250 resultados para ~(13)C NMR
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本文测定了在三种不同稀土离子(镧La~(3+)、钬Ho~(3+)和镱Yb~(3+)的水溶液中甘氨酰-缬氨酸的~1H和~(13)C稀土诱导位移。计算了Ho、Yb与甘氨酰-缬氨酸配合物的稳定常数,讨论了稀土与该配体的配位作用及对配合物构象进行研究,发现配位后的甘氨酰-缬氨酸以一种空间位阻较小的伸展构象存在。
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测定了在11种稀土离子(La~(3+)、Pr~(3+)、Nd~(3+)、Eu~(3+)、Tb~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)、Yb~(3+)和Lu~(3+)存在下羟脯氨酸~(13)C的诱导位移和抗磁性稀土配合物体系的~(1)H化学位移与偶合常数。对配合物构象分析表明,在水溶液中羟脯氨酸以空间位阻小的“外向”构象存在,通过羧基与稀土离子形成双齿配位结构,Ln~(3+)-O键长为2.1。在水溶液中巳配位的与游离的氨基酸和水分子间的快速配位交换平衡导致稀土氨基酸配合物具有有效轴对称性。
A broad deglacial delta C-13 minimum event in planktonic foraminiferal records in the Okinawa Trough
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The equatorial Pacific upwelling zone has been suspected of playing an important role in the global atmospheric CO2 changes associated with glacial-interglacial cycles. In order to assess the influencing scope of the surface water deglacial delta(13)C minimum in the tropical low-latitude Pacific, the core DGKS9603, collected from the middle Okinawa Trough, was examined for 4513 C records of planktonic foraminifera N. dutertrei and G. ruber. The planktonic foraminiferal delta(13)C records show a clear decreasing event from 20 to 6 cal. kaBP., which is characterized by long duration of about 14 ka and amplitude shift of 0.4 x 10(-3). Its minimum value occurred at 15.7 cal kaBP. The event shows fairly synchrony with the surface water deglacial delta(13)C minimum identified in the tropical Pacific and its marginal seas. Because there is no evidence in planktonic foraminiferal fauna and 45180 records for upwelling and river runoff enhancement, the broad deglacial delta(13)C minimum event in planktonic foraminiferal records revealed in core DGKS9603 might have been the direct influencing result of the deglacial surface water of the tropical Pacific. The identification for the event in the Okinawa Trough provides new evidence that the water evolution in the tropical low-latitude Pacific plays a key role in large regional, even global carbon cycle.
