An enantiomerically pure hydrogen-bonded assembly

Chiral molecules have asymmetric arrangements of atoms, forming structures that are non-superposable mirror images of each other. Specific mirror images ('enantiomers') may be obtained either from enantiomerically pure precursor compounds, through enantioselective synthesis, or by resolution of so-called racemic mixtures of opposite enantiomers, provided that racemization (the spontaneous interconversion of enantiomers) is sufficiently slow. Non-covalent assemblies can similarly adopt chiral supramolecular structures, and if they are held together by relatively strong interactions, such as metal coordination, methods analogous to those used to obtain chiral molecules yield enantiomerically pure non-covalent products. But the resolution of assemblies formed through weak interactions, such as hydrogen-bonding, remains challenging, reflecting their lower stability and significantly higher susceptibility to racemization. Here we report the design of supramolecular structures from achiral calix[4]arene dimelamines and cyanurates, which form multiple cooperative hydrogen bonds that together provide sufficient stability to allow the isolation of enantiomerically pure assemblies. Our design strategy is based on a non-covalent 'chiral memory' concept, whereby we first use chiral barbiturates to induce the supramolecular chirality in a hydrogen-bonded assembly, and then substitute them by achiral cyanurates. The stability of the resultant chiral assemblies in benzene, a non-polar solvent not competing for hydrogen bonds, is manifested by a half-life to racemization of more than four days at room temperature.     

Controlling molecular deposition and layer structure with supramolecular surface assemblies

Selective non-covalent interactions have been widely exploited in solution-based chemistry to direct the assembly of molecules into nanometre-sized functional structures such as capsules, switches and prototype machines. More recently, the concepts of supramolecular organization have also been applied to two-dimensional assemblies on surfaces stabilized by hydrogen bonding, dipolar coupling or metal co-ordination. Structures realized to date include isolated rows, clusters and extended networks, as well as more complex multi-component arrangements. Another approach to controlling surface structures uses adsorbed molecular monolayers to create preferential binding sites that accommodate individual target molecules. Here we combine these approaches, by using hydrogen bonding to guide the assembly of two types of molecules into a two-dimensional open honeycomb network that then controls and templates new surface phases formed by subsequently deposited fullerene molecules. We find that the open network acts as a two-dimensional array of large pores of sufficient capacity to accommodate several large guest molecules, with the network itself also serving as a template for the formation of a fullerene layer.     

Stacking of conical molecules with a fullerene apex into polar columns in crystals and liquid crystals

Polar liquid crystalline materials can be used in optical and electronic applications, and recent interest has turned to formation strategies that exploit the shape of polar molecules and their interactions to direct molecular alignment. For example, banana-shaped molecules align their molecular bent within smectic layers, whereas conical molecules should form polar columnar assemblies. However, the flatness of the conical molecules used until now and their ability to flip have limited the success of this approach to making polar liquid crystalline materials. Here we show that the attachment of five aromatic groups to one pentagon of a C(60) fullerene molecule yields deeply conical molecules that stack into polar columnar assemblies. The stacking is driven by attractive interactions between the spherical fullerene moiety and the hollow cone formed by the five aromatic side groups of a neighbouring molecule in the same column. This packing pattern is maintained when we extend the aromatic groups by attaching flexible aliphatic chains, which yields compounds with thermotropic and lyotropic liquid crystalline properties. In contrast, the previously reported fullerene-containing liquid crystals all exhibit thermotropic properties only, and none of them contains the fullerene moiety as a functional part of its mesogen units. Our design strategy should be applicable to other molecules and yield a range of new polar liquid crystalline materials.     

六元瓜环与D,L-色氨酸配合物的晶体结构分析

本文对制备得的六元瓜环(Q[6])与D,L-色氨酸(Try)包结配合物晶体进行了分析.结果表明,该晶体主客体间通过氢键作用、离子-偶极作用形成配合物,位于配合物间的水分子将其连接成超分子链,并呈有规律的层状排列,层与层之间分布着Try分子与大量的水分子.     

