The fluid phenomena in the crystallization of the protein crystal

This paper reports that an optical diagnostic system consisting of Mach-Zehnder interferometer with a phase shift device and image processor has been used for study of the kinetics of protein crystal growing process. The crystallization process of protein crystal by vapour diffusion is investigated. The interference fringes are observed in real time. The present experiment demonstrates that the diffusion and the sedimentation influence the crystallization of protein crystal which grows in solution, and the concentration capillary convection associated with surface tension occurs at the vicinity of free surface of the protein mother liquor, and directly affects on the outcome of protein crystallization. So far the detailed analysis and the important role of the fluid phenomena in protein crystallization have been discussed a little in both space- and ground-based crystal growth experiments. It is also found that these fluid phenomena affect the outcome of protein crystallization, regular growth, and crystal quality. This may explain the fact that many results of space-based investigation do not show overall improvement.     

Molecular dynamics simulations of the formation for NaCl cluster at the interface between the supersaturated solution and the substrate

Molecular dynamics simulations of supersaturated aqueous NaCl solution including the Pt(100) or NaCl(100) crystal surfaces have been performed at an average temperature of 298 K. The behavior of the NaCl cluster produced in the solution have been studied through the consideration of the water dielectric property near the crystalline surfaces for understanding the role of crystal growth on the surface. The surfaces in the solutions greatly influence heterogeneous nucleation in crystallization process. Density profile of the supersaturated solution and polarization of water molecules was calculated in order to describe the effect of the surfaces on the solution structure at the solid–liquid interfaces. The formation levels of NaCl clusters heavily depended on the water orientation at the interfaces. NaCl clusters were easily formed near the Pt(100) surface compared with the NaCl(100) surface owing to a different construction of water molecules between the platinum and NaCl surface.     

Kinetics and growth mechanism of gallium arsenide crystals in gas-phase epitaxy

Conclusion In conclusion, we note that gallium arsenide itself is the material with which the physicochemical and crystallophysical fundamentals of gas-phase epitaxy are presently being developed. It is hoped that the basic principles or crystal growth in gas-phase systems discovered in gallium arsenide will prove sufficiently general to be applied to other analogous systems.The complex multistage processes occurring on a crystal surface during gas-phase crystallization require development of a more general theory of crystal growth — one which considers heterogeneous reactions and participation in the surface processes of noncrystallizing atoms and molecules. On the other hand, for construction of such a theory and its comparison to experiment information will be required not only on the composition of the gaseous phase and the growth kinetics, but also on the composition and structure of the adsorption layer and the crystallization surface, the acquisition of which in gas-phase systems is complicated in comparison to, for example, molecular-beam epitaxy systems. It is possible that these difficulties will be overcome with time. A certain part of the information on composition and structure of the surface in contact with the complex gas phase can apparently be obtained under conditions close to equilibrium. This part of the problem of gas-phase epitaxy research merges completely with problems of the characterization of the physicochemical state of semiconductor surfaces in general.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 23–37, January, 1980.     

The platelet integrin alpha(IIb) beta(3) imaged by atomic force microscopy on model surfaces

The platelet membrane receptor alpha(IIb) beta(3) binds to adsorbed protein ligands including fibrinogen, von Willebrand factor and fibronectin, and is critically important in mediating platelet adhesion to damaged subendothelium and to synthetic biomaterial surfaces. This receptor is a member of the integrin family, a highly prevalent class of heterodimeric molecules consisting of a single alpha and beta subunit. In an ongoing effort to understand the mechanisms underlying platelet adhesion events, high-resolution atomic force microscopy (AFM) under dynamic conditions was used to obtain images of alpha(IIb) beta(3) molecules as well as aggregates of the protein. Images of integrin molecules were obtained by tapping mode AFM under aqueous buffer conditions following adsorption on a series of ultrasmooth model surfaces. On a model hydrophobic surface, detergents stabilizing the protein in solution competed for surface adsorption sites. When this detergent was removed from the system, the protein was predominantly seen as aggregates with head groups pointing outward. A limited number of individual integrin molecules were observed, and were found to have dimensions consistent with those reported previously by electron microscopy studies. Integrin molecules showed weak adhesion to the two hydrophilic surfaces used in the study, although formation of a lipid bilayer around surface-adsorbed molecules improved the resolution. At longer time periods, the integrin molecules embedded in this lipid bilayer exhibited sufficient mobility to form molecular aggregates. The structural measurements described in this study not only reveal three-dimensional features of the molecule, they represent an important step towards dynamic adsorption experiments and visualizing the integrin interacting with surface-adsorbed proteins as in biomaterial-induced thrombogenesis.     