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本实验对三种萝藦科植物通光散(Marsdenia tenacissima)、黑水藤(Biondia insignis Tsiang)和徐长卿(Cynanchum Paniculatum)中的C21甾体化合物进行了研究。从通光散藤茎乙酸乙酯提取物的水解产物中,分离得到两类八个C21甾类甙元。经光谱鉴定,它们的结构分别为11α-O-(2-甲基)-丁酰基-12β-O-顺芷酰通光藤甙元乙(1),11α-O-乙酰基-12β-O-乙酰基通光藤甙元乙(2),11α-O-(2-甲基)-丁酰基-12β-O-乙酰基通光藤甙元乙(3), 11α-O-苯甲酰基-12β-O-乙酰基通光藤甙元乙(4), 11α-O-顺芷酰基-12β-O-乙酰基通光藤甙元乙(5)11α-O-顺芷酰基-12β-O-顺芷酰基通光藤甙元乙(6),12β-O-乙酰基通光藤甙元甲(7)和12β-O-顺芷酰基通光藤甙元甲(8)。其中,化合物2和8为新化合物。从黑水藤乙醇提取物的水解产物中,分离得到了两个C21甾体化合物。经1D、2D NMR技术鉴定,分别为(3β,14β,15β,17β)-3, 14-二羟基-15,16-裂-孕甾-5-烯-15-醛-16-半缩醛-20-酮(1)和白前甙元C(2)。其中1为15,16-裂环的新骨架类型的C21甾体化合物,命名为黑水藤甙元甲。从采购于昆明、浙江、湖南三地药材市场的徐长卿的根及根茎中,分离得到了18个化合物(其中昆明徐长卿6个,浙江徐长卿9个,湖南徐长卿3个)。经光谱数据分析,这些化合物被鉴定为:cynapanoside-C (1), cynapanoside-A (2), 白前甙元B 3-O-β-D-磁嘛吡喃糖甙(3),白前甙元C 3-O-β-D-葡萄吡喃糖基-(1 → 4)-α-L-2-脱氧洋地黄吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-夹竹吡喃糖甙(4),白前甙元C3-O-β-D-葡萄吡喃糖基-(1 → 4)-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-夹竹桃吡喃糖甙(5),白前甙元C 3-O-β-D-葡萄吡喃糖基-(1 → 4)-β-D-葡萄吡喃糖基-(1 → 4)-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-夹竹桃吡喃糖甙(6),cynatratoside-B (7),cynatratoside-C (8);glaucoside A(9),新白薇甙元B 3-O-β-L-磁嘛吡喃糖基-(1 → 4)-β-D-洋黄吡喃糖基-(1 → 4)-β-D-夹竹桃吡喃糖甙(10),白前甙元 A 3-O-α-L-磁嘛吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(11),白前甙元 B 3-O-α-L-磁糖基吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(12),白前甙元D 3-O-α-L-磁嘛吡喃糖基(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(13),白前甙元 C 3-O-β-D-葡萄吡喃糖基-(1 → 4)-β-D-葡萄吡喃糖基-(1 → 4)-α-L-2-脱氧洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖基-(1 → 4)-β-D-夹竹桃吡喃糖甙(14),白前甙元 C 3-O-β-D-葡萄吡喃糖基-(1 → 4)-β-D-葡萄吡喃糖基-(1 → 4)-α-L-磁嘛吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-夹竹桃吡喃糖甙(15),白前甙元 B 3-O-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(16),白前甙元 D 3-O-α-D-夹竹桃吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(17),白前甙元月B 3-O-α-L-磁嘛吡喃糖基-(1 → 4)-β-D-洋地黄吡喃糖基-(1 → 4)-β-D-磁嘛吡喃糖甙(18)。其中,化合物3-6,10-18为新化合物,10的甙元为一个新甙元,命名为新白薇甙无B。
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近年来对稀土冠醚络合物的研究日益受到重视文献曾报导了12-冠-4,15-冠-5,18-冠-6等冠醚与稀土的固体络合物的合成性质及结构的研究,但大部分工作侧重于研究冠醚空腔与稀土离子直径的匹配程度对络合物稳定性的影响,而对于冠醚具有的取代基、空间构型及其配位阴离子等对络合物稳定性、组成结构的影响尚注意得很不够,对溶液中络合物的研究工作较少;特别是冠醚对稀土元素萃取性质的研究未见系统报导。本论文以瑞士进口的二环已基18-冠-6(DCC)混合物为原料进行异构体的分离。得到纯异构体A、B、D的~(13)C谱,不同位置的五种碳原子的谱线清析可辨,其化学位移值与计算值比较,确定了谱线的归属,利用单一异构体测定结果,对异构体A、B、D混合物进行鉴定得到满意结果。利用分离得到的纯异构体A、B及北京五所提供的异构体D合成了与轻稀土硝酸盐络合物。元素分析结果指出,除1:1络合物外,首次得到非1:1组成的络合物。La(NO_3)_3·DDC(DCC=Ia,Id),[Ln(NO_3)_3]_3(DCC)_2 (Ln=Ce,Pr,Nd,DCC=Ia,Id)而异构体B得到全部3:2的络合物。