用高分辨NMR对聚甲基硅氧烷-聚脲嵌段共聚物以及聚氰丙基甲基硅氧烷-聚脲嵌段共聚物结构进行表征,对NH形成的各种氢键进行详细的研究,同时观察了氢键在力学性能中的作用,结果发现氢键强烈地影响着力学性能。用固体¹H宽线研究这类材料的相分离状况,并总结影响相分离的因素。保持硬段含量不变,增加软段分子量使相分离程度增加;保持软段分子量不变,增加硬段含量使相分离程度降低。软、硬段之间的相互作用(如氢键)使相分离程度降低。

测定了二个顺磁性化合物(Ph₄P)[V₃(mp)₆](Ⅰ)和(Ph₄P)₂[NaV(mp)₃(MeCN)(MeOH)](Ⅱ)(H₂mp=邻巯基苯酚,o-HO1C₆H₄SH)的固态和/或溶液中的顺磁波谱。(Ⅰ)的77K固态谱及(Ⅱ)的室温固态谱均经模拟计算,认为它们的钒原子处在S=l/2的Ⅰ=7/2状态,(Ⅱ)的低温(77K)溶液谱(乙腈)与Ⅱ的固态谱相同,均有特征的八条精细结构,认为非配对电子基本上定域在钒原子的周围。

由于谱峰拥挤和重迭、关附庚素的一部分¹H和¹³C谱峰用一般核磁共振方法难于确定归属。本工作采用选择性远程DEPT、一维COSY和-维接力COSY等新技术作了研究,其¹H和¹³C谱峰归属全部得到确定。结果有助于此类化合物的化学结构测定。

本文首次报道了从祁州漏芦中分离得到的一种新的蜕皮甾酮类化合物的化学结构,主要利用各种核磁共振方法并结合其它光谱数据,确定其结构为2β,3β,11α,14α,20,22,24-七羟基-5β(20R,22R,24S)-胆甾-7-烯-6-酮,命名为漏芦甾酮(Rhapontisterone)。

本文对周口店北京猿人遗址的动物牙齿化石进行了辐照产生的陷阱捕获电子的热稳定性研究和釉质样品及牙质样品的热稳定性对比实验。得到釉质样品中g=2.0016 ESR峰的寿命为7.1×10⁶年(20℃)。说明了取该峰进行ESR年代测定的可信性和用釉质样品进行ESR年代测定的必要性。

本文解析了同位素标记的⁶³Cu-¹⁴N-HAP,⁶⁵Cu-¹⁴N-HAP,⁶³Cu-¹⁵N-HAP。⁶⁵Cu-¹⁵N-HAP,和Cu-¹⁵N-HAP,等五种配合物在四氢呋喃中,在77K温度下测得的分辨较好的ESR波谱。从图上不仅得到了⁶³Cu和⁶³Cu的超精细分裂,而且还得出分辨较好的¹⁴N和¹⁵N的超超精细分裂。比较合理地确定了g_x,g_y,g_z;A_x⁶⁵,A_y⁶⁵,A_z⁶⁵和A_x⁶³,A_y⁶³,A_z⁶³以及A_⊥¹⁵,A_⊥¹⁵和A_⊥¹⁴,A_⊥¹⁴等张量参数。利用测得的波谱参数计算了键参数,并讨论了配合物的电子结构及成键特性,得到了较满意的结果。

以对应的光学活性四氢β-咔啉在相转移条件下经Aldol缩合、脱水生成的光学活性吲哚喹嗪,与例如丙二酸二甲酯发生Michael加成时,显示高度的立体专属性。作为有广泛用途的建筑块,本文提供了六个代表性化合物的2D-NMR的同核二维相关谱(COSY)和同核欧沃豪斯谱(NOESY)。根据实验测得的NOE关系,满意地指定了化合物中新引人的手性碳的构型,借助分子模型,讨论了它们的构象及Michael反应的反应活性差异。

本文用远程异核化学位移相关谱(COLOC-S脉冲序列)和异核化学位移相关谱研究了香茶菜属二萜类化合物冬凌草甲素和香茶菜醛的化学结构,并对这两个化合物的¹³C和¹HNMR谱线进行了归属。

本文分别测定了东北天蚕茧和龙蛓天蚕茧各内,中,外三层茧层的固态¹³C CP-MASNMR波谱,对其谱峰进行了归属,估算了谱峰区主要谱线在该区所占的比例,还计算了各个茧层丝蛋白中无定形状态所占的百分含量。谱图显示了东北天蚕茧层与龙(蛓)天蚕茧层丝蛋白结构的差异。

