聚甲基丙烯酸乙酯链结构核磁共振(NMR)研究

本文用~1H-NMR,~(13)C-NMR和化学位移相关谱(COSY)研究了聚甲基丙烯酸乙酯(PEMA)的链结构.虽然质子峰的重叠给谱的识别带来一些困难,但是利用H-H COSY和C-H COSY提供的信息讨论了PEMA的~1H谱和~(13)C谱中各谱峰的归属.归属β-CH_2的四元组立构序列仍有一些问题.最后计算了无规PEMA的五元组立构序列分布.

水溶液中甘氨酰替亮氨酸与Ho(ClO_4)_3和Yb(ClO_4)_3相互作用的NMR研究(英文)

本文用~(13)C NMR方法研究了水溶液中三价顺磁性稀土离子Ho~(3+)和Yb~(3+)与二肽甘氨酰替亮氨酸之间的相互作用。对稀土诱导位移中的接触位移和偶极位移进行了分离。实验表明,与羧基相连的碳核所受的接触作用很大,因此不能把镱诱导的位移直接用于肽的构象分析。在水溶液中,肽通过羧基与稀土离子配位,在弱酸性条件下肽键和氨基均不参与配位。根据结构因子确定了肽在溶液中的构象,结果表明,分子片段C1-C2-C5-C6,C2-N-C3-C4和C2-C5-C6-C8为反式,而C2-C5-C6-C7和C1-C2-N-C3成旁式。

电子计算机自动结构解析专家系统研究——带有键属性的亚结构与~(13)C—NMR化学位移相关性

本文系统地介绍了利用~(13)C-NMR数据库系统统计法建立带有键属性亚结构与~(13)C-NMR化学位移相关表(结构解析专家系统的约束知识库的一个组成部分)的过程。在亚结构的选择上作了深入的探讨。在亚结构检索上提出了加权码值计算方法。

氮丙啶衍生物的稳定性和固化反应机理的~13C-NMR研究

本文用~(13)C-NMR方法研究了间苯二甲酰二(2-甲基氮丙啶)和癸二酰二(2-甲基氮丙啶)的稳定性和固化反应机理。在常温下,这两种化合物均可缓慢重排为(口恶)唑啉,也可同空气中水发生水解反应。在重排和固化反应过程中,它们的N-CH和N-CH_2键断裂情况是不同的。

水溶液中羟脯氨酸稀土配合物的NMR研究

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。

Laurendecumallenes A-B and laurendecumenynes A-B, halogenated nonterpenoid C-15-Acetogenins from the marine red alga Laurencia decumbens

Four new halogenated nonterpenoid C-15-acetogenins, 4:7,6:13-bisepoxy-9,10-diol-1,12-dibromopentadeca-1,2-diene (1, laurendecumallene A), 4:7,6:12-bisepoxy-9,10-diol-1,13-dibromopentadeca-1,2-diene (2, laurendecumallene 13), (3Z)-6:10,7:13-bisepoxy-12-bromo-9-hydroperoxylpentadeca-3-en-1-yne (3, laurendecumenyne A), and (3Z)-6:10,9:13-bisepoxy-12-bromo-7-chloropentadeca-3-en-1-yne (4, laurendecumenyne 13), together with one known halogenated C-15-acetogenin elatenyne (5) were isolated and identified from the organic extract of the marine red alga Laurencia decumbens. Their structures and relative stereochemistry were established by means of spectroscopic analysis including UV, IR, high-resolution electrospray ionization mass spectrometry (HRESIMS), and ID and 2D NMR techniques. All these metabolites were submitted for the cytotoxic assay against tumor cell line A549 (human lung adenocarcinoma), but all of them were found inactive (IC50 > 10 mu g/mL).

Halogenated Terpenes and a C-15-Acetogenin from the Marine Red Alga Laurencia saitoi

Seven parguerane diterpenes: 15-bromo-2,7,19-triacetoxyparguer-9(11)-en-16-ol (1), 15-bromo-2,7,16,19-tetraacetoxyparguer-9(11)-ene (2), 15-bromo-2,19-diacetoxyparguer-9(11)-en-7,16-diol (3), 15-bromo-2,16,19-triacetoxyparguer-9(11)-en-7-ol (4), 15bromo-2,16-diacetoxyparguer-9(11)-en-7-ol (5), 15-bromoparguer-9(11)-en-16-ol (6), 15-bromoparguer-7-en-16-ol (7), two polyether triterpenes: thyrsiferol (8) and thyrsiferyl 23-acetate (9), and one C15-acetogenin, neolaurallene (10), were isolated from a sample of marine red alga Laurencia saitoi collected off the coast of Yantai. Their structures were established by detailed NMR spectroscopic analysis and comparison with literature data.

A new naphthoquinoneimine derivative from the marine algal-derived endophytic fungus Aspergillus niger EN-13

Cultivation of an endophytic fungus Aspergillus niger EN-13 that was isolated from the inner tissue of the marine brown alga Colpomenia sinuosa resulted in the characterization of a new naphthoquinoneimine derivative, namely, 5,7-dihydroxy-2-[1-(4methoxy-6-oxo-6H-pyran-2-yl)-2-phenylethylaniino]-[1,4]naphthoquinone. The structure of the new compound was established on the basis of various NMR spectroscopic analyses including 2D NMR techniques, EI-MS, and HR-ESI-MS. This compound displayed moderate antifungal activity. (c) 2007 Bin Gui Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

New sphingolipids with a previously unreported 9-Methyl-C-20-sphingosine moiety from a marine algous endophytic fungus Aspergillus niger EN-13

Asperamides A (1) and B (2), a sphingolipid and their corresponding glycosphingolipid possessing a hitherto unreported 9-methyl-C-20-sphingosine moiety, were characterized from the culture extract of Aspergillus niger EN-13, an endophytic fungus isolated from marine brown alga Colpomenia sinuosa. The structures were elucidated by spectroscopic and chemical methods as (2S,2'R,3R,3'E,4E,8E)-N-(2'-hydroxy-3'-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (1) and 1-O-beta-D-glucopyranosyl-(2S,2'R,3R,3'E,4E,8E)-N-(2'-hydroxy-3'-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (2). In the antifungal assay, asperamide A (1) displayed moderate activity against Candida albicans.

