Cleavage of crystals

Cleavage of crystals, in particular of calcite CaC03, and the law of rational indices generated the idea of the periodicity of crystal structures and the theory of translational lattices ... 

Mass loss 21% is calc, for cleavage of crystal solvent EtOH plus that of the ligand incomplete decomposition ... 

Fig. 27. Evidence for one-dimcnsional chain growth in layer perovskites Fibrous structure of polymerized compound 99a, obtained upon mechanical cleavage of crystals shown in Fig. 25. Insert Electron diffraction pattern of a polymeric fiber...

Gilman [124] and Westwood and Hitch [135] have applied the cleavage technique to a variety of crystals. The salts studied (with cleavage plane and best surface tension value in parentheses) were LiF (100, 340), MgO (100, 1200), CaFa (111, 450), BaFj (111, 280), CaCOa (001, 230), Si (111, 1240), Zn (0001, 105), Fe (3% Si) (100, about 1360), and NaCl (100, 110). Both authors note that their values are in much better agreement with a very simple estimate of surface energy by Bom and Stem in 1919, which used only Coulomb terms and a hard-sphere repulsion. In more recent work, however, Becher and Freiman [126] have reported distinctly higher values of y, the critical fracture energy. ... 

Inhibitors as well as substrates bind in this crevice between the domains. From the numerous studies of different inhibitors bound to serine pro-teinases we have chosen as an illustration the binding of a small peptide inhibitor, Ac-Pro-Ala-Pro-Tyr-COOH to a bacterial chymotrypsin (Figure 11.9). The enzyme-peptide complex was formed by adding a large excess of the substrate Ac-Pro-Ala-Pro-Tyr-CO-NHz to crystals of the enzyme. The enzyme molecules within the crystals catalyze cleavage of the terminal amide group to produce the products Ac-Pro-Ala-Pro-Tyr-COOH and NHs. The ammonium ions diffuse away, but the peptide product remains bound as an inhibitor to the active site of the enzyme. 

Orthoboric acid, B(OH)3, is the normal end product of hydrolysis of most boron compounds and is usually made ( 160 000 tonnes pa) by acidification of aqueous solutions of borax. Price depends on quality, being 805 per tonne for technical grade and about twice that for refined material (1990). It forms flaky, white, transparent crystals in which a planar array of BO3 units is joined by unsymmetrical H bonds as shown in Fig. 6.25. In contrast to the short O—H O distance of 272 pm within the plane, the distance between consecutive layers in the ciystal is 318 pm, thus accounting for the pronounced basal cleavage of the waxy, plate-like ciystals, and their low density (1.48 g cm ). B(OH)3 is a very weak monobasic acid and acts exclusively by hydroxyl-ion acceptance rather than proton donation ... 

Cleavage of the acetals 9 provides crystalline amino diol hydrochlorides. Remarkably, the (S.S.S)-diastereomer crystallized preferentially leading to a considerable enhancement of d.r. values. 

Reaction of the dimer with Na(acac) leads to cleavage of the bridge giving yellow crystals of Rh(alkene)2(acac) ... 

The various techniques which may be used to provide optimum conditions for the examination of specimens have been described [202—205]. If the sample is opaque, then microscopic investigation is limited to the surface. The depths of penetration for the study of transparent crystals are controlled by the limited depth of field of the optical microscope at high magnifications. This limitation can sometimes be overcome by cleavage of the crystal at an appropriate value of a and examination of the surfaces exposed [120],... 

A crystal structure of the C02 derivative of (8), K[Co(salen)( 71-C02)], haso been reported in which the Co—C bond is 1.99 A, the C—O bonds are both equivalent at 1.22 A and the O-C-O angle is 132°.125 Carboxylation of benzylic and allylic chlorides with C02 in THF-HMPA was achieved with (8) electrogenerated by controlled-potential electrolysis,126 in addition to reductive coupling of methyl pyruvate, diethyl ketomalonate and / -tolylcarbodiimide via C—C bond formation. Methyl pyruvate is transformed into diastereomeric tartrates concomitant with oxidation to the divalent Co(salen) and a free-radical mechanism is proposed involving the homolytic cleavage of the Co—C bond. However, reaction with diphenylketene (DPK) suggests an alternative pathway for the reductive coupling of C02-like compounds. 

The fragment ions at m/z 571,557,526,512,498, and 484 correspond to consecutive cleavages of 45 (COOIF), 59 (CHT OOIF) or 73 (CH2CH2COOH ) from M+ that are directly correlated with the heme structure. Hemin, synthetic (l-hematin (heme crystals), and parasite-derived heme crystals yield... 

Fig. 7.1 Greatly simplified model of the formation of crystal layers by the alternation of growth and cleavage...

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