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.     

Influence of gel inclusions on the mechanical behaviour of Gypsum

In a single test tube system, gypsum crystals grown in alcoholic gel comprise of interpenetration twinned crystals at the interface towards the gel, whereas untwinned tabular crystals are observed at greater depths inside the gel. By indentation of the crystals with a microhardness tool and recording the indentation impressions by means of a scanning electron microscope (SEM) and a transmission electron microscope (TEM) it is found that the hardness of the tabular crystals is of the same order of magnitude as those of natural crystals of gypsum, whereas interpenetration twinned crystals show a remarkable increase in hardness. On studying the morphology of cleavage faces and on carrying out energy dispersive X-ray analysis (EDXA), it is concluded that the increase in hardness of interpenetration twinned crystals with respect to tabular and natural crystals may be due to the role of the inclusion of gel particles during the growth. The implications are discussed.     

Deuterated hen egg-white lysozyme crystals: Optimization of the growth conditions and morphology

Deuterated and protonated tetragonal lysozyme crystals are grown using the hanging-drop vapor-diffusion method. The size of the lysozyme crystals grown is determined as a function of the concentration of sodium chloride used as a precipitant. It is found that crystallization leads to the formation of lysozyme crystals with three different habits. Morphological and X-ray diffraction analyses of the deuterated and protonated lysozyme crystals demonstrate that, despite the different habits, all the crystals grown belong to the tetragonal crystal system. The simple forms of lysozyme crystals are revealed. It is shown that the habits of the lysozyme crystals are determined by the specific combinations of simple forms. The mechanisms responsible for the formation of lysozyme crystals with different habits are discussed.     

Morphology of PbI2 Crystals Grown by Gel Method

The single crystals of Lead Iodide have been grown by gel method. X‐ray diffraction studies on these crystals shows that the lattice parameters of grown crystals are almost matching with reported values. The results of detailed studies made on the microstructures of Lead Iodide crystals, have been described. The observations of the faces of these crystals revealed that they have grown by layer as well as spiral mechanisms. The probable role of these parameters is explained along with the surface microstructures on these various shaped crystals.     

生长温度对KDP晶体光学性质影响的研究

用降温法在不同的温度下快速生长KDP晶体,并测量其透过光谱、光学均匀性、金属杂质含量和光散射性能.结果表明随着生长温度的提高,KDP晶体的紫外光吸收和光散射点密度明显降低,但均匀性和杂质金属离子含量并无明显变化.     

A survey of research on KTP and its analogue crystals

This paper reviews the growth and properties of KTiOPOP₄ (KTP) and its analogue crystals including its isomorphous crystals and doped crystals. Based on the calculation of the refractive indices and phase matching of KTP crystals, it is shown that non-critical phase matching can be achieved theoretically. In a 4%Nb-doped KTP crystal, non-critical phase matching was obtained with a pulsed Nd:YAG laser in an efficiency of ca. 4%. Most of the isomorphous and doped KTP crystals possess similar physical, optical and nonlinear optical properties as those of KTP.RbTiOPO₄, KTiOASO₄ and RbTiOASO₄ crystals have better electrooptical figure of merit and RbTiOPO₄ crystals have a fast ion conductor character. Some doped KTP crystals have shown high second harmonic generation efficiencies and damage thresholds. But the homogeneity of KTP analogue crystals is poorer than that of KTP. On the base of damage threshold tests using a CW Argon laser, it is concluded that the best second harmonic generation crystal among all the KTP analogue crystals is still KTP itself. Special care must be taken to eliminate impurity centers to avoid the formation of gray track and photorefractive centers.     

Crystal Growth and Structural Refinements of the Y2SiO5, Y2Si2O7 and LaBSiO5 Single Crystals

The laser crystals of chromium doped yttrium oxyorthosilicate (YSO) were grown from the melt by Czochralski technique. The crystals of YSO, yttrium pyrosilicate and stillwellite-like lanthanum borosilicate were obtained from high temperature solutions. Lithium and potassium di- and trimolybdates were used as fluxes in the growth experiments on silicate crystals. In the case of borosilicate crystals, the choice of fluxes was based on the potassium trimolybdate with an excess of potassium fluoride. The composition of grown crystals was studied by electron microprobe analysis, and structural characteristics were determined for all the single crystals.     

