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Straightforward synthesis of two pairs of enantiomeric butenolides 3-tetradecyl- and 3-hexadecyl-5-methyl-2(5H)-furanone. 两对对映丁烯内酯3-十四烷基和3-十六烷基-5-甲基-2(5H)-呋喃酮的直接合成。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212189
Bu-bing Zeng, T. Hu, W. Yun, Yikang Wu, Yu‐lin Wu
Based on the synthetic method of optically active 3-alkyl-5-methyl-2(5H)-furanones from lactic acid, two pairs of chiral butenolides 3-tetradecyl- and 3-hexadecyl-5-methyl-2(5H)-furanone have been straightforwardly synthesized from methyl stearate and methyl palmitate respectively by aldol condensation with (R)- or (S)-O-tetrahydropyranyl lactal prepared from corresponding ethyl lactate and beta-elimination.
根据乳酸合成旋光性3-烷基-5-甲基-2(5H)-呋喃酮的方法,以硬脂酸甲酯和棕榈酸甲酯为原料,分别与(R)-或(S)- o -四氢吡喃乳酸通过醛醇缩合直接合成了3-十四烷基和3-十六烷基-5-甲基-2(5H)-呋喃酮两对手性丁烯内酯。
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引用次数: 1
Structure-chiroptical properties relationship in oxabicyclic beta-lactam derivatives. 氧环-内酰胺衍生物的结构-热带性质关系。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212200
J. Frelek, R. Lysek, K. Borsuk, J. Jagodziński, B. Furman, A. Klimek, M. Chmielewski
The relationship between molecular structure of 5-dethia-5-oxacephams and clavams and their chiroptical properties was investigated by means of X-ray diffraction analysis, molecular modeling calculations and circular dichroism spectroscopy. It was found that the amide chromophore of the beta-lactam unit in these compounds is nonplanar with nitrogen atom having a pyramidal configuration. It was also found that the helicity of the lactam moiety in investigated oxacephams and clavams is controlled by the absolute configuration at the C-6 and C-5 carbon atom, respectively. Thus, the applicability of helicity rule correlating a positive (negative) torsional angle of the beta-lactam subunit O=C-N-C with a negative (positive) sign of the n-->pi* CE, previously applied to oxacephams, is now extended to clavams.
采用x射线衍射分析、分子模拟计算和圆二色光谱等方法研究了5-dethia-5-oxacephams和clavams的分子结构与热学性质的关系。发现这些化合物中-内酰胺单元的酰胺发色团是非平面的,氮原子具有锥体构型。研究还发现,所研究的oxacephams和clavams中内酰胺部分的螺旋度分别受C-6和C-5碳原子的绝对构型控制。因此,将β -内酰胺亚基O=C-N-C的正(负)扭转角与n- >pi* CE的负(正)符号相关联的螺旋度规则的适用性,以前应用于oxacephams,现在扩展到clavams。
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引用次数: 15
Evaluation of the origins of the selectivity of polymers imprinted with a HIV protease inhibitor using infrared spectroscopy and high performance liquid chromatography. 利用红外光谱和高效液相色谱法评价HIV蛋白酶抑制剂印迹聚合物选择性的来源。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212193
T. O'brien, N. Grinberg, G. Bicker, J. Wyvratt, N. Snow
This work investigates the origins of enantioselectivity of polymers imprinted with the HIV protease inhibitor, Indinavir. For the preparation of imprints of the drug, the critical interactions between the functional monomer, methacrylic acid, and Indinavir were characterized by infrared (IR) spectroscopy to explore the optimum functional monomer concentration for the polymerization. It was shown that a polymer with high selectivity and minimum non-selective binding for Indinavir was obtained when prepared with enough functional monomer to hydrogen bond with all of the functional groups of the drug without using an excess of monomer. This observation is explained in terms of a balance that is achieved in the monomer-template equilibrium during the polymerization that yields a polymer with highly selective sites and minimal non-selective sites. This paper further demonstrates that IR spectroscopy can be a valuable tool in the design and syntheses of molecular imprinted polymers.
