Crystallization, basic principles

Buque-Taboada, E.M., Straathof, A.J.J., and Heijnen, J.J., and van der Wielen, LA.M. (2006) In-situ product recovery (ISPR) by crystallization basic principles, design, and potential applications in whole-cell biocatalysis. Appl. Micmb. Biotechnol., 71, 1-12. 

In this chapter we describe the basic principles involved in the controlled production and modification of two-dimensional protein crystals. These are synthesized in nature as the outermost cell surface layer (S-layer) of prokaryotic organisms and have been successfully applied as basic building blocks in a biomolecular construction kit. Most importantly, the constituent subunits of the S-layer lattices have the capability to recrystallize into iso-porous closed monolayers in suspension, at liquid-surface interfaces, on lipid films, on liposomes, and on solid supports (e.g., silicon wafers, metals, and polymers). The self-assembled monomolecular lattices have been utilized for the immobilization of functional biomolecules in an ordered fashion and for their controlled confinement in defined areas of nanometer dimension. Thus, S-layers fulfill key requirements for the development of new supramolecular materials and enable the design of a broad spectrum of nanoscale devices, as required in molecular nanotechnology, nanobiotechnology, and biomimetics [1-3]. 

We have described for a number of molecular single crystals the basic principles and techniques which were involved in the optimization of their nonlinear efficiency and crystalline quality. Certainly, other types of molecules or material processing techniques can be used. In particular, it could be worthwile to try and by-pass the difficulty of growing large single crystals for applications which are less demanding in terms of optical quality parametric oscillation. 

CXRS entered the commercial market in the mid-to-late 1990s after a long development period. The basic principles have been known for many years, but practical development faced many hurdles. Most explosives have a crystalline structure. Because the crystals are small and randomly orientated, the structure is sometimes referred to as poly crystalline. These crystals exhibit a strong coherent scatter at certain angles that depend on the X-ray energy and the crystal lattice spacing. This coherent scatter (also called diffraction) is a property of the crystal lattice and is unrelated to... 

If we place n- and p-type semiconducting crystals in contact (a p-n junction), we create a device that conducts electricity preferentially in one direction this is the basis of action of the semiconductor diodes used in the electronics industry, although specially refined silicon (Section 17.8.2) is usually employed rather than Ge. Transistors and electronic chips are designed using similar basic principles—typically with n-p-n or p-n-p junctions. We consider chemical aspects of electronic devices in more detail in Chapter 19. 

This book outlines the basic principles needed to understand the mechanism of explosions by chemical explosives. The history, theory and chemical types of explosives are introduced, providing the reader with information on the physical parameters of primary and secondary explosives. Thermodynamics, enthalpy, free energy and gas equations are covered together with examples of calculations, leading to the power and temperature of explosions. A very brief introduction to propellants and pyrotechnics is given, more information on these types of explosives should be found from other sources. This second edition introduces the subject of Insensitive Munitions (IM) and the concept of explosive waste recovery. Developments in explosive crystals and formulations have also been updated. This book is aimed primarily at A level students and new graduates who have not previously studied explosive materials, but it should prove useful to others as well. I hope that the more experienced chemist in the explosives industry looking for concise information on the subject will also find this book useful. 

Before discussing the energetics of lattice formation, it will be instructive to examine some of the most common arrangements of ions in crystals. Although only a few of the many possible arrangements are discussed, they indicate some of the possibilities available for the formation of lattices. We shall return to the subject of structure after some basic principles have been developed. 

The crystal is a supermolecule which Nature offers to us [16], Our problem is to synthesize crystals, and to achieve this, we have to know the grammar of crystal packing (i.e., the rules by which the molecules are put together in periodic arrays). It is recognized that hierarchization is one of the basic principles of constructing anything. In crystal syntheses, the hierarchization involves building a complex assembly out of a simpler atoms— molecules— supramolecular assembly. To achieve this, we need to know all about the noncovalent intermolecular in-... 

Aconitase was the first protein to be identified as containing a catalytic iron-sulfur cluster [24-26]. It was also readily established that the redox properties of the [4Fe-4S](2+ 1+) cluster do not play a role of significance in biological functioning the 1 + oxidation state has some 30% of the activity of the 2+ state [25], Since then several other enzymes have been identified or proposed to be nonredox iron-sulfur catalysts. They are listed in Table 2. It appears that all are involved in stereospecific hydration reactions. However, these proteins are considerably less well characterized than aconitase. In particular, no crystal structural information is available yet. Therefore, later we summarize structural and mechanistic information on aconitase, noting that many of the basic principles are expected to be relevant to the other enzymes of Table 2. 

It is hoped that the illustrative examples presented here will serve to crystallize the basic principles and will motivate the readers to apply exergy efficiency analysis and exergy accounting — taking advantage of these methods for their own practical purposes, while also advancing the state of the art. 

Order and Mobility are two basic principles of mother nature. The two extremes are realized in the perfect order of crystals with their lack of mobility and in the high mobility of liquids and their lack of order. Both properties are combined in liquid crystalline phases based on the selforganization of formanisotropic molecules. Their importance became more and more visible during the last years in Material science they are a basis of new materials, in Life science they are important for many structure associated functions of biological systems. The main contribution of Polymer science to thermotropic and lyotropic liquid crystals as well as to biomembrane models consists in the fact that macromolecules can stabilize organized systems and at the same time retain mobility. The synthesis, structure, properties and phototunctionalization of polymeric amphiphiles in monolayers and multilayers will be discussed. 

Chemical symmetry has been noted and investigated for centuries in crystallography which is at the border between chemistry and physics. It was more physics when crystal morphology and other properties of the crystal were described. It was more chemistry when the inner structure of the crystal and the interactions between its building units were considered. Later, descriptions of molecular vibrations and the establishment of selection rules and other basic principles happened in all kinds of spectroscopy. This led to another uniquely important place for the symmetry concept in chemistry with practical implications. 

Although the basic principle and procedure of diastereomeric resolution are not difficult to understand, the chiral discrimination mechanism involved in the selective crystallization of one diastereomer from the mixture is very complicated. The chiral discrimination mechanism for diastereomeric resolution changes in accord with the resolving system, since not only the properties of diastereomeric crystals but also the conditions for crystallization strongly influence the chiral discrimination mechanism. In particular, the polymorphism of crystal, the severe solvent effect on solubility, and the kinetic factor for crystal growth are still not perfectly understood regarding this chiral discrimination phenomenon. The study is therefore limited in its investigation of the chiral discrimination mechanism for the diastereomeric resolution, as the mechanism involves both the crystal and solution properties of diastereomers.7... 

In order to understand the basic principles of operation of the many different kinds of LCDs being developed and/or manufactured at the present time, it is necessary to briefly describe the liquid crystalline state and then define the physical properties of direct relevance to LCDs. First, the nematic, smectic and columnar liquid crystalline states will be described briefly. However, the rest of the monograph dealing with liquid crystals will concentrate on nematic liquid crystals and their physical properties, since the vast majority of LCDs manufactured operate using mixtures of thermotropic, non-amphiphilic rodlike organic compounds in the nematic state. 

---