Selective assembly on a surface of supramolecular aggregates with controlled size and shape.

The realization of molecule-based miniature devices with advanced functions requires the development of new and efficient approaches for combining molecular building blocks into desired functional structures, ideally with these structures supported on suitable substrates 1-4.Supramolecular aggregation occurs spontaneously and can lead to controlled structures if selective and directional non-covalent interactions are exploited. But such selective supramolecular assembly has yielded almost exclusively crystals or dissolved structures 5; the self-assembly of absorbed molecules into larger structures 6-8, in contrast, has not yet been directed by controlling selective intermolecular interactions. Here we report the formation of surface-supported supramolecular structures whose size and aggregation pattern are rationally controlled by tuning the non-covalent interactions between individual absorbed molecules.Using low-temperature scanning tunnelling microscopy, we show that substituted porphyrin molecules adsorbed on a gold surface form monomers, trimers, tetramers or extended wire-like structures. We find that each structure corresponds in a predictable fashion to the geometric and chemical nature of the porphyrin substituents that mediate the interactions between individual adsorbed molecules.Our findings suggest that careful placement of functional groups that are able to participate in directed non-covalent interactions will allow the rational design and construction of a wide range of supramolecular architectures absorbed to surfaces.     

DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response

Matter structured on a length scale comparable to or smaller than the wavelength of light can exhibit unusual optical properties. Particularly promising components for such materials are metal nanostructures, where structural alterations provide a straightforward means of tailoring their surface plasmon resonances and hence their interaction with light. But the top-down fabrication of plasmonic materials with controlled optical responses in the visible spectral range remains challenging, because lithographic methods are limited in resolution and in their ability to generate genuinely three-dimensional architectures. Molecular self-assembly provides an alternative bottom-up fabrication route not restricted by these limitations, and DNA- and peptide-directed assembly have proved to be viable methods for the controlled arrangement of metal nanoparticles in complex and also chiral geometries. Here we show that DNA origami enables the high-yield production of plasmonic structures that contain nanoparticles arranged in nanometre-scale helices. We find, in agreement with theoretical predictions, that the structures in solution exhibit defined circular dichroism and optical rotatory dispersion effects at visible wavelengths that originate from the collective plasmon-plasmon interactions of the nanoparticles positioned with an accuracy better than two nanometres. Circular dichroism effects in the visible part of the spectrum have been achieved by exploiting the chiral morphology of organic molecules and the plasmonic properties of nanoparticles, or even without precise control over the spatial configuration of the nanoparticles. In contrast, the optical response of our nanoparticle assemblies is rationally designed and tunable in handedness, colour and intensity-in accordance with our theoretical model.     

水环境下α-丙氨酸分子手性的转变机制

基于密度泛函理论考察水环境下α-丙氨酸分子手性转变机制,通过寻找水环境下α-丙氨酸手性转变过程过渡态及中间体等极值点的结构,绘制水环境下α-丙氨酸分子手性碳上氢原子转移及形成中间体异构过程的反应势能面.结果表明:与孤立条件的手性转变过程相比,以单个和两个水分子为桥梁的氢原子从手性碳向羰基氧转移过程的能垒从325.5kJ/mol分别降为200.6,173.0kJ/mol;氢原子从羰基氧再迁移到手性碳另一侧的能垒从229.2kJ/mol分别降为105.3,73.5kJ/mol.这是由于水分子在α-丙氨酸分子对映体手性转变过程中具有催化作用,即生命体内存在微量右旋丙氨酸的机制是水参与了左旋丙氨酸手性转变过程,降低了反应能垒所致.     