选择硝酸镧与三种异构体的络合物进行了热分析,结果指出3:2与1:1络物物表现出完全不同的热分解行为。3:2络物合只有一步分解,且比1:1络物合具有更高的热分解温度1:1络合物分两步分解,首先发生向3:2络合物的转变。络合物的红外光谱研究表明,络合物中冠醚与自由冠醚的红外光谱图呈现明显区别,冠醚环上COC反对称伸展振动在生成络合物后向低频产生50~70 cm~(-1)的位移,其中3:2比1:1络合物位移量略大,络合物中硝酸根的振动吸收全部呈现配位硝酸根的特征谱带,并且3:2与1:1络合物之间呈现明显差别。另外在远红外区观察到Ln-O(NO_3~-)的振动谱带。用NMR研究冠醚与稀土在非水溶剂中的络合反应。首先测定了12-冠-4,15-冠-5与位移试剂Pr(fod)_3,Eu(fod)_3,Yb(fod)_3体系中冠醚次甲基上'H及~(13)C的化学位移值Δδ,得到了谱线随稀土与冠醚浓度比改变的变化规律。位移方向,对于Pr向高场移动,对于Eu、Yb向低场移动,位移量及谱线宽度的大小为Yb>Pr>Eu。且Δδ~(13)C>Δδ~1H符合几何因素的规律,即正比于(3COS~2θ-1)/~r~3。利用二种方法计算了不同温度下络合物的稳定常数。对于不同冠醚,K值次序为冠-5>冠-4>冠-6,对于不同位移试剂为Pr>Eu>Yb。利用不同温度的K_1值,计算并讨论了平衡反应的热力学函数ΔG°,ΔH°,ΔS°。实验考察了微量水存在下络合物的结构和作用机理,在高氯酸盐与冠醚体系的研究中,观察到与位移试剂体系完全相反的规律。还发现在高氯酸稀土与冠醚的体系中快和慢两种交换过程共存,通过对单一交换体系的络合物稳定常数计算方法的改进,提出了适合混合交换体系的计算方法,并计算了18C6与Pr(clo_4)_3络合物在20℃时的稳定常数,K_1=164升/摩乐。系统地研究了12-冠-4,15-冠-5,18-冠-6的衍生物及其二苯并24-冠-8等11种冠醚对单一稀土苦味酸盐的萃取,制备了15个稀土的苦味酸盐,考察了冠醚的空腔大小及取代基和空间构型对冠醚萃取稀土能力的影响,得到了B15C5,B18Cb,DCC萃取15个稀土元素的规律性,测定了相邻稀土元素间的分离因数,讨论了各种因素对DCC异构体萃取分离Pr Nd的影响,指出异构体A具有更大选择性。最大分离因数β_(Nd)~(Pr)=3.5,上述结果将为今后发展冠醚在稀土分离液膜萃取等方面的应用提供基础数据。
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本工作对几个不同类型的聚合物/聚合物共混体系-PS/SBR,EVA/CPE,PVF_2/PEMA和PMAA/PEO-的相容性和共混物中分子基团的相互作用进行了探讨和研究。主要结果有:(1)对不同PS分子量的PS/SBR聚合物共混体系进行了形态观察和Tg测量,结果表明共混物的相容性随PS组分的分子量、组成和温度变化。(2)用固体NMR测量进一步证实了EVA/CPE是分子之间均匀混合的相容共混体系。T_1值在测试温度范围内都符合自旋强相互作用偶合的加和式。(3)对PVF_2/PEMA共混体系进行了固体NMR研究,测量得到~1H的T_1和T_2随温度的变化曲线,用PC/MAS技术得到共混体系的高分辨~(13)C MNR谱,并从各个化学位移峰强对交叉极化接触时间的变化曲线拟合得到不同基团的~1H T_(1p)和T_(CH)。(4)用二维NMR技术通过质子自旋交换相互作用,考察了聚电解质与水溶性聚合物的共混物PMAA/PEO中各个化学基团之间的空间接近程度。
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本文研究了酸性磷(膦)酸酯对稀土及相关元素的萃取(包括协同萃取)机理,利用核磁共振(NMR)测试手段对HEH/EHP(III)、BTMPPA-Yb(III)的萃合物结构进行了~1H、~(13)C、~31P NMR谱的测定,获得了一些新的结构信息。
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Urea bridged organic-inorganic hybrid mesoporous SiO2 materials (U-BSQMs) were synthesized through a sol-gel procedure by co-condensation of bis(triethoxysilyl propyl) urea (BSPU) under basic conditions using cetyltrimethylammonium bromide (CTAB) as organic template. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the mesoporous structure of the sample. Fourier-transform infrared spectroscopy (FT-IR), solid state CP-MAS NMR spectroscopy of Si-29 (Si-29, CP-MAS NMR) and C-13 (C-13 CP NMR) indicated that most of the Si-C bonds are unbroken during the synthesis process.