Lysozyme crystallization in hydrogel media under ultrasound irradiation

Sonocrystallization implies the application of ultrasound radiation to control the nucleation and crystal growth depending on the actuation time and intensity. Its application allows to induce nucleation at lower supersaturations than required under standard conditions. Although extended in inorganic and organic crystallization, it has been scarcely explored in protein crystallization. Now, that industrial protein crystallization is gaining momentum, the interest on new ways to control protein nucleation and crystal growth is advancing. In this work we present the development of a novel ultrasound bioreactor to study its influence on protein crystallization in agarose gel. Gel media minimize convention currents and sedimentation, favoring a more homogeneous and stable conditions to study the effect of an externally generated low energy ultrasonic irradiation on protein crystallization avoiding other undesired effects such as temperature increase, introduction of surfaces which induce nucleation, destructive cavitation phenomena, etc. In-depth statistical analysis of the results has shown that the impact of ultrasound in gel media on crystal size populations are statistically significant and reproducible.     

MOLECULAR MORPHOLOGY AND CRYSTALLIZATION IN THE QUANTUM LIMIT

The effects of phonons on crystallization and crystal morphology are investigated. It is shown that the commensuration of the lattice vibrations with the lattice will favor certain crystal morphologies. Vibrational effects can also be important for the molecular structure of chain molecules. In this case, the contribution from quantum mode forces to denaturation is estimated by using a simple phenomenological model describing the molecule as a continuum. The frequencies of the vibrational modes depend on the molecular dimensionality; hence, the zero-point energies for the folded and the denatured protein are estimated to differ by several electron volts. For a biomolecule, such energy is significant and may contribute to cold denaturing as seen for proteins. This is consistent with the empirical observation that cold denaturation is exothermic and hot denaturation endothermic.     

Characterization of crystal growth using a spiral nucleation model

Classical concepts of two-dimensional nucleation and spiral growth are used together with recent findings on the dynamics of dislocation spirals to derive a new crystal growth model. Initial growth nuclei result from the organization of adsorbed molecules in spirals around surface dislocations. The energetic barrier for the activation of the spiral nuclei is considerably lower than the admitted by classical two dimensional nucleation models. Stable nuclei evolve into bigger growth hillocks in supersaturated media through the incorporation of adsorbed units into their steps. The displacement velocity of steps during solution and vapour growth is calculated by different kinetic approaches, taking into consideration the distinct role of surface diffusion in each process, and avoiding known limitations of conventional theories. A generalized expression is obtained relating the crystal growth rate with main variables such as supersaturation, temperature, crystal size, surface topology and interfacial properties. At the end of the paper, the crystallization kinetics of sucrose measured at 40 °C is interpreted in the light of the new perspectives resulting from the proposed model. The application example illustrates how to estimate interfacial and topological properties from the experimental crystal growth results.     

Photobleaching on Photonic Crystal Enhanced Fluorescence Surfaces

The effect of resonant fluorescent enhancement from a photonic crystal surface upon the fluorescent photobleaching rate of Cyanine-5 labeled protein has been investigated. We show that the enhanced excitation mechanism for photonic crystal enhanced fluorescence, in which the device surface resonantly couples light from an excitation laser, accelerates photobleaching in proportion to the coupling efficiency of the laser to the photonic crystal. We also show that the enhanced extraction mechanism, in which the photonic crystal directs emitted photons approximately normal to the surface, does not play a role in the rate of photobleaching. We show that the photobleaching rate of dye molecules on the photonic crystal surface is accelerated by 30x compared to an ordinary glass surface, but substantial signal gain is still evident, even after extended periods of continuous illumination at the resonant condition.     

