Morphological evolution of inorganic crystal into zigzag and helical architectures with an exquisite association of polymer: a novel approach for morphological complexity

The morphology of potassium sulfate (K(2)SO(4)) crystals grown in a viscous polymer solution of poly(acrylic acid) (PAA) was remarkably changed from the tilted columnar assembly into zigzag and helical architectures with increasing PAA concentration. The habit modification of orthorhombic K(2)SO(4) with adsorption of PAA molecules on a specified crystal face fundamentally led to the formation of tilted unit crystals. Concurrently with the habit modification, a diffusion-limited condition controlling the assembly of tilted units was achieved in the presence of PAA molecules in the matrix. Various complex morphologies, including zigzag and helical assembly, emerged through the formation of twinned crystals with the variation of the diffusion condition. Understanding the morphogenesis observed in this report would provide a novel approach for sophisticated crystal design by using an exquisite association of organic and inorganic materials.     

Structures of Fibrous Supramolecular Assemblies Constructed by Amino Acid Surfactants: Investigation by AFM, SANS, and SAXS

Aqueous gel-like solutions of N-acyl-L-aspartic acids (C(n)Asp, n=14, 16, 18) and N-dodecanoyl-beta-alanine (C(12)Ala) were prepared at pH 5-6 at room temperature. Structures of supramolecular assemblies in the solutions were investigated by atomic force microscopy (AFM), small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS). The cross-sectional radii, 22-30 ?, of helical, fibrous assemblies were obtained from analysis of SANS for 1% gel-like C(n)Asp solutions. Three Bragg spacings were observed in a SANS spectrum for a 6% C(16)Asp solution. C(n)Asp molecules are associated into the unit chain of a helical bilayer strand with a diameter of 50-60 ?. Unit chains where linear bilayers twist form a double strand with helical sense of approximately 650-? pitch. It was confirmed from AFM images that cylindrical fibers in a gel-like C(12)Ala solution had a circular cross-section. The SAXS spectrum showed characteristic Bragg spacings. Cylindrical C(12)Ala fibers consist of multilamellar layers of period approximately 34-?. The fibers are laterally organized with period 365-380 ?. Copyright 2000 Academic Press.     

Single crystals of amylose V complexes. II. Crystals with 71 helical configuration

It has been shown that lamellar crystals of amylose V complexes with 7₁ helical configuration can be obtained by using complexing agents larger in cross section than n-butanol. The electron diffraction studies indicated a new unit cell for the unheated lamellar crystals which are composed of molecules with 7₁ helical configuration and hold water molecules on the exterior of the helix. Furthermore, from a throughly dried specimen at 100°C. in vacuo we obtained a pattern which showed only three Debye rings. Its spacings were explained by a two-dimensional hexagonal unit cell having a = b = 14.7 A. proposed by Zaslow. It was also found that when the crystals were dispersed in methanol at room temperature, their electron diffraction pattern was the same as that of the anhydrous amylose V complex of n-butanol.     

Amplification of chirality from molecules into morphology of crystals through molecular recognition

We have found a novel type of morphological chiral tuning on inorganic helical crystals through stereochemical recognition of organic molecules. Helical forms consisting of twisted twins emerged from triclinic crystals under diffusion-limited conditions. The proportion of the right- and left-handed helices was precisely tuned with the addition of a specified amount of chiral molecules, such as d- and l-glutamic acids. The chiral molecules recognized the enantiomeric surface of the triclinic crystal and then changed the growth behavior of the helical morphology. As a result, the microscopic chiral information, at a molecular level, was amplified into the macroscopic helices consisting of inorganic achiral components.     

Spontaneous chiral resolution of N,N′-diarylsquaramides: Formation of various types of one-handed helical networks during crystallization

N,N′-Bis(ortho-substituted phenyl)squaramides afforded chiral crystals, in which squaramide molecules are arranged in one-handed helical networks, upon simple recrystallization. Three types of crystals with different helices were obtained, depending on the substituents or recrystallization solvent. Folded-type intermolecular hydrogen-bonding interactions of squaramides play a key role in forming the helical networks.     

