Chiral symmetry breaking in unstirred crystallization

Statistics of nucleation of chiral forms of sodium bromate from unstirred aqueous solutions was studied. It was established that bimodal, trimodal and unimodal distributions of enantiomers are obtained in unstirred crystallization. It was also found out that probabilities of the creation of L or D crystals and racemates R, as well as the presence of D, L, and R peaks in distributions depend on crystallizer size, supersaturation and temperature. Nucleation at low supersaturations in small, closed crystallizers leads to the formation of pure enantiomers, and to bimodal distributions with D and L peaks at any temperature. At high supersaturations in large, open crystallizers the formation of racemates and unimodal distributions with racemate R peaks results. In open crystallizers at the lowest temperatures and at the highest temperatures used in crystallization from aqueous solution racemates of sodium bromate are preferentially formed, but in a wide range of intermediate‐temperatures apart from racemates, pure enantiomers are efficiently formed which leads to trimodal distributions. The spontaneous formation of pure enantiomers in crystallization from unstirred, unseeded solutions is caused by the chiral symmetry breaking phenomenon, the same as that discovered in stirred crystallization. The conservation of chiral symmetry is, in unstirred crystallization, one of the two possibilities, and the other one is the breakage of symmetry. Both of them occur in nature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chiral Symmetry Breaking in Sodium Chlorate Crystallization from Unstirred Solution

Statistics of nucleation of chiral forms of sodium chlorate from unstirred, achiral solutions was studied. The trimodal distribution of enantiomers was obtained in which apart from the peak for the same probability of the creation of L and D crystals, two other maxima for the large enantiomeric excesses of L and D forms were present. The first nucleated crystals govern the handedness of the secondary crystals and the formation of pure enantiomers and high enantiomeric excesses in crystallization from unstirred, unseeded solutions are caused by the process of chiral symmetry breaking rather than statistical fluctuations.     

氯酸钠晶体生长的手性对称破损研究

我们使用非搅拌的氯酸钠晶体水溶液,研究了晶体的手性对称破损问题.氯酸钠晶体溶液是通过溶解分析纯 NaClO3 粉末于去离子水中配制而成.采用 Mach-Zehnder 干涉方法和称重法测定晶体的溶解度.使用偏光显微镜鉴定了11545颗晶体的手性.这些晶体是从不同pH条件下的90个自发成核和生长实验中获得.实验结果表明:溶液的pH值可影响到氯酸钠晶体的手性分布.晶体手性分布的pH效应,可用随机动力学理论和胚晶凝聚二次成核理论来定性解释.     

Enantiomorphism in sodium chlorate crystals

Creation of enantiomorphous forms in sodium chlorate and enantiomorphous nature of surface micromorphology were studied by optical microscopy. It was shown that when the small number of crystals nucleates spontaneously in unstirred, unseeded solutions then exclusively left- (L) or right-handed (D) crystals can be formed. At the large number of nucleated crystals the probability of the creation of L and D form is nearly the same. L and D crystals can be distinguished by the shape of growth or dissolution centers.     

Morphology Change in Crystallization of α L-Glutamic Acid in the Presence of L-Phenylalanine

Abstract

Effect of L-phenylalanine(L-Phen) on the precipitation behavior and morphology of a L-glutamic acid (L-Glu) crystals, and inclusion of L-Phen in L-Glu crystals were investigated. L-Phen suppresses both nucleation rate and growth rate of L-Glu. The morphology of L-Glu was observed to change depending on L-Phen concentration. Two predominant morphologies were obtained, which have the large (111) face and the new face of (110), respectively. Irregular increase of the molar ratio of L-Phen to L-Glu in nucleated crystals was detected and it was attributed to the morphology change of L-Glu crystals. Dependence of R on L-Phen concentration appeared to be different between the nucleated crystals and seed crystals.     

Optimization of the local crystallization processes of preparing chiral drugs in periodic crystallizers

The regularities of periodic processes of local crystallization of enantiomers and the kinetics of nucleation and growth of crystals are considered. The criteria for optimization of technological processes of preparing chiral drugs with the aim of attaining the maximum yield of final products with a required optical purity are formulated on the basis of experimental data.     