Terrestrial and space-grown HAP and OCP crystals: effect of growth conditions on perfection and morphology

This paper reports comparative characterizations of calcium phosphate crystals grown on earth and in space. At the CaCl2 and KH2PO4 + K2HPO4 solution concentrations and the pH used, only hydroxyapatite (HAP) crystals grow under terrestrial condition while both HAP and octacalcium phosphate (OCP) crystals grew during the space experiment. The space-grown OCP crystals reach 3 mm in size, the space-grown HAP crystals reach sizes up to 100 times larger than the earth-grown crystallites. It was found also that the space-grown crystallites are more perfect than the terrestrial ones, being more stable under electron beam during HRTEM examination. Spherolites of hydroxyapatite consist of small and thin HAP crystals with different orientations. Space-grown OCP crystals containing almost pure OCP phase show strong striations along the c direction due to thickness variations. Terrestrial OCP crystals grown at lowest supersaturation on earth may be almost as large as the space-grown ones, possess a regular habit and are homogeneous in thickness. However, they always contain substantial regions of HAP structure. Also, in these crystals electron irradiation induces phase transformation from crystalline to amorphous (disordered) state during transmission electron microscopy observations. In the space-grown crystals, such transformation needs longer radiation time. We believe that the differences described above come from much lower supersaturation and different pH for crystals nucleating and growing in space compared to those formed on earth.     

Growth of dl-malic acid-doped ammonium dihydrogen phosphate crystal and its characterization

Single crystals of dl-malic acid-doped ammonium dihydrogen phosphate have been grown using slow evaporation method and also by Sankaranarayanan–Ramasamy (SR) method with the vision to improve the properties of the ADP crystals. The characterization of grown crystals was made by single-crystal X-ray diffraction, powder X-ray diffraction, UV–vis. spectroscopy, Fourier transform infrared spectroscopy (FTIR), differential thermal analysis (DTA), Vicker's microhardness, dielectric measurements, high-resolution X-ray diffraction (HRXRD) and second-harmonic studies. Structural difference between pure and doped crystal has been studied by XRD analysis. Functional groups were identified by FTIR spectroscopy. The grown crystals were found to be transparent in the entire visible region. Decomposition temperatures of the grown crystals were measured by DTA. Vicker's hardness study carried out on (0 0 1) face at room temperature shows increased hardness of the doped crystals and SR-method-grown crystals. Dielectric measurements reveal that SR-method-grown DLM-doped ADP crystals have low dielectric loss. Crystalline perfection of the grown crystals is analyzed using HRXRD. Preliminary measurements indicate that the second harmonic generation efficiency of the doped crystals at a fundamental wavelength of 1064 nm is roughly 1.5 times greater than that of pure ADP.     

Effect of Ultrasonics on Agglomeration

Crystal size distribution of potassium aluminium sulphate dodekahydrate prepared under various conditions has been used for characterization of the degree of agglomeration of crystals. Six series of batch precipitation experiments with batch times from 2 to 80 minutes have been represented by a) dried crystals, b) the same crystals partially de-agglomerated before the measurement, c) wet crystals taken directly from the batch, d) the same crystals partially de-agglomerated before the measurement, e) wet crystals taken directly from the batch occurring under ultrasonic action, and f) these crystals partially de-agglomerated just before the measurement. Degree of agglomeration decreases in this sequence.     

Investigation of growth kinetics and morphology of sodium fluorosilicate ice‐analogue crystals in solutions and gels

The effect of growth method (solution or gel growth) and growth conditions on the morphology of ice analogue crystals (sodium fluorosilicate) has been studied. Many habits typical for atmospheric ice crystals (hexagonal columns, plates, different types of stars or dendrites) were obtained during experiments. The dependence of growth rate of basal and prism faces of columnar crystals on supersaturation was measured for crystals growing by evaporation of solvent. The experiments establish evaporation rate and growth rate ranges at which appearance of certain types of crystals is most probable. The experiments have also shown that good quality sodium fluorosilicate crystals can be obtained in TMS gel. These crystals were significantly bigger than those obtained in solution. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Water-soluble ferroelectric crystals with inhomogeneous impurity distribution

Stabilization of the unipolar state via the formation of inhomogeneous impurity distribution in crystal bulk is considered. Possible growth of crystals with stable characteristics is demonstrated on triglycine sulfate (TGS) crystals with a regular inhomogeneous impurity distribution. The properties of TGS crystals with an inhomogeneous distribution of chromium ions grown above and below the Curie temperature T_C are studied. Inhomogeneous TGS crystals of three types are obtained: type-I crystals with a smooth variation of the concentration gradient along the growth direction, type-II crystals with a periodic layer variation of the impurity concentration, and type-III crystals with a sawtooth-like variation of the impurity concentration along the sample length. The TGS crystals with the regular inhomogeneous impurity distribution in the ferroelectric phase are characterized by higher values of the internal bias field E _b , unipolarity coefficient k, and pyroelectric coefficient γ than the inhomogeneous crystals in the paraelectric phase and the crystals with the statistic impurity distribution grown by the conventional method.     

