-tribromo -1H-indole (34),2,3,5-tribromo-1-methylindole (35),其中化合物1-9为新化合物,化合物10-15、20和化合物24-30均为首次从该种海藻中得到。对新化合物1-9进行PTP1B酶抑制剂活性筛选,新化合物1、3、7显示强的PTP1B酶抑制活性。 对红藻齐藤凹顶藻Laurencia saitoi乙酸乙酯萃取物进行分离纯化,从中得到单体化合物11个,通过波谱学方法(IR、MS、NMR等)鉴定了他们的结构,分别为:2-hydroxyl-Luzofuranone (1),2-hydroxyl-Luzofuranone B (2),4-hydroxyl-Palisudin C (3),2-bromo-γ-ionone (4),Aplysistatin (5),5-Acetoxypalisadin B (6),Palisadin B (7),Palisadin A (8),Pacifigorgiol (9),豆甾-4-烯-3α,6β-二醇 (10),2, 3, 5, 6-四溴-吲哚 (11),其中化合物1-4为新化合物,所有化合物均为首次从该种海藻中得到。通过MTT法对分离得到的新化合物1-4进行肿瘤细胞毒活性筛选,结果显示4个新化合物对所测肿瘤细胞株均无明显的活性。 对红藻瘤状软骨凹顶藻Chondrophycus papillous乙酸乙酯萃取物进行分离纯化,从中得到单体化合物5个,通过波谱学方法(MS、NMR等)鉴定了他们的结构,分别为邻苯二甲酸二丁酯 (1),邻苯二甲酸二异辛酯 (2),胆甾醇 (3),3,7,11,15-tetramethyl-hexadec-2-en-1-ol (4),4-羟基苯甲醛 (5),所有化合物均为首次从该种海藻中得到。 对海洋放线菌M159乙酸乙酯萃取物进行分离纯化,从中得到单体化合物13个,通过波谱学方法(MS、NMR等)鉴定了他们的结构,分别为:5-(4',6'-dihydroxy-6-methyloctyl)furan-2(5H)-one (A),phenethyl alcohol (1),4-羟基苯甲醛(2),anthranilic acid (3),4-Hydroxy-3-methoxy- phenyl-propionic acid (4),5-(6,7-dihydroxy-6-methyloctyl)furan-2(5H)-one (5),p-Hydroxyphenylethyl alcohol (6),3-Indoleacrylic acid (7),Indol-3-carboxylic acid (8),Adenine cordyceposide (9),腺嘌呤核苷(10),尿嘧啶核苷(11),Thymidine (12),其中化合物A为新化合物。所有化合物均为首次从该株放线菌中得到。 对海洋放线菌L211乙酸乙酯萃取物进行分离纯化,从中得到单体化合物15个,通过波谱学方法(MS、NMR等)鉴定了7个结构,分别为:spatozoate (1),anthranilic acid (2),3-Indolylethanol (3),1-Acetyl-β-carbolin (4),p-Hydroxyphen- ylethyl alcohol (5),Indole-3-acetic acid (6),Indol-3-carboxylic acid (7),所有化合物均为首次从该株放线菌中得到。

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One new sesquiterpene, (4E)-1-bromo-5-[(1'S*, 3'R*)-3'-bromo-2',2'-dimethyl-6'-methylenecyclohexyl]-3-methylpent-4-ene-2,3-diol (1), and fifteen known sesquiterpenes, isopalisol (2), luzonensol (3), palisadin B (4), aplysistatin (5), palisadin A (6), 4-hydroxyl-palisudin C (7), 5-acetoxypalisadin B (8), 10-hydroxyaristolan-9-one (9), aristol-8-en-1-one (10), aristolan-9-en-1-one (11), aristolan-1(10)-en-9-one (12), aristolan-1( 10)-en-9-ol (13), aristolan-1(10), 8-diene (14), aristolan-1,9-diene (15) and aristofone (16), were isolated from a sample of marine red alga Laurencia similis. Their structures were established by detailed NMR spectroscopic analysis and comparison with literature data. Compounds 2-9, and 16 were isolated for the first time from this species. All these metabolites were submitted for a cytotoxicity assay against the tumor cell line BEL7402 (human liver adenocarcinoma), but all of them were found inactive (IC50 > 10 mu g/mL).