Crystal Structure Analysis of Betti Base 1-((2-hydroxynaphthalen-1-yl)(2-hydroxyphenyl)methyl)urea•2DMF Solvate

A novel Betti base compound, 1-((2-hydroxynaphthalen-1-yl)(2-hydroxyphenyl)methyl)urea, UBB, was synthesized and characterized by spectral, structural and thermal studies. Single crystal X-ray diffraction studies reveal that the racemic mixture of the compound, when crystallized from DMF, yields R-isomer preferentially (prismatic crystals), whereas, when crystallized from 5:1 (v/v) mixture of DMF-THF, it yields S-isomer (rectangular shaped crystals) with two molecules of DMF, included in both the cases. The crystal structure is discussed in terms of supramolecular interactions and molecular modeling. Both R and S enantiomeric DMF solvate crystals are in their chiral triclinic P1 space group.     

Hollow rhombohedral calcite crystals encompassing CO2 microcavities nucleated in solution

A new way for heterogeneous nucleation of crystals from the solution is described: 3D crystalline structure can nucleate and grow encompassing gaseous cavities, formed on solid substrates in the aqueous solution, so giving rise to crystal bubbles. The double surface of a crystal bubble is made, in this case, by the faces of the cleavage calcite rhombohedron separating the solution from the enclosed gas cavity. The faces thickness and the edges length amount to a few nanometers and to about 5 μm, respectively. Then, the surface-to-volume ratio is the highest obtained for 3D crystals, amidst the consulted literature. Bubbles’ shape is explained through the equilibrium properties of crystal–cavity and crystal–solution interfaces and in terms of growth mechanisms operating on the separate interfaces. The nucleation of the crystals around gas cavities can provide new insight on those mineralization phenomena where the gas phase participate in crystal growth. Potential applications are also envisaged concerning the nucleation of the gas cavities on peculiar templates which impose 1D (or 2D) periodicity to crystal bubbles, in order to obtain 1D and/or 2D photonic crystals.     

Polymorphism of Compound Existing as Both Racemic Compound Crystals and Mixed Crystals of Enantiomers

Abstract

By recrystallization of certain racemic compound (ST), racemic compound crystals, mixed crystals of two enantiomers, or a mixture of these two types of crystals were obtained, depending on the recrystallization conditions employed. Their crystal forms were determined by X-ray diffraction of the single crystals and powdered materials. The space group and lattice parameters of the mixed crystals were identical with those of the enantiomeric crystals. This polymorphism of ST crystals would be ascribed to the small difference in the thermodynamic stability between the enantiomeric and racemic crystals. The physicochemical properties of ST are described, too.     

Temperature control of protein crystal nucleation

The thermal variant of the classical nucleation‐growth‐separation principle is shown, both theoretically and experimentally, to be a reliable tool for studying protein crystal nucleation. The classical nucleation theory is used to elucidate the temperature dependence of crystal nucleus size. A one‐to‐one ratio of the number density of nuclei formed to crystals grown to visible size is achieved using the nucleation‐growth‐separation method. The experiments conducted in such a way show that new nuclei are prevented from appearing while avoiding any crystal loss due to dissolution. The same method is used to study experimentally the interval of growth temperatures where the number density of (nucleated) crystals is relatively insensitive to the growth temperature. It is argued that this temperature interval corresponds to the width of the so‐called metastable zone.     

Statistical analysis of threshold load for radial crack nucleation by Vickers indentation in commercial soda-lime silica glass

The threshold load for nucleation of primary radial cracks in commercial soda-lime silica glass was investigated at room temperature by using Vickers indentation. The Weibull statistics with three-parameters was employed to analyze the number of cracks nucleated around each indentation as function of the applied load. The used probability estimator was (n − 0.5)/N, where n is the total number of radial cracks nucleated at a specific load and N is the total number of possible cracks. The minimum applied load for radial crack nucleation that best fitted the experimental data was equal to 180 mN. Comparison between experimental data distribution and the binomial distribution was also performed. The results were interpreted according to the fracture mechanics models for sub-threshold indentation flaws of Lathabai et al. and for crack initiation in elastic/plastic indentation of Lawn and Marshall.     