液晶显示用取向材料聚甲基丙烯酸肉桂酰氧基乙酯的光控取向研究

通过实验研究了光聚合物材料聚甲基丙烯酸肉桂酰氧基乙酯（ＣＥＭＣ）的光化学反应过程, 以及对液晶材料ＬＣ－６７１０Ａ 的取向能力． 通过原子力显微镜（ＡＦＭ）观察了取向层表面在光化学反应前后的变化, 测量了光控取向膜液晶盒中液晶分子的预倾角及单面光控取向扭曲向列液晶显示器（ＴＮＬＣＤ）的电光特性和时间响应特性曲线, 研究了液晶分子排列取向的机理．     

升温在位红外研究物理老化对间规聚苯乙烯结晶行为的影响

通过在位红外光谱测量研究了物理老化对非晶和δ晶型的间规聚苯乙烯（ＳＰＳ）升温结晶过程的影响。发现对于晶样品来说,在物理老化前后,其结晶（即非晶→α晶型）的温度区间变化不大;但对于δ晶型的样品而言其物理老化后的晶型转变（即δ晶型→γ晶型）温度区间是１０４～１２７℃,与未物理老化的晶型转变温度区间９０～１１２℃相比,转变温度升高了约１４℃,这充分说明了物理老化使溶致型的δ晶型更加稳定,其溶剂与晶体的结     

金纳米粒子的电化学合成及光谱表征

采用电化学方法合成各种形状的金纳米粒子,生成的金纳米粒子形貌与施加电流有关,通过匀速递增电流电解的方法,可制备得到哑铃形,球形以及棒状金纳米粒子,采用恒电流电解方法主要获得球形及哑铃形纳米粒子。利用透射电镜、紫外-可见光谱及拉曼光谱对金纳米粒子进行相关表征。紫外-可见光谱研究发现金纳米棒出现位于近红外区间的吸收峰(985 nm),由此推测棒的长径比约为6。以结晶紫为探针分子,研究了金纳米粒子的表面增强拉曼光谱(SERS)效应,并分析得出其平躺的吸附模式。根据形貌表征的结果推断了纳米粒子的生长机理。     

Optimization of salt concentration in PEG-based crystallization solutions

Although polyethylene glycol (PEG) is the most widely used precipitant in protein crystallization, the concentration of co-existing salt in the solution has not been well discussed. To determine the optimum salt concentration range, several kinds of protein were crystallized in a 30% PEG 4000 solution at various NaCl concentrations with various pH levels. It was found that, if crystallization occurred, the lowest effective salt concentration depended on the pH of the protein solution and the pI of the protein molecule; that is, higher salt concentrations were required for crystal growth if the difference between pH and pI was increasing. The linear relationship between the charge density of the protein and the ionic strength of the crystallization solution was further verified. These results suggested that the lowest effective concentration of salt in a crystallization solution can be predicted before performing a crystallization experiment. Our results can be a tip for tuning crystallization conditions by the vapor-diffusion method.     

AlN晶体物理气相传输法生长坩埚的热场分析

采用物理气相传输法在钨制坩埚上制备AlN单晶.通过采用COMSOL软件中的固体传热和磁场模块,对AlN晶体生长的坩埚的热场进行仿真,同时针对不同的线圈直径以及不同的线圈位置对坩埚热场的影响进行模拟,提出了相应的处理方式.结果表明:当线圈直径增大,坩埚结晶区和升华区的温度在相同的加热时间下会增加,并且增加的温度存在峰值.当线圈的垂直位置发生变化的时候,结晶区和升华区的温度场也会发生变化,从上向下移动的过程中仍然存在温度的峰值,并且结晶区和升华区的温度关系会发生翻转,导致温度梯度阻碍晶体生长.在晶体生长过程中升华区和结晶区的温度关系依旧会发生翻转.但是通过线圈跟随籽晶表面生长层的变厚而同步移动,可以保持相对稳定的温度关系,维持晶体正常持续生长.     

Two-stage crystallization on the surface of smectic nanofilms

The influence of the surface and finite size on crystallization in nanofilms of a smectic C liquid crystal with thicknesses between two and several tens of molecular layers has been studied. Transitions in a single surface molecular layer have been detected by optical methods. It has been found that transitions on the film surface take place at a temperature 8°C higher than the crystallization temperature in a bulk sample. Two-stage crystallization has been detected in surface layers where the surface induces a transition to an intermediate structure different from the structure of the phases of the bulk sample.     

Plasmon electro-optic effect in a subwavelength metallic nanograting with a nematic liquid crystal

The electro-optic effect in hybrid structures based on subwavelength metallic nanogratings in contact with a layer of a nematic liquid crystal has been experimentally studied. Metallic gratings are fabricated in the form of interdigitated electrodes, which makes it possible to use them not only as optical elements but also for the production of an electric field in a thin surface region of the layer of the liquid crystal. It has been shown that, owing to the electric-field-induced reorientation of molecules of the liquid crystal near the surface of the grating, it is possible to significantly control the spectral features of the transmission of light, which are caused by the excitation of surface plasmons. The electro-optic effect is superfast for liquid crystal devices because a change in the optical properties of the system requires the reorientation of molecules only in a very thin surface layer of the liquid crystal.     