Single-Crystal-to-Single-Crystal Topochemical Synthesis of a Collagen-inspired Covalent Helical Polymer

There is much demand for crystalline covalent helical polymers. Inspired by the helical structure of collagen, we synthesized a covalent helical polymer wherein the repeating dipeptide Gly-Pro units are connected by triazole linkages. We synthesized an azide and alkyne-modified dipeptide monomer made up of the repeating amino acid sequence of collagen. In its crystals, the monomer molecules aligned in head-to-tail fashion with proximally placed azide and alkyne forming supramolecular helices. At 60 °C, the monomer underwent single-crystal-to-single-crystal (SCSC) topochemical azide-alkyne cycloaddition polymerization, yielding a covalent helical polymer as confirmed by single-crystal X-ray diffraction (SCXRD) analysis. Compared to the monomer crystals, the polymer single-crystals were very strong and showed three-fold increase in Young's modulus, which is higher than collagen, many synthetic polymers and other materials. The crystals of this covalent helical polymer could bear loads as high as 1.5 million times of their own weight without deformation. These crystals could also withstand high compression force and did not disintegrate even at an applied force of 98 kN. Such light-weight strong materials are in demand for various technological applications.     

Vaporization-condensation-recrystallization process-mediated synthesis of helical m-aminobenzoic acid nanobelts

One-dimensional (1D) helical organic nanostructures were synthesized by a modified vapor-solid (VS) process, called the vaporization-condensation-recrystallization (VCR) process. The conventional solution-phase synthetic methods generally mediate self-assemblies of repeating unit molecules. To provide enough intermolecular interaction forces among the unit molecules, such strategy requires specific designs and syntheses of complex unit molecules as they possess numerous functional groups including phenyl rings, hydroxyl groups, long aliphatic chains, etc. On the contrary, we found that small and simple organic molecules, for example, m-ABA, could be self-assembled by the VCR process, resulting in 1D helical organic nanostructures. When m-aminobenzoic acid (m-ABA) powders were vaporized and transported to be condensed on a cooler region, the condensates were recrystallized into 1D helical nanobelts. Each step of the VCR process was confirmed from control experiments performed by varying reaction times, substrate types, and reaction temperatures. Powder XRD data, SAED analysis, and theoretical calculations revealed that dimers of m-ABA molecules have repeating units, and the growth axis of m-ABA nanohelices is [100].     

Memory effects in chiral nematic liquid crystals doped with functionalised single-walled carbon nanotubes

Octadecylamine-functionalised single-walled carbon nanotubes (SWCNTs) were dispersed into nematic liquid crystals (LCs) doped with chiral molecules. The collective orientation of nematic LC molecules in helical layers was manipulated by varying dopant concentration. Highly anisotropic nature of SWCNTs enhanced the anisotropy of the LC as confirmed by polarised fluorescence spectroscopy. The π–π interaction of SWCNTs present in the planar alignment layers and twisted nematic LC molecules affects the molecular relaxation process. An irreversible electro-optic memory in the material has been observed.     

Crystal structure of the trigonal form of isotactic polypropylene as an example of density-driven polymer structure

Propene-hexene copolymers crystallize in a new polymorphic form of isotactic polypropylene when the concentration of hexene is higher than nearly 10-15 mol %. The hexene units are included in the crystals, inducing an increase of density that allows crystallization of 3-fold helical chains in a trigonal unit cell according to the space group R3c or Rc, where the helical symmetry of the chains is maintained in the crystal lattice. The structure of this new form is similar to those of isotactic polybutene and polystyrene and does not crystallize in polypropylene homopolymer because it would have too low density. The crystal structure of isotactic polypropylene is therefore no longer an exception to the principles of polymer crystallography, but the new structure represents the fulfillment of these principles and indicates that the packing of polymer molecules is mainly driven by density.     

Formation mechanism of achiral amphiphile-templated helical mesoporous silicas

A series of achiral cationic and anionic amphiphiles employed as templates for mesoporous silica, all showed an excellent ability to form highly ordered helical mesoporous silica (HMS) crystals. It was supposed that the helical mesostructure may originate from the helical propeller-like micelle formed by the achiral amphiphilic molecules due to their instantaneous asymmetric shape survived in the micelle. The existence of the mirror-imaged conformations of equal proportion may result in the racemic nature of the achiral amphiphile-templated HMSs. The helicity of the HMS greatly depends on the templating molecules which may be modulated by the twisting power of the helical propeller-like packing of the amphiphiles in the micelle. The dependence of the pitch length on different factors was explained by mechanical analysis indicating that the pitch length should be in direct proportion to the rod diameter but inversely proportional to the moment of micelle (M0). Additionally, chiral amphiphiles with opposite charge were used as chiral dopants to control the enantiopurity of the achiral amphiphile-templated HMSs. The absolute enantiomeric excess (ee) of the HMSs increased with increasing amounts of dopant.     

