分子组装体中的手性非线性放大现象

正信息如何在分子间传递是一类重要科学问题.手性非线性放大现象(又名士兵长与士兵效应,the sergeants-and-soldiers effect)是手性信息在分子间传递并放大的现象,由少数手性分子(士兵长)"指挥"大量非手性分子(士兵)形成具较强手性信号的组装体.这种特殊的手性传递效应被广泛应用于不对称催化、手性药物拆分、分子组装等领域,并与手性起源密切关     

生命起源前手性对映体富集与放大的数学规律与实验

生命起源前的原始海洋(池)中，由于没有手性源，手性化合物在合成过程中可能受到其他不对称因素(如手性对称性破缺)等影响，它们几乎都是以极小%ee值的非外消旋体(non-racemic enantiomers)存在。从数学理论出发，结合化学反应原理，推导出这些非外消旋体在通过某种反应后，其较小的%ee值(%ee₁)可以富集到较大的%ee值(%ee₂),尤其在很低%ee值的情况下，理论上其放大倍数(%ee₂/%ee₁)可以是指数级别的增加，而这是生命起源前得到高含量对映体(如L-氨基酸)所需要的。进一步使用约1%ee值的L-色氨酸甲酯(L-TME),通过与双功能基团物质(如乙二醛)发生反应，在0℃～室温条件下，将其放大富集到3.4%(%ee₂)。系列实验表明：最大放大倍数(%ee₂/%ee₁)可达1.9(从6.1%的%ee₁提高到11.7%的%ee₂);单次最大增量(Δ%ee=%ee_2<...     

生物分子手性的观控相对论

分析了生物分子手性的起源后，认为：非平衡态在分支点上的对称破缺诱导下产生手性，而非对称性又造成了新的非平衡态，从而这种不对称被放大。生命就是在这种非平衡态中延续、发展的。生命的结构物质，在不对称中，在时间箭头的方向上不可逆地产生着、发展着。这一演化过程是一个结构和功能不断调整、不断适应的观控相对统一体。     

螺旋结构手性材料的手性参数实验研究

利用微波圆波导测量系统，在８．５～１１．５ ＧＨｚ 频段内测量了螺旋结构手性材料的手性参数．研究了手性掺杂体的螺径、螺距和线径对手性参数的影响．结果表明，随着螺旋体结构参数的变化，有Ｃｏｔｔｏｎ 效应出现． 实验结果为手性材料的设计提供了实验依据．     

相转移催化双不对称诱导合成α—氨基酸（Ⅱ）

在固液两相体系，以手性和非手性报铵盐为相转移催化剂，研究了各种α－溴代脂肪酸龙脑酯与邻苯二甲酰亚胺的Ｇａｂｒｉｅｌ反应，得到４种具有光学活性的α－邻苯二甲酰亚胺基羧酸酯、以肼解、水解后得到４种具有光学活性的α－氨基酸，光学纯度最高为４７．４％，并观察到手性识别和双不对称诱导效应。     

螺旋结构手性材料的手性参数实验研究

利用微波圆波导测量系统，在８．５～１１．５ＧＨｚ频段内测量了螺旋结构手性材料的手性参数。研究了手性掺杂体的螺径、螺距和线径对手性参数的影响。结果表明，随着螺旋体结构参数的变化，有Ｃｏｔｔｏｎ效应出现。实验结果为手性材料的设计提供了实验依据。．     

用手性醇改性的铝锂试剂对芳酮的不对称还原

为开发新型手性铝锂试剂，探讨双不对称诱导效应，选用含杂原子的光学活性氨基酸为辅助配体，与1，2，5，6—二丙酮甘露醇共同修饰LiAIH4，对潜手性芳酮进行不对称还原，得到光学活性醇；通过与α—D-乙酰氧基—L-丙酰氯生成非对映异构体酯，经气相色谱分析，对映体过量在43．6％。N．7％之间。结果表明辅助配体的绝对构型、空间位阻、β位杂原子对光学产率均有影响。     

天冬氨酸分子在水环境下手性转变机理的理论研究

使用密度泛函理论的B3LYP方法和微扰理论的MP2方法,溶剂效应采用离散与连续介质模型,研究了天冬氨酸分子在水环境下的手性转变.反应通道研究发现:天冬氨酸分子在水环境下的手性转变有4个反应通道a,b,c,d.a是以氨基N为桥实现质子转移;b是顺次以羰基O和氨基N为桥实现质子转移;c是只以羰基O为桥实现质子转移;d是羧基内质子迁移后,质子再以羰基O为桥从手性碳的一侧转移到另一侧.势能面计算表明:a通道是最佳通道,3个水分子构成的链作氢迁移媒介,使最高能垒降到108.9kJ·mol-1,对水分子作桥的质子迁移,远程效应不明显;对非质子转移反应,远程作用溶剂效应使能垒明显升高.结果表明:考虑到温度的涨落和分子频繁碰撞等因素,左天冬氨酸在生命体内可以少部分异构成右旋体;水环境下质子迁移反应,可以忽略溶剂的远程效应.     

