生物手性起源和碳同位素记录

生物手性起源是很多因素联合作用的结果．其中主要是：β电子和手性分子的非弹性散射导致的左右不对称性，化学反应动力学的手性放大效应和聚合过程中的手性放大效应．如果原始生命并非发生于极低的温度环境，必须考虑非纯手性的可能性，手性的纯化和生命的进化相平行．这一假设可从沉积岩的碳同位素记录中得到验证．     

生物分子的手性与观控相对论

本分析了生物分子手性的起源，提出了一种新的看法，即非平衡态可诱导产生手性（在分支点的对称破缺），而非对称性又造成了新的非平衡态，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，演化着，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。     

生物多聚体分子手性的起源

本文提出了手性分子聚合的合作理论，给出了各种手性参量的关系．证明生物前进化存在两种基本模式：一是大手性能量和小立体选择性的模式，其手性只能通过化学反应镜对称的自发破缺产生；二是小手性能量和大立体选择性的模式，其手性可通过弱作用产生     

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。     

浅谈生物催化的不对称合成

生物催化手性合成是近些年来备受关注的一个重大课题，生物催化的手性合成反应条件温和、环境友好、高效率和高选择性。这使它成为当今手性合成方法研究的热点和发展方向。本文就近几年来，尤其是2000年以来在这些方面的研究进展作一总结。     

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     

Beta射线与分子手性

本文讨论了极化Beta电子作用下左右手分子的不对称分解率,证明了这将导致氨基酸具有10~(-6)量级的L型手性。用原始地球第一次化学反应时期β电子照射所得到的分子手性作为初始条件,通过非线性化学动力学的放大作用,可以解释生物分子的手性起源。     

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。     

水热生物化学

从水热生物化学角度阐述了水热条件下生命起源的可能性,并综述了化学合成,微生物学,分子系统树,海洋考察等方面的证据以及水热生命起源模型.通过模拟原始环境,由无机小分子出发合成一系列有机生物分子,实现了有机生物分子的非生物合成,并探讨了此过程中的手性起源问题.     

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.     

非共价相互作用对中心手性的影响及中心手性的定义

建立在van't Hoff碳正四面体构型学说基础上的中心手性的概念未涉及非共价相互作用对分子中心手性的影响.可以想像,当某原子连有两个相同的原子或基团(如氢原子)时,可因非共价相互作用(如分子内氢键)的存在(如只与其中的一个氢原子形成氢键)成为不等性原子或基团.考虑到非共价相互作用对分子中心手性可能产生的影响,中心手性的概念似应为:一个原子(如C,N)的四支键分别指向四面体的各顶点,并分别键连四个不等性原子或基团(包括孤电子对)时,则该原子是手性的.     

Free-standing mesoporous silica films with tunable chiral nematic structures

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.     

Structural effects on the magnetic hyperthermia properties of iron oxide nanoparticles

Magnetic iron oxide nanoparticles(IONPs) are heavily explored as diagnostic and therapeutic agents due to their low cost, tunable properties, and biocompatibility. In particular, upon excitation with an alternating current(AC) magnetic field, the NPs generate localized heat that can be exploited for therapeutic hyperthermia treatment of diseased cells or pathogenic microbes. In this review, we focus on how structural changes and inter-particle interactions affect the heating efficiency of iron oxide-based magnetic NPs. Moreover, we present an overview of the different approaches to evaluate the heating performance of IONPs and introduce a new theranostic modality based on magnetic imaging guided–hyperthermia.     

Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold) nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD) properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R)-/(S)-2-phenylpropane-1-thiol, (R)-/(S)-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD) derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of many related nanomaterials.     

Chiral recognition in dimerization of adsorbed cysteine observed by scanning tunnelling microscopy

Stereochemistry plays a central role in controlling molecular recognition and interaction: the chemical and biological properties of molecules depend not only on the nature of their constituent atoms but also on how these atoms are positioned in space. Chiral specificity is consequently fundamental in chemical biology and pharmacology and has accordingly been widely studied. Advances in scanning probe microscopies now make it possible to probe chiral phenomena at surfaces at the molecular level. These methods have been used to determine the chirality of adsorbed molecules, and to provide direct evidence for chiral discrimination in molecular interactions and the spontaneous resolution of adsorbates into extended enantiomerically pure overlayers. Here we report scanning tunnelling microscopy studies of cysteine adsorbed to a (110) gold surface, which show that molecular pairs formed from a racemic mixture of this naturally occurring amino acid are exclusively homochiral, and that their binding to the gold surface is associated with local surface restructuring. Density-functional theory calculations indicate that the chiral specificity of the dimer formation process is driven by the optimization of three bonds on each cysteine molecule. These findings thus provide a clear molecular-level illustration of the well known three-point contact model for chiral recognition in a simple bimolecular system.     

谷氨酸分子的手性转变及溶剂化效应

采用密度泛函理论的B3LYP方法,微扰理论的MP2方法及自洽反应场(SCRF)理论的SMD模型方法,研究两种稳定构型谷氨酸分子的手性转变及水溶剂化效应.结果表明:构型1的优势通道为通道a和通道b,决速步骤自由能垒分别为242.3,245.7kJ/mol;构型2的优势通道为通道a,决速步骤自由能垒为243.5kJ/mol;决速步骤能垒均由质子从手性C向氨基N迁移的过渡态产生;水溶剂化效应使构型1的优势通道决速步骤自由能垒降至101.5kJ/mol;决速步骤的反应速率常数在298.15K时为1.002×10~(-5)s~(-1),在310.00K时为3.802×10~(-5)s~(-1).可见谷氨酸分子在生命体内富水环境下可缓慢地实现旋光异构.     

Reconfigurable self-assembly through chiral control of interfacial tension

From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil-water interfaces. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex topologies.