这项工作调查了印有HIV蛋白酶抑制剂Indinavir的聚合物对映体选择性的起源。为了制备该药物的印迹,利用红外光谱对功能单体、甲基丙烯酸和茚那韦之间的关键相互作用进行了表征,以探索聚合的最佳功能单体浓度。结果表明,当使用足够的功能单体与药物的所有官能团形成氢键而不使用过量的单体时,可以获得对茚那韦具有高选择性和最小非选择性结合的聚合物。这一观察结果的解释是,在聚合过程中,单体-模板平衡达到了一种平衡,这种平衡产生了具有高选择性位点和最小非选择性位点的聚合物。本文进一步证明了红外光谱在分子印迹聚合物的设计和合成中是一种有价值的工具。
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引用次数: 6
The supramolecular structure of self-assembly formed by capsanthin derivatives. 辣椒素衍生物自组装形成的超分子结构。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212194
Z. Bikádi, F. Zsila, J. Deli, G. Mády, M. Simonyi
Carotenoids form structured self-assembly upon aqueous dilution of their organic solutions. In order to test the proposal predicting carotenoid aggregates to be organized in closely packed H-type (card-pack) manner by intermolecular hydrogen bonds, the trihydroxy derivative of capsanthin (1), (6'R)-capsanthol (2) ((all-E,3R,3'S,5'R,6'R)-beta,kappa-carotene-3,3',6'-triol) was acetylated to obtain all varieties of mono-, di- and triacetates and the corresponding supramolecules were studied by UV/Vis- and CD spectroscopy. It was verified that derivatives lacking hydroxyl functions at either of the end-groups form the loosely organized J-type (head-to-tail) aggregates. A model for the structure of the J-type self-assembly is proposed. Evidence was also obtained suggesting that close contacts of carotenoid molecules are not confined to hydrogen bonding.
类胡萝卜素在其有机溶液的水稀释后形成结构化的自组装。为了验证预测类胡萝卜素聚集体通过分子间氢键以紧密排列的h型(卡片包)方式组织的建议,将辣椒素(1)、(6’r)-辣椒酚(2)((all- e,3R, 3s,5’r,6’r)- β、kappa-胡萝卜素-3,3’,6’-三醇)的三羟基衍生物乙酰化,得到了各种单、二、三乙酸酯,并通过紫外/可见光谱和CD光谱研究了相应的超分子。结果证实,在端基中缺乏羟基功能的衍生物形成了松散组织的j型(从头到尾)聚集体。提出了j型自组装的结构模型。也有证据表明类胡萝卜素分子的密切接触并不局限于氢键。
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引用次数: 25
Synthesis and characterization of new chiral calix[4]arenes. 新型手性杯[4]芳烃的合成与表征。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212191
Y. Okada, M. Mizutani, Fuyuhiko Ishii, J. Nishimura*
The unique chiral calixarenes were successfully synthesized by the following two methods: the Williamson ether synthesis and a stepwise ether cleavage with a mild Lewis acid. The high regioselectivity is recognized by the latter stepwise method. The ionophores having oligoethylene glycol unit efficiently extracted larger alkali metal ions like K+, Rb+, and Cs+ than smaller ones like Li+ and Na+. Their ion selectivity apparently changed by the chain length of crown ether. All racemates obtained could be resolved to each enantiomer by HPLC using a chiral column. The calixarenes with planar chirality recognized the chirality of guest molecules. Thus, the (-)-receptor resolved strongly forms 1:1 complex with (R)-(+)-alpha-phenylethylammonium picrate.