A comparative study of pure and potassium doped cadmium mercury thiocyanate single crystals grown in silica gel

Pure and potassium doped cadmium mercury thiocyanate single crystals have been obtained from silica gel by the process of diffusion. The X‐ray diffraction studies reveal the crystal lattice of both pure and doped crystals to be tetragonal. The crystalline perfection of the grown crystals were investigated by high resolution X‐ray diffraction analysis and the quality of the crystals are found to be extremely good. Transmission and Fourier transform infrared spectra were recorded for the grown crystals. The TG/DTA analyses show that the crystals are highly thermally stable. The mechanical strength of the crystals were studied by Vickers microhardness test and a study of their second harmonic generation efficiency in comparison with urea has been made by performing Kurtz powder test. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

氟化钡晶体电注入着色

在不同的温度,电压和时间条件下,经点阴极电注入,有效地使氟化钡晶体着色.在室温下,分别对着色前后的晶体进行系统光谱测量.在着色前的氟化钡晶体中未观测到明显的吸收峰.在着色后的氟化钡晶体中,观测到大量的F和FA色心以及一些未知色心.对不同电注入温度、电压和时间条件下的着色氟化钡晶体光谱进行比较分析,得到了经点阴极电注入着色氟化钡晶体色心强度随着色温度,电压和时间的变化规律并给出了色心形成机理以及色心强度随温度、电压和时间变化机理.     

熔体法生长大尺寸有机晶体

大尺寸有机晶体在太赫兹波产生、中子探测、微波激射等多个关系国计民生、涉及国家安全的领域具有重要应用前景.但大尺寸有机单晶生长一直是国际公认的难题,无论是在生长理论、生长方法还是生长设备方面都远远落后,在整个人工晶体领域相对小众;而且有机晶体硬度低、脆性高、易解理等本征特性为加工和后期应用带来了很多困难,制约了相关领域的...     

Growth of CdBr2 single crystals by zone refining

CdBr₂ has been purified using a 12-pass zone-refining technique. Single crystals grown from the starting material showed arcing in the X-ray oscillation photographs whereas this is absent in the crystals grown from zone refined material. These crystals are found to be 6R type. In order to study the effect of impurities, DC conductivity studies were made on the crystals at various stages of purification. Surface morphology of the crystals have been studied using an optical microscope.     

Effect of ammonium malate on growth rate,crystalline perfection,structural, optical,thermal, mechanical,dielectric and NLO behaviour of ammonium dihydrogen phosphate crystals

The effect of ammonium malate on the growth rate, structural, optical, thermal, mechanical, dielectric properties, crystalline perfection and second harmonic generation (SHG) efficiency of ammonium dihydrogen phosphate single crystals grown by the slow cooling method has been investigated. The lattice parameters of the grown crystals were obtained by the single-crystal X-ray diffraction analysis. Fourier transform infrared studies confirm the functional groups of the crystals. UV–vis study shows that the transparency is increased much by the dopant. Thermal analysis was performed to study the thermal stability of the grown crystals. Vickers hardness measurements reveal the higher hardness of the doped crystals. Low dielectric losses were observed from the dielectric measurements for the doped ADP crystals. The high-resolution X-ray diffraction studies show that the crystalline perfection of the crystals is good. The relative SHG efficiency measurements revealed that the dopant has enhanced the efficiency.     

What is a protein crystal? Can we apply the terminology of classical industrial crystallization to them?

The nature of protein crystals is discussed. Since protein crystals contain not only proteins but also other substances the usage of conventional terms (of industrial crystallization) of naming such crystals is questioned. The proof that there are other components than the protein itself in a protein crystal is given. It is suggested to use a procedure like in biotechnology to guarantee the production of the right protein crystals according to the PAT concept. It is suggested not to use other established names like “hydrates”, “solvates”, “but crystals for proteins since the definitions do not fit the nature of the protein crystals.     

Mechanoluminescence of halogenate crystals

Mechanoluminescence (ML) has been studied in twenty halogenate crystals. All piezoelectric crystals show ML similar to the emission from second positive group of molecular nitrogen, and all the crystals not exhibiting ML are non-piezoelectric. Some of the non-piezoelectric crystals also exhibit nitrogen emission ML which is comparable in intensity to that of piezoelectric crystals. The ML appears only during the different steps developing in the fracture region of the force versus compression curve of the crystals. No considerable change in the ML activity is found due to the number of crystallization or due to the addition of different impurities from 100 to 10.00 ppm. The ML activity per mole of the halogenate crystals varies around four orders of magnitude. It is concluded that in addition to the piezoelectrification of the newly created surfaces there exists some other process of electrification which may cause the ML exitation in halogenate crystals.     

Growth of single crystals of barium iodate and strontium iodate in silica gels

Single crystals of iodates of barium and strontium grown by gel method are reported. Optimum conditions for good quality single crystals are worked out. Different habits of these crystals are reported. A brief report for characterization of these crystals by different methods is given.