Synthesis,bulk growth,polarizability and nonlinear optical properties of γ‐glycine single crystals

The role of sodium acetate, sodium nitrate, sodium hydroxide and malonic acid as additives in assisting the nucleation of γ‐polymorph from solution has been investigated. For the first time large dimensional bulk single crystals of γ‐glycine have been grown at the optimized concentration of the additives by the top seeded slow cooling technique. The bulk growth of single crystals elucidates well the unidirectional growth characteristics and the existence of merohedral twinning in γ‐ glycine. Polarizability, plasmon energy and Fermi energy has been evaluated for the first time for γ‐glycine single crystals based on an analytical approach. Structural affirmation of the nucleated polymorph has been carried out by Powder x‐ray diffraction and the thermal characteristics of the nucleated polymorph are well revealed by Differential Scanning Calorimetry. The non linear optical characteristics of γ‐glycine studied by Kurtz and Perry technique revealed increased SHG efficiency with the highest of about 2.2 in the presence of malonic acid compared to the standard Potassium dihydrogen orthophosphate (KDP).     

利用界面调控制备二维有机半导体晶体及其机制研究

二维有机半导体晶体是利用分子间的范德瓦耳斯力进行自组装生长的单晶材料。本质上的单晶属性使其具备优异的电学特性。更重要的是,二维极限下增强的界面特性能够大幅调控器件行为,为构建多功能界面器件提供可能。此外,充分暴露的电荷输运沟道和极少的晶面内缺陷能够为研究本征的有机电子输运特性创造可能。目前,对于二维有机半导体晶体的生长工艺研究已经取得了较大的进展,但是从理论层面上研究二维晶体生长的自组装过程仍然十分匮乏。本工作利用添加剂辅助结晶技术成功制备出二维有机半导体晶体,并通过偏光显微镜和原子力显微镜对二维晶体进行了全面的表面形貌和结构表征。通过SEM结合EDS技术对关键的形核界面进行了结构和组成的表征以研究晶体生长的机制。研究结果表明:在添加剂界面上,生长材料能够稳定形核,并计算出添加剂构建的有利界面能够将形核势垒降低为SiO₂界面上的1/5。这项工作充分展现了生长界面对于晶体生长的关键作用,并从理论上揭示了界面的调控行为,为二维有机半导体晶体的生长工艺设计提供了可靠的思路。     

新型有机非线性光学晶体-L-苹果酸脲晶体生长的初步探讨

本文初步探讨了新型非线性光学晶体-L-苹果酸脲的晶体生长,研究结果表明,L-苹果酸脲晶体在甲醇、乙醇和水三种介质中的溶解度温度系数均较大,同温度下L-苹果酸脲晶体在水中的溶解度最大,无水甲醇次之,无水乙醇中最小.L-苹果酸脲晶体在无水甲醇中的成核自由能比在无水乙醇中的低得多,因此在无水甲醇中易于成核,晶核数多,晶体尺寸小,而在无水乙醇介质中,虽然成核相对比较困难一些,但有利于制备大的单晶,且发现低温有利于大晶体的生长.因此宜选择无水乙醇为晶体生长介质.L-苹果酸脲晶体在介质中以非均匀成核方式在试管壁成核长大,晶体呈棱柱状,生长过程中呈现台阶生长的特征.     

基于ISIGHT的二维手性声子晶体带隙最优设计

本文首先利用有限元仿真软件COMSOL计算了二维手性声子晶体的带隙,分析了散射体参数与韧带涂层参数变化对带隙的影响规律。在此基础上,确定手性声子晶体带隙最优设计的有效参数设计空间;然后基于ISIGHT优化设计平台嵌入遗传算法,开展二维手性声子晶体带隙的最优设计。在带隙的最优设计过程中,先以二维手性声子晶体的有效构型参数为设计变量,相对带隙宽度最大为目标,设计手性声子晶体单胞构型。再以此优化单胞构型为初始构型,以手性声子晶体的有效材料参数为设计变量,相对带隙宽度最大为目标,进一步实现二维手性声子晶体带隙的最优设计。本工作极大限度地挖掘了二维手性声子晶体带隙最优设计潜能,为充分发挥手性声子晶体在减振降噪中的作用提供了可靠有效的分析设计方法。     

Influence of drawing temperature on the strength of fluoride glass fibers

The tensile strength of fluorozirconate glass fibers was measured as a function of fiber drawing temperature, and strengths ranging from 60–220 MPa were observed. Statistical analysis of the strength data points to a bimodal behavior in the fibers drawn at high temperatures, while the mode of fracture is essentially unimodal for fibers drawn at lower temperatures. SEM examination of the fibers drawn at high temperatures revealed the presence of crystals in the fibers, and these crystals were associated with flaws which gave rise to the observed low strength distribution.     