采用Williamson醚合成和温和Lewis酸逐级醚裂解两种方法成功合成了独特的手性杯芳烃。后一种方法具有较高的区域选择性。以低聚乙二醇为单元的离子载体对K+、Rb+、Cs+等较大碱金属离子的萃取效率高于Li+、Na+等较小碱金属离子。它们的离子选择性明显受冠醚链长的影响。所得的所有外消旋物均可通过手性柱的高效液相色谱拆分为各对映体。具有平面手性的杯芳烃能够识别客体分子的手性。因此,(-)受体与(R)-(+)- -苯基乙基苦味酸铵强烈地形成1:1的配合物。
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引用次数: 7
Determination of the absolute configuration of rubroflavin by comparison of measured and calculated CD spectra of its thermolysis product 3-methanesulfinyl-5-methylmercaptophenol. 通过对红黄素裂解产物3-甲磺酸基-5-甲基巯基苯酚CD谱的比较测定红黄素的绝对构型。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212197
G. Raabe, Charlotte Repges, Yuekui Wang, J. Fleischhauer
The absolute configuration of rubroflavin has been determined indirectly by comparison of the measured and the calculated CD spectrum of its thermal decomposition product 3-methanesulfinyl-5-methylmercaptophenol. Performing geometry optimizations at the HF/6-31+G* level we found fifteen local minima for the (R)-isomer of 3-methanesulfinyl-5-methylmercaptophenol. The CD spectrum of the compound was then obtained as a superposition of the Boltzmann-weighted spectra for each structure calculated with the non-empirical CIS method. The corresponding Boltzmann factors have been calculated employing the relative energies of these minima determined at the ZPE + MP2/6-31+G*//HF/6-31+G* level of ab initio theory. Comparing the signs of the observed and calculated longest wave length Cotton effect we assign an absolute configuration to the thermolysis product. Since additional calculations revealed that the tricoordinate sulfur atom in rubroflavin and in its decomposition product is configurationally stable under the conditions of thermolysis we conclude that the absolute configuation at the corresponding sulfur atom of rubroflavin is the same.
通过比较其热分解产物3-甲磺酸基-5-甲基巯基苯酚的CD谱,间接确定了红黄素的绝对构型。在HF/6-31+G*水平上进行几何优化,我们发现3-甲磺酸基-5-甲基巯基苯酚的(R)-异构体有15个局部最小值。然后,用非经验CIS方法计算每个结构的玻尔兹曼加权光谱的叠加得到化合物的CD谱。利用从头算理论在ZPE + MP2/6-31+G*//HF/6-31+G*能级上确定的这些最小值的相对能量,计算了相应的玻尔兹曼因子。通过比较观察到的和计算得到的最长波长棉花效应的标志,我们给出了热解产物的绝对构型。由于进一步的计算表明,在热解条件下,红黄素及其分解产物中的三配位硫原子的构型是稳定的,因此我们得出结论,红黄素相应的硫原子的绝对构型是相同的。
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引用次数: 2
Synthesis of calix[4]arene and porphyrin tethering four chiral five-membered cyclic carbonates. 杯[4]芳烃和卟啉系四手性五元环碳酸盐的合成。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212195
T. Takata, H. Takagi, Yoshio Furusho
Calix[4]arene tethering four chiral five-membered cyclic carbonates 1c was synthesized by O-glycidylation of p-tert-butylcalix[4]arene 1a with (R)-glycidyl tosylate, followed by carbonation with carbon dioxide catalyzed by lithium bromide. Porphyrin tethering chiral five-membered cyclic carbonates 2c was similarly synthesized.
以杯[4]芳烃对叔丁基杯[4]芳烃1a为原料,用(R)-缩水甘油酯进行o -缩水甘油化反应,然后在溴化锂催化下用二氧化碳羰基化,合成杯[4]芳烃系四手性五元环碳酸酯1c。卟啉系链手性五元环碳酸酯2c也用类似方法合成。
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引用次数: 4
Strategic placement of stereogenic centers in molecular materials for second harmonic generation. 二次谐波生成分子材料中立体中心的战略性放置。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212190
P. Gangopadhyay, D. Rao, I. Agranat, T. Radhakrishnan
Basic aspects of the nonlinear optical phenomenon of second harmonic generation (SHG) and the assembly of molecular materials for SHG are reviewed. Extensive use of chirality as a convenient tool to generate noncentrosymmetricity in molecular lattices, an essential requirement for the development of quadratic nonlinear optical materials, is noted. An overview of our investigations of chiral diaminodicyanoquinodimethanes is presented, which provides insight into a systematic approach to the effective deployment of chirality to achieve optimal molecular orientations for enhanced solid state SHG. Extension of these ideas to the realization of strong SHG in materials based on helical superstructures is outlined.