Numerical simulation of water vapor nucleation on electrically neutral nanoparticles

Atomic-level Monte Carlo simulations are performed to calculate the free energy, entropy, and work of nucleation for clusters of more than 6 × 10³ water molecules growing on silver iodide crystalline particles of size up to 4 nm at a temperature of 260 K. The Hamiltonian of the system includes explicit expressions for hydrogen bonding energy and Coulomb, dispersion, exchange, and polarization interactions. The work of nucleation exhibits complex behavior depending on the nucleation-site size. With increasing nanoparticle size, clusters become less stable and the probability of crystallization increases. Mutual polarization enhances the bonding between a cluster and a crystalline particle. Cluster growth on relatively large nanoparticles involves two stages characterized by two critical sizes: monolayer growth on the surface and growth normal to the surface. Spontaneous microdroplet polarization involving domain formation is found to occur at the crystal surface. The dependence of the ice-forming activity of an aerosol on particulate size observed in experiments is explained by combined effects of several competing factors, the dominant ones being the stabilizing and destabilizing effects of the nanoparticle electric field.     

聚酰亚胺LB膜上液晶表面锚定的研究

通过测试光延迟研究了聚酰亚胺ＬＢ膜的光学各向异性，分析了在ＬＢ膜成膜过程中成膜分子的流动取向特性，并研究了液晶的表面锚定能，分析了ＬＢ膜上液晶的取向机制．聚酰亚胺ＬＢ膜的链段的取向程度较强摩擦情形的聚酰亚胺表面的链段取向要差．强摩擦的聚酰亚胺会比聚酰亚胺ＬＢ膜具有更好的排列液晶分子的能力．ＬＢ膜的流动取向模式使得聚酰亚胺成膜分子沿拉伸方向形成一定的有序排列，并诱导液晶分子定向排列，液晶和聚合物分子相互作用是液晶表面排列的主要动力 关键词：     

Sonocrystallization: effect on lactose recovery and crystal habit

Sonocrystallization is the use of power ultrasound to control the crystallization process, commonly used during the nucleation phase of crystallization. However, in the present study a different approach has been tried, in which the whole process of lactose crystallization from model reconstituted lactose solutions was completed rapidly with the aid of ultrasound, in the presence of 'ethanol' as an anti-solvent, at temperature of 30+/-2 degrees C (ambient temperature). The lactose recovery and crystal properties from sonicated samples were compared with non-sonicated samples. For optimization of sonocrystallization process for rapid lactose recovery, variations in the time of sonication, lactose concentration, protein concentration and pH were tried. A lactose recovery of 91.48% was obtained in 5 min of sonication time, from a reconstituted lactose solution (17.5% w/v, pH 4.2) as against 14.63% under only stirring. Lactose recovery decreased with lowering of pH from 4.2 to 2.8. The protein showed maximum influence on lactose recovery even at concentration of 0.2% w/v. A rapid process of crystallization gave a better uniformity in crystal size distribution of lactose samples.     

Single-nucleus polycrystallization in thin film epitaxial growth

We have observed, by use of low-energy electron microscopy, the first direct evidence of self-driven polycrystallization evolved from a single nucleus in the case of epitaxial pentacene growth on the Si(111)-H terminated surface. In this Letter we demonstrate that such polycrystallization can develop in anisotropic systems (in terms of crystal structure and/or the intermolecular interactions) when kinetic growth conditions force the alignment of the intrinsic preferential growth directions along the density gradient of diffusing molecules. This finding gives new insight into the crystallization of complex molecular systems, elucidating the importance of nanoscale control of the growth conditions.     

Protein crystal growth: An approach based on phase diagram determination

There is an increasing need to rationalize protein crystal growth, mostly carried out so far by trial-and-error. The phase rule gives the number of conditions necessary to specify the state of protein crystallization in equilibrium. Unsaturated and supersaturated regions are distinguished in phase diagrams. Examples of such diagrams for protein crystals are tabulated. To determine the phase diagrams reliably, the following items are discussed: (1) proper crystallization methods, (2) the length of time needed for establishing equilibrium, and (3) the importance of specifying the kind of solid state. Various crystallization methods are compared as to their effect on the solution system by using the phase diagrams, and the potential usefulness of the diagrams for crystallizing new proteins is discussed.