PubMed · 12618812
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Gautam R Desiraju. 2002. Cryptic crystallography.. https://doi.org/10.1038/nmat726
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During layerwise growth of crystals, capillarity governs the generation of new crystal layers. Theory predicts that the line tension of the layer edge determines, via the characteristic two-dimensional capillary length L(c), the rates of generation and initial growth of the new layers. To test the correlation between L(c) and the rate of layer generation, we used in situ Tapping Mode Atomic Force Microscopy (TM-AFM) to study the generation and spreading of layers during crystallization of rhombohedral, R3, porcine insulin. We show that crystallization of this insulin form is uniquely suitable for such an investigation due to the linear kinetics of step growth it exhibits. This linear kinetics reflects the abundance of the incorporation sites along the rough steps, the lack of long-range step-step interactions, and the transport control of the growth kinetics. The kinetic coefficients are 7 x 10(-)(3) and 4 x 10(-)(2) cm s(-)(1), respectively, in the absence and presence of the cosolvent acetone-somewhat high for proteins and comparable to values for inorganic systems. We show that (i). the relevant capillary length, the size of a critical quadrangular 2D nucleus L(c), is the main scaling factor for the density of growth steps, while (ii). all steps longer than L(c) grow with a rate determined only by the supersaturation and independent of their length. We explain the divergence of (ii). from theoretical predictions with the high supersaturations typical of the growth of this protein system.
Three techniques have been used to study dislocations in ice: etch pitting-replication, transmission electron microscopy, and X-ray topography (XT). It is shown that, because ice is a weak absorber of X-rays and can be produced with a low dislocation density, allowing relatively thick specimens to be studied, the most useful technique is XT. The observations that have been made with conventional XT are briefly outlined. However, the introduction of high-intensity synchrotron radiation, with its concomitant short exposure times, showed that images obtained through conventional XT observations were of dislocations that had undergone recovery. The important dynamic observations and measurements that have been made using synchrotron X-ray topography are presented. Dynamic synchrotron X-ray topography observations of ice single crystals undergoing deformation in situ have shown that slip mainly occurs by the movement of screw and 60 degrees (1/3) [1120] dislocations on the basal plane, although non-basal slip by edge dislocations can also occur. The operation of Frank-Read and other dislocation multiplication sources have been clearly demonstrated and dislocation velocities have been measured. In contrast, in polycrystals, dislocation generation occurred at grain boundaries where there are stress concentrations before lattice dislocation generation mechanisms operate. Faulted dislocation loops have been determined to be mainly interstitial in both polycrystals and single crystals.
Current theories of snow metamorphism indicate that sublimating snow crystals have rounded shapes, while growing crystals have shapes that depend on growth rates. At slow growth rates, crystals are rounded. At moderate rates, they have flat faces with rounded edges. At fast growth rates, crystals have flat faces with sharp edges, and they have hollow faces at very fast growth rates. The main growth/sublimation mechanism is thought to be by the homogeneous nucleation of new layers at or near crystal edges. It was also suggested that the equilibrium shape of snow crystals would be temperature dependent: rounded above -10.5 degrees C, and faceted below. To test these paradigms, we have performed SEM investigations of snow samples having undergone metamorphism under natural conditions, and of snow samples subjected to isothermal metamorphism at -4 degrees and -15 degrees C in the laboratory. In general, current theories predicting crystal shapes as a function of growth rates, and of whether crystals are growing or sublimating, are verified. However, the transition in equilibrium shapes from rounded to faceted at -10.5 degrees C is not observed in our isothermal experiments that reveal a predominance of rounded shapes after more than a month of metamorphism at -4 and -15 degrees C. Some small crystals with flat faces that also have sharp angles at -15 degrees C, are observed in our isothermal experiments. These faces are newly formed, and contradict current theory. Several hypotheses are proposed to explain their occurrence. One is that they are due to sublimation at emerging dislocations.