High resolution solid state NMR techniques (such as MAS, CP/MAS and CRAMPS) were employed to study the nature of organic molecules adsorbed on porous solids.
A magic angle spinning system was achieved for sealed samples with a spinning speed from 2KHz to 4.2KHz. Using this technique, high resolution ¹H MAS spectra of organic molecules and H₂S adsorbed on charcoal were obtained. Experimental results suggest that for high coverage of adsorbed organic molecules, the spectral lines were resolved very well. But for low coverage, the spectral lines could not be separated completely. As the organic molecules condensed in pores (liquid-like phase) dominate for high coverage, the spectra could be easily resolved under lower spinning speed rate. While for low coverage, the portion of molecules adsorbed on solid surface (solid-like phase) is relatively larger and the resonance lines could not be narrowed even under higher spinning speed rate due to the increase in various kinds of interactions of adsorbed molecules. We could not obtain further narrowed spectrum by CRAMPS technique. The contribution to the residual spectral width was discussed.
A modified Goldman-shen pulse sequence was provided to measure the ¹H spin diffusion times of toluene (MB) and tetrahydrofuran (THF) adsorbed on a series of porous solids (charcoal, SiO₂ and Al₂O₃). In the experiment, the two peaks of THF and MB were selectively reversed to produce effective spin diffusion. The spin diffusion times of MB and THF adsorbed on different types of solids vary in a wide range (from several milliseconds to several hundreds of milliseconds). This implies that the motions of molecules adsorbed on different solids experience different degrees of hindrance owing to their molecular structures and adsorbed states. For THF and MB adsorbed on Al₂O₃,biexponential behavior was observed in the recovery processes of the negative peaks. This was attributed to the existence of two different kinds of spin diffusion processes. One was the intramolecular spin diffusion of adsorbed molecules, the other was the intermolecular one between molecules adsorbed on solid surface and acidic groups of Al₂O₃. It is owing to the adsorbed state the bi-exponential character was obvious in the cases of THF and MB adsorbed on Al₂O₃.It is possible that the oxygen atom of THF and aromatic ring of MB are closely connected to Lewis acid sites, the neighbour acidic groups of Bronsted sites (or a small tiny amount of coadsorbed water molecules) will affect the protons of those molecules adsorbed on surface and enhance their spin diffusion. In addition, the intermolecular ¹H spin diffusion between charcoal and adsorbed THF molecules was confirmed by the indirect measurement proposed by Tekely et al.
The ¹³C-¹³C spin diffusion between enriched methanol (30%) and charcoal was investigated by ¹³C CP/MAS combining with selective excitation methods. The experimental results and ¹³C T₁ measurement show that there is no obvious ¹³C-¹³C spin diffusion and the relaxation of methanol carbon appears to be bi-exponential recovery which was assigned to two different kinds of adsorbedstates.
DNP (Dynamic Nuclear Polarization) was used to study CO (natural abundance) adsorbed on Co-Mo/Al₂O₃ catalysts. After only several hundreds of accumulation, the enhanced ¹³C signal was obtained. But the experiment could not be reproduced. The experimental details were discussed and some suggestion for further investigation was provided.

鸦胆子油在治疗颈癌、胃癌、肺癌等方面,已取得较好的疗效^[1,2]。本文用¹H NMR测定了该油的各组峰面积积分。为纠正最强峰C CH₂C对其两侧弱峰的干扰,作者提出一个经验公式以扣除基团重叠部分的积分值。并按文献[3]的方法,计算了鸦胆子油中每摩尔所含各功能团的个数、各功能团间的比率、酯化度、不饱和度、结合脂肪酸基平均碳数和平均分子量等。并从所测得结合脂肪酸的含量,估算出鸦胆子油中的油酸的含量,结果与文献[4]相符。

本文用¹H-NMR,¹³C-NMR,同核化学位移相关2D、异核化学位移相关2D技术,测定了两种环丁酮的衍生物,求出其优势构象并归属了化合物中所有氢及碳的化学位移。

本文提出两条等价性定理,用来判别不同排列的相位循环是否等价。又提出一种新的设计相位循环的方法-脉冲单元法,克服了由多线相干转移路径引起的多值性困难。

由我国东北产的苦参中分离出七种生物碱。由MS、IR及2D-NMR鉴定为:(+)-苦参碱、(+)-氧化苦参碱、5α-羟基苦参碱、N-甲基金雀儿碱、9α-羟基苦参碱及氧化槐根碱。另一个生物碱(6)的化学结构尚在鉴定之中。本课题采用了二种2D-NMR技术,H-H相关谱(300、400及500MHz)及C-H相关谱(H:300MHz;C:75MHz)。先发表其中两个生物碱的2D-NMR,其它将陆续发表。

本文研究了在手性位移试剂Eu(tfc)₃存在下,绿柱虫二萜二醇A(clavudiol A)(1)中各甲基的化学位移变化,并对19-甲基和20-甲基的¹H-NMR进行了归属。

用溶剂CCl₄,在室温(22℃)条件下,对三种乙丙橡胶共聚物进行¹³C-NMR测定,得到分辨率较高的图谱,标识了各种类型C原子,确定了共聚单体组成和序列分布。结果表明,样品A、B具有嵌段丙烯和嵌段乙烯序列结构可能性较大,样品C具有交替丙烯-乙烯-丙烯序列的倾向较大。用两种统计模型对三个样品的三元组分布进行处理来推测聚合反应机理。

本文测定了几种二茂铁有机锡衍生物的¹¹⁹Sn,¹³C NMR谱。对其中几种衍生物的¹³C NMR谱进行了归属,从而进一步验证了这类化合物的结构。着重讨论了结构如化合物中取代基X的改变对¹¹⁹Sn化学位移的影响。并对结构如
类化合物N→Sn异侧配位的问题进行了讨论。