综述了二次谐波非线性光学现象的基本研究进展和二次谐波分子材料的制备。广泛使用手性作为一种方便的工具来产生分子晶格中的非中心对称性,这是二次非线性光学材料发展的基本要求。概述了我们对手性二氨基二氰醌二甲烷的研究,这为有效部署手性以实现增强固态SHG的最佳分子取向提供了系统的方法。概述了这些思想在基于螺旋超结构的材料中实现强SHG的推广。
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引用次数: 6
CD of single-stranded, double-stranded, and G-quartet nucleic acids in complexes with a single-stranded DNA-binding protein. 单链、双链和g -四重奏核酸与单链dna结合蛋白复合物的CD。
Pub Date : 2002-03-01 DOI: 10.1080/10242430212192
D. Gray, C. Gray, T. Mou, J. Wen
We review CD studies of a single-stranded DNA binding protein, g5p, of the Ff group of bacterial viruses. The CD spectrum of the g5p is dominated by a positive tyrosine La band at 229 nm, to which all five of the protein tyrosines contribute. The La band becomes much less positive upon binding of g5p to nucleic acids. CD spectra of mutant proteins identified a single tyrosine, Y34, that is largely responsible for this CD perturbation. At >250 nm, CD perturbations of nucleic acids can be monitored during g5p binding, and CD titrations have identified two distinct modes of binding of the g5p at physiological ionic strength (0.2 M NaCl). SELEX selection of sequences bound preferentially by g5p yielded a G-rich sequence that is closely related to telomere sequences and has CD properties of a G-tetraplex. CD spectroscopy showed that the presumed G-quadruplex form is maintained within saturated g5p x DNA complexes.
我们回顾了细菌病毒Ff群的单链DNA结合蛋白g5p的CD研究。g5p的CD光谱在229 nm处以酪氨酸La带为主,5种蛋白酪氨酸都参与其中。当g5p与核酸结合时,La带的正电性大大降低。突变蛋白的CD光谱鉴定出一个单独的酪氨酸Y34,这是造成CD扰动的主要原因。在>250 nm处,可以监测到核酸在g5p结合过程中的CD扰动,并且CD滴定鉴定出生理离子强度(0.2 M NaCl)下g5p的两种不同结合模式。SELEX选择g5p优先结合的序列,得到了与端粒序列密切相关的富含g的序列,并具有g -四联体的CD特性。CD光谱显示,假定的g -四重体形式在饱和的g5px DNA复合物中保持。
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引用次数: 16
Quantitative analysis of incomplete HPLC resolution of enantiomers. Fit of polarimetric detection for D- and L-phenylalanine to a gaussian function. 对映体不完全高效液相色谱的定量分析。D-苯丙氨酸和l -苯丙氨酸的偏振检测符合高斯函数。
Pub Date : 2002-01-01 DOI: 10.1080/10242430210703
T. J. Edkins, P. C. Meier, R. Shah, D. R. Bobbitt, H. Saranadasa, Romeo D Lodevico
This report compares laser-based polarimetric and UV data for quantitating incompletely resolved enantiomers by HPLC. Using L- and D-phenylalanine as a working model, response data is shown across the entire detection region while emphasizing the regions at or near 100% L, 100% D and 50:50 L:D at resolutions between 0.4 and 1.4. In general, the poorer the resolution, the greater the improvement in detectability with the polarimeter when compared to UV detection. This is due to the inherent bipolar nature of the polarimetric signal, which creates a well-defined crossing point for integration of an enantiomeric pair. In our previous work, we described the improvement in measurement precision when applying a bipolar gaussian peak model to the raw chromatographic peak data. This study will measure the model's effect on improving accuracy. This study should be applicable to other chiroptical detection strategies that produce a bipolar signal for enantiomers, such as circular dichroism and circularly polarized luminescence.
本报告比较了用高效液相色谱法定量不完全分辨对映体的激光偏振和紫外数据。使用L-和D-苯丙氨酸作为工作模型,响应数据显示在整个检测区域,同时强调在0.4和1.4之间分辨率为100% L, 100% D和50:50 L:D或接近的区域。一般来说,分辨率越差,与紫外检测相比,偏振计的可检测性改进越大。这是由于极化信号固有的双极性性质,这为对映体对的整合创造了一个定义良好的交叉点。在我们之前的工作中,我们描述了将双极高斯峰模型应用于原始色谱峰数据时测量精度的提高。本研究将测量模型对提高准确性的影响。这项研究应该适用于其他对映体产生双极性信号的chiroptic检测策略,如圆二色性和圆偏振发光。
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引用次数: 6
期刊
Enantiomer
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