Topochemical methods

Common approaches for the tailoring of nonmetallic (ceramic) materials properties involve topochemical methods (those where the crystal structure remains largely unaffected) and the preparation of phases in which one or more sublattices are alloyed. In principle, such materials are within the realm of CALPHAD. On the other hand, as has already been stated, extrapolation does not really aid the discovery of new or novel phases, with unique crystal structures. Furthermore, assessed thermochemical data for the vast majority of ceramic systems, particularly transition metal compounds, are presently not available in commercial databases for use with phase diagram software. This does not necessarily preclude the use of the CALPHAD method on these systems However, it does require the user to carry out their own thermodynamic assessments of the (n — 1 )th-order subsystems and to import that data into a database for extrapolation to nth-order systems, which is not a trivial task. 

Micron-scale platelet (Na.KjNbOa particles were synthesized from the platelet precursor KjNbeOiy in a KCl medium using a topochemical method. The salt took part in the reaction and affected the composition of the products. Stoichiometric (Nao.sKo.slNbOs could be accurately synthesized by controlling the amount of the reactant Na2C03- X-ray diffraction analysis revealed that the crystallographic (010) plane of... 

Another topochemical method for preparation of hydrated oxides consists of an extension of the procedure proposed by Raney in the case of metals. The required starting mixtures may be obtained by fusion of the components or by coprecipitation. A commercial fusion procedure yields Vycor glasses with interesting adsorptive and catalytic properties [4, 5, 9]. The fusion procedure is also used to obtain sodium ferrite-aluminate mixed crystals these then yield hydrated iron (III) oxide skeletal structures showing considerable chemical activity (reacting with hot aqueous NaOH) provided the starting mixture contains an excess of aluminate [7]. The activity of such structures is due both to the small particle size of the product and to a strongly distorted crystal lattice due to frozen thermal vibrations [8]. 

The analysis of the regioselective reactivity of olefins in identical topochemical environments by three computational methods concludes that both steric factors (cavity and potential energy) and electronic factors (perturbation energy from orbital interactions) play important cooperative roles in determining which C—C double bond in a molecule reacts first in [2-1-2] photodimerization. The steric factor is considered to be effective in the movement of olefins at an early stage of the reaction, whereas the electronic factors are effective in the adduction of olefins at a later stage of the reaction. 

It is well known that the structure, distribution and properties of protolignin in cell walls vary according to cell type and morphological location. This is based upon extensive studies on topochemical properties of lignin using various methods such as ultraviolet microscopic photometry (1,2), bromination-SEM-EDXA (3) and other physical or chemical analyses of isolated tissue fractions (4). 

Particle-Particle Interactions. Loss of strong acid content of aerosol particles can also occur because of reactions between co-collected acidic and basic particles impacted together on the collection surface. This phenomenon most frequently occurs as the result of interaction of coarse (>2.5 xm diameter), alkaline, soil-derived particles with fine (<2.5 xm diameter) acidic sulfate particles (66). Particle-particle interactions with net neutralization can be reduced in many cases by sampling with a virtual impactor or a cyclone to remove coarse particles, although this procedure does not prevent the effect if external mixtures of fine particles of different acid contents are sampled. In situ methods with shorter sampling times can be used such that these topochemical reactions are less likely to occur. 

The subsequent paragraphs will focus on the preparation of C2-substituted malonyl derivatives for the incorporation into PMRI-peptides. In the classical method, C2 alkylation of a malonic acid diester is followed by partial hydrolysis to generate the C2-alkylated monoalkyl malonate (Scheme 7). The malonyl-derived topochemical replacements for Phe, Lys, Trp, Leu, Ala, His, and Met residues have been successfully prepared by this strat-egyJ48 57 ... 

Prior to the development of tether-directed functionalization methods, Krautler and co-workers developed a very elegant topochemically controlled, solid-state group-transfer synthesis [12,13] to obtain the trans-1 bisanthracene adduct 9 (Figure 2). 

Two types of transformations can be very broadly distinguished. The first is the formation of a solid solution, in which solute atoms are inserted into vacancies (lattice sites or interstitial sites) or substitute for a solvent atom on a particular sublattice. Many types of synthetic processes can result in this type of transformation, including ion-exchange reactions, intercalation reactions, alloy solidification processes, and the high-temperature ceramic method. Of these, ion exchange, intercalation, and other so-called soft chemical (chimie douce) reactions produce no stmctural changes except, perhaps, an expansion or contraction of the lattice to accommodate the new species. They are said to be under topotactic, or topochemical, control. 

In custom-designing materials with tailored properties, it is often necessary to s)m-thesize metastable phases that will be kinetically stable under the temperature and conditions of use. These phases are obtainable only through kinetic (chemical) control. In many cases, kinetic control has been achieved via the soft chemical low-temperature (e.g. electrochemical synthesis, sol-gel method) and/or topochemical routes (e.g. intercalation, ion exchange, dehydration reactions), since these routes use nuld synthetic conditions. It should be noted that not all soft chemical routes are topochemical. A reaction is said to be under topochemical control only if it follows the pathway of minimum atomic or molecular movement (Elizabe et al., 1997). Accordingly, topochemical reactions are those in which the lattice of the solid product shows one or a small number of... 

Some important aspects of topochemical polymerizations can be understood by inspection of Eq. (1), All reactivity comes about by very specific rotations of the monomers and by 1,4-addition of adjacent units and an extended, fully conjugated polymer chain is formed. The unique feature of the topochemical polymerization of diacetylenes is the fact that in many cases the reaction can be carried out as a single phase process. This leads to macroscopic, defect-free polymer single crystals which cannot be obtained, in principle, by crystallization of ready-made polymers by conventional methods. Thus, polydiacetylenes are ideal models for the investigation of the behaviour of macromolecules in their perfect three dimensional crystal lattice. 

The molecular assemblies described above have inspired us, in recent years, to develop finite assemblies in the solid state that exhibit chemical reactivity. Specifically, we,69 and others,70 have been utilizing principles of molecular recognition and self-assembly to develop a method to direct the formation of covalent bonds in organic solids. The method builds on the work of Schmidt on the reactivity of cinnamic acids in the organic solid state.45 Specifically, Schmidt has described topochemical postulates that dictate geometry criteria for a [2 + 2] photodimerization to occur in a solid. The postulates state that two carbon-carbon double (C=C) bonds should be aligned in parallel and separated by a distance <4.2 A to react. 

There are several alternative methods for the synthesis of optically active polymers from achiral or racemic monomers that do not involve polymerization catalysts. Optically active polymers have been formed from achiral dienes immobilized in a chiral host lattices [ 106]. In these reactions, the chiral matrix serves as a catalyst and can be recovered following the reaction. For example, 1,3-penta-dienes have been polymerized in perhydrotriphenylene and apochoUc acid hosts, where asymmetric induction occurs via through-space interactions between the chiral host and the monomer [107,108]. The resultant polymers are optically active, and the optical purities of the ozonolysis products are as high as 36%. In addition, achiral monomers have been found to pack in chiral crystals with the orientations necessary for topochemical soHd-state polymerization [109]. In these reactions, the scientist is the enantioselective catalyst who separates the enantiomeric crystals. The oligomers, formed by a [27H-27i] asymmetric photopolymerization, can be obtained in the enantiomeric pure form [110]. 

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