需求信息预测与处理中的牛鞭效应

研究了在不稳定的市场需求下，生产商和零售商所组成的供应链系统中的牛鞭效应存在问题．提出了当零售商采用一次平滑指数法或简单移动平均法获得需求信息的过程中，不存在波动放大现象．证明了在生产商和零售商都采用固定间隔库存策略处理需求信息的过程中，显著存在波动放大现象，从零售商到生产商的信息传递过程中，存在着牛鞭效应现象．需求过程中的牛鞭效应主要是由于生产商和零售商利用各自库存策略处理信息的结果．     

手性胶束中Salen—Mn（Ⅲ）配合物对末端烯烃的催化环氧化反应

在表面活性剂（－）—（１Ｒ，２Ｓ）—Ｎ—甲基—Ｎ—十六烷基麻黄素溴化物的手性胶束体系中，在Ｓａｌｅｎ－Ｍｎ（Ⅲ）配合物的催化下，末端烯烃可被氧化为旋光性的环氧化合物．对非手性和手性的Ｓａｌｅｎ配合物及若干种氧化剂的作用行为进行了探讨     

论生物手性的起源

在综述生物大分子手性起源的各种理论的基础上，提出了手性起源的三步理论，     

Enantioselective magnetochiral photochemistry

Many chemical and physical systems can occur in two forms distinguished solely by being mirror images of each other. This phenomenon, known as chirality, is important in biochemistry, where reactions involving chiral molecules often require the participation of one specific enantiomer (mirror image) of the two possible ones. In fact, terrestrial life utilizes only the L enantiomers of amino acids, a pattern that is known as the 'homochirality of life' and which has stimulated long-standing efforts to understand its origin. Reactions can proceed enantioselectively if chiral reactants or catalysts are involved, or if some external chiral influence is present. But because chiral reactants and catalysts themselves require an enantioselective production process, efforts to understand the homochirality of life have focused on external chiral influences. One such external influence is circularly polarized light, which can influence the chirality of photochemical reaction products. Because natural optical activity, which occurs exclusively in media lacking mirror symmetry, and magnetic optical activity, which can occur in all media and is induced by longitudinal magnetic fields, both cause polarization rotation of light, the potential for magnetically induced enantioselectivity in chemical reactions has been investigated, but no convincing demonstrations of such an effect have been found. Here we show experimentally that magnetochiral anisotropy--an effect linking chirality and magnetism--can give rise to an enantiomeric excess in a photochemical reaction driven by unpolarized light in a parallel magnetic field, which suggests that this effect may have played a role in the origin of the homochirality of life.     

生物手性是生命起源的指示灯

将生命的发生看作一种相变 ,在此过程中序参量 (手性参数 f L)从 0突变到 1 .讨论了效率作为序参量的函数的可能形式 :η≈ exp{-k(1 -f2L) }和 η～ exp{k1 -f2L}.在前一形式中原始生命的相变点可能发生于 |f L|<1 ,通过世代更新 ,最后达到 |f L|=1的完整生命 .后一形式中生命必须是一奇异事件 ,只能产生于手性纯的系统中 .     

Thermodynamic control of asymmetric amplification in amino acid catalysis

Ever since Pasteur noticed that tartrate crystals exist in two non-superimposable forms that are mirror images of one another--as are left and right hands--the phenomenon of chirality has intrigued scientists. On the molecular level, chirality often has a profound impact on recognition and interaction events and is thus important to biochemistry and pharmacology. In chemical synthesis, much effort has been directed towards developing asymmetric synthesis strategies that yield product molecules with a significant excess of either the left-handed or right-handed enantiomer. This is usually achieved by making use of chiral auxiliaries or catalysts that influence the course of a reaction, with the enantiomeric excess (ee) of the product linearly related to the ee of the auxiliary or catalyst used. In recent years, however, an increasing number of asymmetric reactions have been documented where this relationship is nonlinear, an effect that can lead to asymmetric amplification. Theoretical models have long suggested that autocatalytic processes can result in kinetically controlled asymmetric amplification, a prediction that has now been verified experimentally and rationalized mechanistically for an autocatalytic alkylation reaction. Here we show an alternative mechanism that gives rise to asymmetric amplification based on the equilibrium solid-liquid phase behaviour of amino acids in solution. This amplification mechanism is robust and can operate in aqueous systems, making it an appealing proposition for explaining one of the most tantalizing examples of asymmetric amplification-the development of high enantiomeric excess in biomolecules from a presumably racemic prebiotic world.     