Novel Ligands Incorporating Phosphinoxide Groups as Particularly Efficient Sensitizers for Lanthanide Emission

Helical molecular assemblies of bile acids and their derivatives were systematically investigated. These molecules have a common asymmetric structure with three different directions, and form characteristic inclusion crystals with the following hierarchical structure. First, such molecules arrange along their helical axes to yield the helical tapes with a definite direction. Second, the helical tapes are combined in a parallel fashion by using their side-chains through hydrogen bonds to produce chiral sheets. Third, the sheets stack together through van der Waals forces in a parallel or antiparallel fashion. Fourth, there exist chiral spaces for including guests among their sheets. Such hierarchical structure enables us to explain a role of the side-chains with different hydrogen bonding groups and length.     

Supramolecular Tilt Chirality Derived from Symmetrical Benzene Molecules: Handedness of the 21 Helical Assembly

Achiral molecules can form aggregates with chirality. This depends on the relative position of the molecules, in other words, the tilt of the molecules (so‐called supramolecular tilt chirality). In this paper, we describe supramolecular chirality appearing in a 2₁ column composed of symmetrical benzene molecules, which is formed in the host cavity of inclusion crystals of cholic acid. Moreover, we determined the handedness, that is, right or left, of the 2₁ helical column of benzene on the basis of the molecular tilt. Determination of the 2₁ helical handedness was performed on assemblies of other benzene derivatives in cholic acid crystals and benzene assemblies in other host frameworks selected from the Cambridge Structural Database. Finally, we demonstrated complementarity of the handedness between the 2₁ symmetrical host framework of cholic acid and the benzene column.     

苄醚型树枝化碳水化合物的合成与液晶性

选取3种不同结构的苄醚型树枝状分子为分枝,以N-乙酰氨基葡萄糖为内核,合成出一类树枝化碳水化物;利用DSC、热台偏光显微镜、XRD和CD／UV光谱等手段研究该类化合物的液晶性,并命名为树状碳水化合物液晶。研究表明,连接有楔形树枝状单元的化合物形成手性柱状六方相或者向列相,连接有锥形树枝状单元的化合物未能如预期形成立方相,而仍然形成手性柱状六方相．超分子手性很可能源于树枝状单元与糖内核的协同自组装,使得树状分子沿着柱轴螺旋式堆砌;而糖环内核则对超分子柱的手性起调控作用,从而避免了外消旋的发生．该类化合物为研究碳水化合物诱导手性超分子聚集体提供了新的思路．     

Self-assembly of semifluorinated dendrons attached to electron-donor groups mediates their pi-stacking via a helical pyramidal column

Semifluorinated first-generation self-assembling dendrons attached via a flexible spacer to electron-donor molecules induce pi-stacking of the donors in the center of a supramolecular helical pyramidal column. These helical pyramidal columns self-organize in various columnar liquid crystal phases that mediate self-processing of large single crystal liquid crystal domains of columns and self-repair their intracolumnar structural defects. In addition, all supramolecular columns exhibit a columnar phase at lower temperatures that maintains the helical pyramidal columnar supramolecular structure and displays higher intracolumnar order than that in the liquid crystals phases. The results described here demonstrate the universality of this concept, the power of the fluorous phase or the fluorophobic effect in self-assembly and the unexpected generality of pyramidal liquid crystals.     

On the Helical Crystals of Cholesterol Monohydrate

We review in this short perspective the history of cholesterol crystals and crystal structures. We address in particular the helical crystals that form in vitro and in pathology from environments rich in bile acids or from phospholipid membranes. We review the known mechanisms leading to crystals with chiral morphology, from screw-dislocation mediated growth to mechanisms involving asymmetric mechanical strain. We propose a mechanism for cholesterol helical crystal development based on the monoclinic cholesterol monohydrate crystal structure. We suggest that curvature arises in few layers thick crystals due to the tension induced between the hydrophobic layer and the ice-like H-bonded lattice of the water molecules with the cholesterol hydroxy groups. Helicity would ensue through a combination of the curvature and the fast growth of a thin ribbon in one crystal direction.     