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目的:建立测定牛尾蒿油滴丸中β-蒎烯含量的方法。方法:气相色谱法,采用填充色谱柱(3m×3mm),固定相为8%二乙二醇丁二酸酯,汽化温度180℃,柱温120℃,载气(氮气)流速10mL•min^-1。结果:β-蒎烯的理论塔板数为2106,回归方程为Y=2.705×10^5X-3.544×10^3(r=0.9999),线性范围为0.2163—3.460mg•mL^-1,平均回收率±RSD为99.16%±0.59%。结论:以该法测定主要有效成分β-蒎烯的含量,理论塔板数较高、分离度较好。该方法可用于牛尾蒿油滴丸的质量控制。

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本文对鬼灯檠属Rodgersia Gray的染色体数、花粉体积和纹饰、萼片数目、萼片脉序和脉型、萼片腹面毛被、花梗和花序轴毛被、叶的类型等关键性状进行了分析,确定了其进化顺序;依据性状的系统发生,绘制了鬼灯檠属的瓦格勒尔系统树;确认本属有5种和3变种,其中以R.podophylla为最原始, R.nepalensis为最进化,而R.aesculifolia,R.sambucifolia和R.pinnata则居于两者之间。本属分两组Sect.Rodgersia,仅含R.podophylla;Sect.Sambuclfolia J.T.Pan,含R.aesculifolia,R.sambucifolia,R.pinnata,R.nepalensis。依据种的主要分布区,划本属植物为4个分布类型,即:日本-朝鲜间断分布,秦岭-大巴山分布,横断山分布和东喜马拉雅分布。笔者认为, 本属的起源地在日本一朝鲜一带, 横断山地区是其现代分布中心和分化中心本属的散布路线是自日本一朝鲜, 经秦岭一大巴山, 通过横断山地区而进入东喜马拉雅本属的起源时间, 当在晚第三纪以前晚白要世至早第三纪。此外, 还报道了鬼灯集属植物的花粉形态。

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There are two major problems that have been concerned all the times, which are the mechanics characters of joint rock mass and the criterion for stability of engineering rock. Aim at the two problems, several works were conducted as follow: (1) Firstly, the mechanics characters of rock mass was studied by means of the Distinct Element Code. Subsequently, it was studied that the sensibility of joint surface roughness, strength of joint wall, joint stiffness ( i.e. tangential and normal stiffness) on the rock mass strength. (2) Based on the experimental rock mass classification methods of RMR and GSI, the program of “Parameters Calculation of the Rock Mass ” was developed. It has realized the rapid choice of rock mass parameters. (3) The concept of Representive Element Volume was induced based on the study of dimensional effect of rock mass. The Representive Element Volume of the horizontal and vertical pillar (ab. Two Pillars ) in the 2nd zone of Jinchuan mine were gained by the Geology Statistic Method and the Distinct Element Code. And then, the strength and deformatiom parameters of rock mass of the Two Pillars were obtained through numerical experiment. (4) From the confining depressure after thriaxial compression test of rock sample, it was concluded that the failure of rock is caused mainly by the lateral deformation and energy release happened during the confining depressure processure. The criterion of plastic energy catastrophe of rock engineering failure was proposed and validated. Subsquently, the stability of the horizontal pillar and Qianjiangping landslide in Three Gorges was judged by means of above-mentioned method. (5) Based on the fact there is a phenomenon of increasing energy concentration while the rock mass was compressed, rock information entropy (i.e. energy distribution entropy) was proposed. And it was revealed that there was change of energy distribution entropy while the rock mass was compressed to failure.