A_a-B_b-C_c型氢键体系的网络结构参数

利用高分子反应统计理论对氢键溶液的模型体系进行研究,给出了Aa-Bb-Cc型氢键溶液体系在凝胶点后的溶胶分子数、悬吊链节数、弹性有效链节数、有效交联点数和弹性有效链数等各结构参数的计算方案,并对A2-B3-C2型氢键溶液体系进行了相应的数值计算.结果显示溶胶中的链节数随着反应程度的增加而逐渐减少,网络中弹性有效链数、弹性有效链节数和有效交联点数都是随着反应程度的增加而逐渐增加,而悬吊链节数是先随反应程度的增加而增加,然后随反应程度的增加减小,表明网络结构在逐渐趋于紧致.进一步分析可得知给体的活性对凝胶点后的氢键体系的网络结构有一定影响,这为控制氢键网络的结构提供了可能的方法.     

含醇溴化锂水溶液汽液界面的分子模拟

为研究界面活性剂在溴化锂吸收机组中对吸收过程的强化机理,采用分子动力学方法模拟303 K时的水、质量分数为60%的溴化锂水溶液以及分别添加不同量的乙醇、正辛醇(1-octanol)、仲辛醇(2-octanol)、异辛醇(2-ethyl-1hexanol)的水或溴化锂水溶液的汽液界面,并且分别对其密度分布、微观结构进行研究,计算分别添加上述醇类的溴化锂水溶液的汽液界面张力,计算结果与实验值相符.模拟结果显示:正辛醇、仲辛醇、异辛醇分子吸附在汽液界面并在界面处呈优势取向,即疏水烃基指向气相,亲水羟基指向液相;醇分子的亲水基尽可能多地趋向水分子,二者在界面处以氢键相互作用;醇分子的添加量为某一特定范围时,醇分子的烃基链在界面处产生较大摆动.     

Catalytic enantioselective reactions driven by photoinduced electron transfer

Photoinduced electron transfer is an essential step in the conversion of solar energy into chemical energy in photosystems I and II (ref. 1), and is also frequently used by chemists to build complex molecules from simple precursors. During this process, light absorption generates molecules in excited electronic states that are susceptible to accepting or donating electrons. But although the excited states are straightforward to generate, their short lifetimes makes it challenging to control electron transfer and subsequent product formation-particularly if enantiopure products are desired. Control strategies developed so far use hydrogen bonding, to embed photochemical substrates in chiral environments and to render photochemical reactions enantioselective through the use of rigid chiral complexing agents. To go beyond such stoichiometric chiral information transmission, catalytic turnover is required. Here we present a catalytic photoinduced electron transfer reaction that proceeds with considerable turnover and high enantioselectivity. By using an electron accepting chiral organocatalyst that enforces a chiral environment on the substrate through hydrogen bonding, we obtain the product in significant enantiomeric excess (up to 70%) and in yields reaching 64%. This performance suggests that photochemical routes to chiral compounds may find use in general asymmetric synthesis.     

水环境下布洛芬分子的手性转变机理

基于密度泛函理论, 在B3LYP/6-31+g(d,p)水平上研究水环境下布洛芬分子的手性转变机理, 确定水环境下布洛芬分子从S型向R型转变过程中的过渡态和中间体等极值点结构; 在MP2/6-31++g(d,p)水平上计算各稳定点和过渡态体系的单点能, 并对体系能量进行零点振动能修正; 绘制水环境下布洛芬分子手性
转变反应路径上H转移和中间体异构过程的势能面. 结果表明： 水环境下布洛芬分子手性转变有两条路径, 其H转移过程均可通过1个和2个水分子作为桥梁实现, 最高能垒均来自于手性C的H向羰基O的转移过程, 且均以2H₂O为桥梁时能垒最低.     

甲酸和水(1∶2)弱相互作用的理论研究

采用DFT和MP2方法,在6 - 311++g(d ,p)基组水平上,对甲酸和两个水分子之间的相互作用进行了研究,找到了6种稳定结构,其中环状双氢键结构最稳定.对于6种结构的几何构型和振动频率进行了分析,给出了复合物的结合能,并对其进行了基集超位误差(BSSE)校正.     