Influence of a Change in Helical Twisting Power of Photoresponsive Chiral Dopants on Rotational Manipulation of Micro‐Objects on the Surface of Chiral Nematic Liquid Crystalline Films

Herein we report a group of five planar chiral molecules as photon‐mode chiral switches for the reversible control of the self‐assembled superstructures of doped chiral nematic liquid crystals. The chiral switches are composed of an asymmetrically substituted aromatic moiety and a photoisomerizing azobenzene unit connected in a cyclic manner through methylene spacers of varying lengths. All the molecules show conformational restriction in the rotation of the asymmetrically substituted aromatic moiety in both the E and Z states of the azobenzene units resulting in planar chirality with separable enantiomers. Our newly synthesized compounds in pure enantiomeric form show high helical twisting power (HTP) in addition to an improved change in HTP between the E and Z states. The molecule with a diphenylnaphthalene unit shows the highest ever known initial helical twisting power among chiral dopants with planar chirality. In addition to the reversible tuning of reflection colors, we employed the enantiomers of these five compounds in combination with four nematic liquid crystalline hosts to study their properties as molecular machines; the change in HTP of the chiral dopant upon photoisomerization induces rotation of the texture of the liquid crystal surfaces. Importantly, this study has revealed a linear dependence of the ratio of the difference between HTPs before and after irradiation against the absolute value of the initial HTP, not the absolute value of the change in helical twisting power between two states, on the angle of rotation of micro‐objects on chiral nematic liquid crystalline films. This study has also revealed that a change in irradiation intensity does not affect the maximum angle of rotation, but it does affect the speed of rotational reorganization of the cholesteric helix.     

正交晶型江浙蝮蛇毒碱性磷脂酶A2初步结晶学研究

The basic phospholipase A2 from the venom of Agkistrodon halys pallas possesses the ability to cause hemolysis in contrast to the other two phospholipase A2 from the same venom. A new form of crystals of this enzyme was grown. The crystals belong to space group of P212121 with unit cell parameters of a=9.175nm, b=10.080nm , c=2.287nm.The crystals diffract to high resolution, and are suitable for detailed structural studies. The data were collected up to 0.25nm resolution using synchrotron radiation-imaging plate-Weissenberg camera system. Preliminary analysis reveals the presence of two molecules in the asymmetric uint and the molecule may pack with the smallest dimension approximately parallel to the c axis. The new crystal form is more attractive than the monoclinic one previously reported for crystallographic structure determination as it contains fewer molecules in the asymmetric unit.     

Inequivalent molecules in a two-dimensional crystal

Physisorbed monolayers formed at solution-solid interfaces are two-dimensional crystals sharing many structural characteristics, such as packing motifs and reactivity, with their three-dimensional counterparts. Study of these monolayers with scanning tunneling microscopy (STM) offers a promising tool for exploring crystallization phenomena. Although the analogy between the structures of two-dimensional and three-dimensional crystals is becoming clearer with the imaging of increasing numbers of molecules with STM, the occurrence of inequivalent molecules in a unit cell has been limited to three-dimensional crystals. We report that the monolayer of 1,3-dinonadecanoyl benzene formed at the solution-HOPG interface possesses a unit cell with 1.5 inequivalent molecules (Z' = 1.5) demonstrating that, as in the case of three-dimensional crystals, simple molecules can give rise to inequivalent packing in the solid state.     

全同立构聚丙烯晶体结构的对称性研究

本文利用对称理论,研究了全同立构聚丙烯的α(型)晶及β(型)晶的可能的晶体结构.1.推导了与C2/c空间群有关的有色空间群,研究了聚丙烯分子链在它们中的排布,得出其中5种是聚丙烯α(型)晶晶体结构可能存在的空间群;2.从晶畴理论出发,得出具有Cc空间群与P2_(1/c)空间群的两种晶畴共存于一个体系中,3.聚丙烯β(型)晶的晶体结构的可能排列方式是聚丙烯分子链按R型晶胞的半无规排列。     

Enantioselective Synthesis of a Chiral Coordination Polymer with Circularly Polarized Visible Laser

Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL‐responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL‐induced enantioselective synthesis. By irradiation with either left‐handed or right‐handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left‐handed CPL resulted in crystals with a left‐handed helical structure, and right‐handed CPL led to crystals with a right‐handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.