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A series of novel fluorine surfactants, a, b, c, d, e and their acrylates, A, 13, C, D and E, were synthesized via poly( ethylene oxide) ( PEG) ( 200, 600, 1000, 2000, 5000) and perfluorooctane poly (ethylene oxide) ether as the main starting materials. Their chemical structures were characterized by means of FTIR and H-1 NMR. The surface activity and surface tension( y) of surfactants a, b, c, d and e were evaluated by maximum bubble pressure method. Surfactants A, 13, C, D and E were adopted as the grafting monomers of linear low density polyethere( LLDPE), and grafting reaction was carried out by melt reactive extrusion procedure. Their surface properties were characterized with measuring contact angle and XPS. It was found that the hydrophilic property of the graft copolymers was better than the palin LLDPE. Thermal properties of graft copolymers were studied by DSC. It was found that their crystalline temperatures of graft copolymers were faster than that of the plain LLDPE.
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用一维NMR方法研究了电化学发光物质六氟磷酸二(2,2’-联吡啶)·(4,4’-二甲基-2,2’-联吡啶)合钌(Ⅱ)的立体结构,借助二维~1H-~1H COSY和~1H-~(13)C COSY实验技术对其氢谱和碳谱进行了完全的归属,并给出了其氢谱和碳谱的化学位移值.
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本文应用取代基参数(SCS)方法处了15个EV共聚物的~(12)C NMR谱.它们是:(1)乙烯-α-烯烃共聚物,即乙烯-丙烯共聚物.乙烯-丁烯-1共聚物,乙烯-4-甲基-1-戊烯共聚物,乙烯-己烯-1共聚物和乙烯-辛烯-1共聚物;(2)乙烯-含氧乙烯基共聚物,即乙烯-甲基丙烯酸N,N-二甲基胺乙酯共聚物,乙烯-丙烯酸甲酯共聚物.乙烯-丙烯酸共聚物,乙烯-乙酸乙烯酯,乙烯-乙烯醇,乙烯-氧化碳共聚物(ECO)(?)乙烯-卤代乙烯共聚物及其它EV共聚物,即乙烯-氯化乙烯共聚物(包含氯化聚乙烯),乙烯-溴化乙烯共聚物,乙烯-苯乙烯共聚物(包含氢化丁二烯-苯乙烯共聚物)和乙烯-丙烯腈共聚物、得到了15种取代基的SCS参数.
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The miscibilities of blends of homopolystyrene/styrene-butadiene/styrene (PS/SBS) and PS/SB-4A (4-arm star block copolymer) have been studied by dynamic mechanical analysis (DMA) and C-13 CPMAS NMR techniques. The results indicate that the miscibilities o
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本文用NMR波谱方法研究了无规共聚醚(EPO)的链结构。首先对EPO的~1H和~(13)CNMR谱进行了讨论。并从序列结构随环氧丙烷(PO)含量的改变,分析了EPO的二元组序列和三元组序列结构,从~(13)C实验谱中归纳出EPO的取代基参数(SCS),清楚地揭示了EPO的~(13)C谱,SCS参数和序列结构之间的关系,在此基础上计算了EPO系列共聚物的序列分布和数均序列长度。
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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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Thiol-functionalized mesoporous ethane-silicas with large pore were synthesized by co-condensation of 1,2-bis(trimethoxy-sily)ethane (BTME) with 3-mercaptopropyltrimethoxysilane (MPTMS) using nonionic oligomeric polymer C1H (OCH(2)-CH(2))(10)OH (Brij-76) or poly(alkylene oxide) block copolymer (P123) as surfactant in acidic medium. The results of powder X-ray diffraction (XRD), nitrogen gas adsorption, and transmission electron microscopy (TEM) show that the resultant materials have well-ordered hexagonal mesoscopic structure with uniform pore size distributions. (29)Si MAS NNR, (13)C CP-MAS NMR. FT-IR, and UV Raman spectroscopies confirm the attachment of thiol functionalities in the mesoporous ethane-sificas. The maximum content of the attached thiol group (-SH) in the mesoporous framework is 2.48mmol/g. The ordered mesoporous materials are efficient Hg(2+) adsorbents with almost every -SH site accessible to Hg(2+). In the presence of various kinds of heavy metal ions such as Hg(2+), Cd(2+), Zn(2+), Cu(2+) and Cr(3+), the materials synthesized using poly(alkylene oxide) block cooollxmier (Pluronic 123) g(2+), as surfactant show almost similar affinity to Hg(2+), Cd(2+), and Cr(3+), while the materials synthesized using ofigomeric polymer C(18)H(37)(OCH(2)CH(2))(10)OH (Brij-76) as surfactant exhibit high selectivity to Hg(2+). (C) 2004 Elsevier Inc. All rights reserved.