Chiral resolution in bent-core nematic liquid crystals

This paper presents the currently available experimental evidence for the occurrence of chiral resolution in bent-core nematic liquid crystals. The observation of chiral domains in these systems is discussed in context with other indications for the unique character of the nematic phase in bent-core materials, which challenge our understanding of nematic phase behaviour. Two possible mechanisms for the emergence of macroscopically chiral domains are exposed; the spontaneous resolution of chiral bent-core conformers and the occurrence of helical twist bend deformations due to a unique propensity for spontaneous bending of the nematic director in bent-core materials. The latter proposition is put into context with the recently developed cluster model, as overall it appears more appropriate to consider bent-core nematic systems as self-assembling-self-organising fluids with a hierarchical domain structure.     

Chiral phases in a system of biaxial molecules

Chiral phases in a system of biaxial molecules are investigated based on a theory of biaxial liquid crystals, which we have presented in past work. Four chiral phases are identified, corresponding to a uniaxial nematic phase, two biaxial nematic phases, and a discotic phase, respectively. We find that in the chiral uniaxial nematic phase, the pitch of the chiral structures does not depend on temperature. In contrast, in the two chiral biaxial nematic phases, as well as in the chiral discotic phase, the pitch is temperature-dependent.     

Nucleating characteristics of Pseudomonas aeruginosa above 0 °C and the role of l-leucine

It has been reported earlier that the bacteria Pseudomonas aeruginosa have the ability to nucleate ice over a long temperature range below 0 °C. In the present work, the same bacteria are shown to have nucleating ability even above 0 °C. It is found to reach a peak at 4 °C and then gradually falls off as the temperature is raised, vanishing altogether at 12 °C. When the bacteria are irradiated by UV-rays, the nucleating ability above 0 °C has the same variational pattern with change of temperature, though the ability is significantly less. When the bacterial medium is boiled for 20 min, the bacteria loose their nucleating ability completely.Since ice cannot exist above 0 °C, some supporting experiments are performed to establish the identity of the nucleated crystals:

• (a)Crystals grown around a small sample of cultured P. aeruginosa in an incubator were shown to be identical with the nucleated crystals in the Cold Room experiments.
• (b)X-ray diffraction (XRD) spectrum of the grown crystals is found to be consistent with the presence of amino acids like l-leucine, isoleucine and l-isoleucine, amongst which l-leucine is the most abundant.

When droplets of an aqueous solution of l-leucine are seeded, their nucleation characteristics are similar to those with P. aeruginosa. From XRD, nuclear magnetic resonance (NMR) and thermal analysis, one can conclude that the crystals formed by P. aeruginosa above 0 °C are hydrate crystals with water phase caging around the seeded agent; the amino acid l-leucine present in the protein of the bacteria plays the dominant role in the nucleation.     

The precipitation of lead sulphate from aqueous and aqueous alcohol solutions: Nucleation,final sizes and morphology

The precipitation of lead sulphate was studied from 0.0001 to 0.01 M aqueous solutions (supersaturations 3 to 600) and from 20% aqueous ethanediol, methanol and ethanol solutions, in polypropylene beakers, at ambient temperature: the experimental techniques were conductivity measurements and optical microscopy. The precipitations were heterogeneously nucleated at low supersaturations and homogeneously nucleated at intermediate to high supersaturations. New crystal morphologies generally developed at some what higher supersaturations in the aqueous alcohol systems. The final crystal lengths at first increased with increasing initial metal salt concentration and then decreased with this parameter; the largest crystals at any concentration were obtained from solutions in which lead sulphate solubility was highest. The critical supersaturations (for the onset of homogeneous nucleation) increased from 36 (in water) to 50 (in 20% aqueous ethanol): the surface energies for the formation of nuclei correspondingly increased from 90 to 110 mJ m⁻² in good agreement with the Nielsen-Söhnel relation. The nucleation and crystal growth processes are taking in an aqueous environment of similar water activity to that of the bulk solutions.