The Obduction of Equatorial 13 degrees C Water in the Pacific Identified by a Simulated Passive Tracer

The obduction of equatorial 13 degrees C Water in the Pacific is investigated using a simulated passive tracer of the Consortium for Estimating the Circulation and Climate of the Ocean (ECCO). The result shows that the 13 degrees C Water initialized in the region 8 degrees N-8 degrees S, 130 degrees-90 degrees W enters the surface mixed layer in the eastern tropical Pacific, mainly through upwelling near the equator, in the Costa Rica Dome, and along the coast of Peru. Approximately two-thirds of this obduction occurs within 10 years after the 13 degrees C Water being initialized, with the upper portion of the water mass reaching the surface mixed layer in only about a month. The obduction of the 13 degrees C Water helps to maintain a cool sea surface temperature year-round, equivalent to a surface heat flux of about -6.0 W m(-2) averaged over the eastern tropical Pacific (15 degrees S-15 degrees N, 130 degrees W-eastern boundary) for the period of integration (1993-2006). During El Nino years, when the thermocline deepens as a consequence of the easterly wind weakening, the obduction of the 13 degrees C Water is suppressed, and the reduced vertical entrainment generates a warming anomaly of up to 10 W m(-2) in the eastern tropical Pacific and in particular along the coast of Peru, providing explanations for the warming of sea surface temperature that cannot be accounted for by local winds alone. The situation is reversed during La Nina years.

Origin and Pathway of Equatorial 13 degrees C Water in the Pacific Identified by a Simulated Passive Tracer and Its Adjoint

The origin and pathway of the thermostad water in the eastern equatorial Pacific Ocean, often referred to as the equatorial 13 degrees C Water, are investigated using a simulated passive tracer and its adjoint, based on circulation estimates of a global general circulation model. Results demonstrate that the source region of the 13 degrees C Water lies well outside the tropics. In the South Pacific, some 13 degrees C Water is formed northeast of New Zealand, confirming an earlier hypothesis on the water's origin. The South Pacific origin of the 13 degrees C Water is also related to the formation of the Eastern Subtropical Mode Water (ESTMW) and the Sub-Antarctic Mode Water (SAMW). The portion of the ESTMW and SAMW that eventually enters the density range of the 13 degrees C Water (25.8 < sigma(theta) < 26.6 kg m(-3)) does so largely by mixing. Water formed in the subtropics enters the equatorial region predominantly through the western boundary, while its interior transport is relatively small. The fresher North Pacific ESTMW and Central Mode Water (CMW) are also important sources of the 13 degrees C Water. The ratio of the southern versus the northern origins of the water mass is about 2 to 1 and tends to increase with time elapsed from its origin. Of the total volume of initially tracer-tagged water in the eastern equatorial Pacific, approximately 47.5% originates from depths above sigma(theta) = 25.8 kg m(-3) and 34.6% from depths below sigma(theta) = 26.6 kg m(-3), indicative of a dramatic impact of mixing on the route of subtropical water to becoming the 13 degrees C Water. Still only a small portion of the water formed in the subtropics reaches the equatorial region, because most of the water is trapped and recirculates in the subtropical gyre.

植物营养元素的含量和δ~(13)C值随海拔而变化的特征及营养元素相互作用对碳同位素分馏作用的影响

为了研究植物营养元素的含量和δ~(13)C值随海拔而变化的相关关系,沿着海拔450 m的贵州茂兰至海拔1330 m的贵州安顺一线,采集和分析研究了C_3植物——小果蔷薇(R.cymosa Tratt)的叶片。分析结果表明,植物叶片中营养元素含量随着海拔的上升而产生的变化是:氮、磷和钾的含量会在增高,而钙和镁的含量却会降低。植物叶片的δ~(13)C值会增大,其变幅为+2.4‰/1000m。

The stability of nanosized HZSM-5 zeolite: a high-resolution solid-state NMR study

The thermal and hydrothermal stabilities of HZSM-5 zeolites with crystal sizes less than 100 nm have been studied by multinuclear solid-state NMR, combined with BET and XRD. As evidenced by Al-27 and Si-29 MAS as well as their corresponding cross-polarization/MAS NMR investigations, the thermal stability of nanosized HZSM-5 is not so good as that of microsized HZSM-5. This is due to two processes concerning dealumination and desilicification involved in the calcination of nanosized HZSM-5, while only the dealumination process is conducted in microsized HZSM-5 under the similar calcination process. The hydrothermal stability of nanosized HZSM-5 is, contrary to what was expected, not so bad as that of the microsized HZSM-5 in the course of steam treatment. The actual resistance of the hydrothermal stability to the crystal size of HZSM-5 can be ascribed to an active reconstruction of zeolitic framework through an effective filling of amorphous Si species into nanosized HZSM-5 during hydrothermal treatment. (C) 2001 Published by Elsevier Science B.V.