The structure of malaria pigment beta-haematin

Despite the worldwide public health impact of malaria, neither the mechanism by which the Plasmodium parasite detoxifies and sequesters haem, nor the action of current antimalarial drugs is well understood. The haem groups released from the digestion of the haemoglobin of infected red blood cells are aggregated into an insoluble material called haemozoin or malaria pigment. Synthetic beta-haematin (FeIII-protoporphyrin-IX)2 is chemically, spectroscopically and crystallographically identical to haemozoin and is believed to consist of strands of FeIII-porphyrin units, linked into a polymer by propionate oxygen-iron bonds. Here we report the crystal structure of beta-haematin determined using simulated annealing techniques to analyse powder diffraction data obtained with synchrotron radiation. The molecules are linked into dimers through reciprocal iron-carboxylate bonds to one of the propionic side chains of each porphyrin, and the dimers form chains linked by hydrogen bonds in the crystal. This result has implications for understanding the action of current antimalarial drugs and possibly for the design of new therapeutic agents.     

聚合物反胶团萃取中的亲油作用和氢键作用

为探索聚合物反胶团萃取亲水溶质的机理以及聚合物与溶质的相互作用，在比较了聚合物胶团萃取和聚合物反胶团萃取的特性基础上，利用热力学分析、红外光谱分析和紫外光谱分析，研究了聚合物反胶团萃取的作用机制，指出并实验验证了聚合物与溶质之间存在着亲油作用和氢键作用。研究结果表明，亲油作用在聚合物反胶团萃取过程中起主导作用。当聚合物与溶质存在氢键作用时，氢键作用对萃取效果有明显的影响。氢键作用较弱时，溶质的萃取受亲油作用支配     

单L-苯丙氨酸衍生物对乙醇/水混合溶剂的凝胶化研究

考察了单L-苯丙氨酸衍生物——L-3-[(3-硬脂胺酰基)-3-苯基-丙酰基]丁酸(SPAB)在乙醇/水混合溶剂中的凝胶行为,结果表明SPAB在乙醇/水的体积比从9:1到2:3的乙醇/水混合溶剂中能形成稳定的、热可逆的超分子凝胶。而在乙醇/水(V/V=1)溶液中的最低凝胶化浓度(MGC)低至1.2 mg/m L。凝胶的相转变温度(TGS)随凝胶因子浓度增加而升高。扫描电镜(SEM)观察到SPAB在乙醇/水混合溶剂中形成了相互交联的带状纤维聚集体。红外光谱(FTIR)结果表明SPAB分子中酰胺基团间的氢键、烷基的疏水作用以及水与SPAB分子中的羧基间的氢键是分子自组装的主要驱动力。     

Light-driven monodirectional molecular rotor.

Attempts to fabricate mechanical devices on the molecular level have yielded analogues of rotors, gears, switches, shuttles, turnstiles and ratchets. Molecular motors, however, have not yet been made, even though they are common in biological systems. Rotary motion as such has been induced in interlocked systems and directly visualized for single molecules, but the controlled conversion of energy into unidirectional rotary motion has remained difficult to achieve. Here we report repetitive, monodirectional rotation around a central carbon-carbon double bond in a chiral, helical alkene, with each 360 degrees rotation involving four discrete isomerization steps activated by ultraviolet light or a change in the temperature of the system. We find that axial chirality and the presence of two chiral centres are essential for the observed monodirectional behaviour of the molecular motor. Two light-induced cis-trans isomerizations are each associated with a 180 degrees rotation around the carbon-carbon double bond and are each followed by thermally controlled helicity inversions, which effectively block reverse rotation and thus ensure that the four individual steps add up to one full rotation in one direction only. As the energy barriers of the helicity inversion steps can be adjusted by structural modifications, chiral alkenes based on our system may find use as basic components for 'molecular machinery' driven by light.     