对称性,手性和旋光化合物的合成

本文以对称性的观点阐述对称性、手性和旋光性化合物合成的相关性，文中分成三个部分：手性与对称性；手性分子的形成；旋光性化合物的合成途径。     

有机手性分子器件的光电特性

目前多种有机手性分子器件虽已研制成功,但其内在的物理机理仍有许多未解之谜,其中手性分子的圆二色性精细结构、手性诱导的自旋选择效应等是有机手性分子研究的核心。为设计基于手性的新型有机功能器件提供理论指导,考虑有机手性分子螺旋势场诱导的自旋-轨道耦合,围绕分子的光电特性及其调控展开了系列研究。根据光致跃迁理论,得到手性分子的光吸收谱和圆二色谱,发现光吸收峰发生劈裂,圆二色谱由轨道磁矩和自旋磁矩共同贡献。此外,从极化子输运的图像解释了手性诱导自旋选择效应的来源,并利用其电输运特性,设计了手性异质结器件,发现其手性电阻可达7%,整流比达48。     

螺旋手性SWCNT尺寸对布洛芬分子旋光异构限域的影响

用量子力学与分子力学组合的ONIOM方法, 考察布洛芬（Ibu）分子限域在螺旋手性单壁碳纳米管(SWCNT)内的手性转变机理. 结果表明： 螺旋手性单壁碳纳米管的直径越小, 限域在其孔道内的布洛芬分子形变越明显; 布洛芬分子在SWCNT(6,4)和SWCNT(7,4)内的旋光异构只有一个反应通道, 在SWCNT(8,5)内的旋光异构有两个反应通道; 布洛芬分子限域在SWCNT(6,4),SWCNT(7,4)和SWCNT(8,5)内时, 旋光异构反应决速步骤的内禀能垒分别为24795,27383,29224 kJ/mol, 总包能垒分别为27896,29191,32588 kJ/mol. 可见S-Ibu的旋光异构易在较小孔径的螺旋手性SWCNT内实现, SWCNT(6,4)可以作为布洛芬分子旋光异构的纳米反应器.     

生命起源中的对称性破缺

生命起源中的对称性破缺——生物分子手性均一性,是生命科学中的长期未解之谜。自然界中组成蛋白质的20种氨基酸(除甘氨酸无不对称碳原子外)全部是L型,组成RNA,DNA中的核糖却全部是D型。对蛋白质和核酸的手性、分子构型(D和L)和旋光(+和-,右旋光和左旋光)概念作了阐明。对当前国际上最著名的两大学说—β粒子极化和手性分子的相互作用与萨拉姆假说以及国内外的研究工作,结合科研组10几年来的实验研究和理论观点作了较为全面的评述。     

Enantiospecific electrodeposition of a chiral catalyst

Many biomolecules are chiral--they can exist in one of two enantiomeric forms that only differ in that their structures are mirror images of each other. Because only one enantiomer tends to be physiologically active while the other is inactive or even toxic, drug compounds are increasingly produced in an enantiomerically pure form using solution-phase homogeneous catalysts and enzymes. Chiral surfaces offer the possibility of developing heterogeneous enantioselective catalysts that can more readily be separated from the products and reused. In addition, such surfaces might serve as electrochemical sensors for chiral molecules. To date, chiral surfaces have been obtained by adsorbing chiral molecules or slicing single crystals so that they exhibit high-index faces, and some of these surfaces act as enantioselective heterogeneous catalysts. Here we show that chiral surfaces can also be produced through electrodeposition, a relatively simple solution-based process that resembles biomineralization in that organic molecules adsorbed on surfaces have profound effects on the morphology of the inorganic deposits. When electrodepositing a copper oxide film on an achiral gold surface in the presence of tartrate ion in the deposition solution, the chirality of the ion determines the chirality of the deposited film, which in turn determines the film's enantiospecificity during subsequent electrochemical oxidation reactions.