Multi-membrane hydrogels

Polysaccharide-based hydrogels are useful for numerous applications, from food and cosmetic processing to drug delivery and tissue engineering. The formation of hydrogels from polyelectrolyte solutions is complex, involving a variety of molecular interactions. The physical gelation of polysaccharides can be achieved by balancing solvophobic and solvophilic interactions. Polymer chain reorganization can be obtained by solvent exchange, one of the processing routes forming a simple hydrogel assembly. Nevertheless, many studies on hydrogel formation are empirical with a limited understanding of the mechanisms involved, delaying the processing of more complex structures. Here we use a multi-step interrupted gelation process in controlled physico-chemical conditions to generate complex hydrogels with multi-membrane 'onion-like' architectures. Our approach greatly simplifies the processing of gels with complex shapes and a multi-membrane organization. In contrast with existing assemblies described in the literature, our method allows the formation of free 'inter-membrane' spaces well suited for cell or drug introduction. These architectures, potentially useful in biomedical applications, open interesting perspectives by taking advantage of tailor-made three-dimensional multi-membrane tubular or spherical structures.     

A supramolecular gel based on an adenine symmetrically grafted Anderson-type polyoxometalate complex

An Anderson-type polyoxometalate was covalently decorated by using adenine on both sides.Through cation substitution,we obtained a new hybrid building block with long alkyl chains for supramolecular gels.According to the synergetic effect of hydrogen bonding of inter adenine units and van der Waals interaction of side alkyl chains,the DODA 3 [A-MnMo 6-A] gelator can stabilize solvent and self-assemble into fibrous structure,forming supramolecular gel.In addition,the reversible sol-gel transformation was achieved by controlling environmental temperature.Scanning electron microscopy,transmission electron microscopy and X-ray diffraction were used to characterize the gel morphology and structure.As a result,we proposed the possible mechanism of gel formation and sol-gel transformation.     

Synthesis, supramolecular structures and luminescent properties of quinacridone derivatives bearing carbazole groups

The syntheses of three carbazyl-containing quinacridone derivatives, N,N’-di((N-carbazyl)-n-butyl) quinacridone (DCBQA), N,N’-di((N-carbazyl)-n-hexyl)quinacridone (DCHQA) and N,N’-di((N-carbazyl)-n-octyl)quinacridone (DCOQA), are reported, and the photoluminescent (PL) characteristics are pre- sented. The single crystal X-ray structures of DCBQA, DCHQA and DCOQA are investigated. The crystal of DCBQA is characterized by intermolecular π…π interactions between quinacridone cores and carbazole moieties result...     

Amplification of chirality in two-dimensional enantiomorphous lattices

The concept of chirality dates back to 1848, when Pasteur manually separated left-handed from right-handed sodium ammonium tartrate crystals. Crystallization is still an important means for separating chiral molecules into their two different mirror-image isomers (enantiomers), yet remains poorly understood. For example, there are no firm rules to predict whether a particular pair of chiral partners will follow the behaviour of the vast majority of chiral molecules and crystallize together as racemic crystals, or as separate enantiomers. A somewhat simpler and more tractable version of this phenomenon is crystallization in two dimensions, such as the formation of surface structures by adsorbed molecules. The relatively simple spatial molecular arrangement of these systems makes it easier to study the effects of specific chiral interactions; moreover, chiral assembly and recognition processes can be observed directly and with molecular resolution using scanning tunnelling microscopy. The enantioseparation of chiral molecules in two dimensions is expected to occur more readily because planar confinement excludes some bulk crystal symmetry elements and enhances chiral interactions; however, many surface structures have been found to be racemic. Here we show that the chiral hydrocarbon heptahelicene on a Cu111 surface does not undergo two-dimensional spontaneous resolution into enantiomers, but still shows enantiomorphism on a mesoscopic length scale that is readily amplified. That is, we observe formation of racemic heptahelicene domains with non-superimposable mirror-like lattice structures, with a small excess of one of the heptahelicene enantiomers suppressing the formation of one domain type. Similar to the induction of homochirality in achiral enantiomorphous monolayers by a chiral modifier, a small enantiomeric excess suffices to ensure that the entire molecular monolayer consists of domains having only one of two possible, non-superimposable, mirror-like lattice structures.