Structural characterization crystallography

Although great progress has been made in study of the mode of action of the azinomycins, a full understanding of their interaction with DNA will require future structural characterization of azinomycin-DNA crosslinks by NMR or X-ray crystallography. 

The increasing tendency of silanols to condense as the number of OH groups on a particular silicon increases means that relatively few silanetriols have been isolated and even fewer structurally characterized. A wide range of substituted arylsilanetriols have been prepared (102), but none have been studied by x-ray crystallography. The first silanetriol to be structurally characterized was c-C6HuSi(OH)3, which has a sheet structure comprising double layers of molecules joined in a... 

Reaction of [cp IrCl2]2 with 2,6-dimethoxyphenyl(diphenylphosphine), mdmpp, gives (222), and with tris(2,6-dimethoxyphenyl)phosphine, tdmpp, gives (223).394 Addition of tcne to a CH2C12 solution of (222) yields the structurally characterized complex (224), in which tcne has inserted into a C—11 aromatic bond.395 The complex (223) reacts with one molar equivalent of tcne to give (225), and with two molar equivalents to give (226) both have been analyzed by X-ray crystallography.396... 

Methyl pyruvate thiosemicarbazone in the presence of zinc chloride or acetate resulted in the formation of complexes with the ligand hydrolyzed or transesterified. The complexes with pyruvate thiosemicarbazone, ZnL2, or ethyl pyruvate thiosemicarbazone, ZnLCl2 were structurally characterized by single-crystal X-ray crystallography showing respectively a distorted octahedral and distorted square pyramidal geometry.874... 

To obtain statistically significant comparisons of ordered and disordered sequences, much larger datasets were needed. To this end, disordered regions of proteins or wholly disordered proteins were identified by literature searches to find examples with structural characterizations that employed one or more of the following methods (1) X-ray crystallography, where absence of coordinates indicates a region of disorder (2) nuclear magnetic resonance (NMR), where several different features of the NMR spectra have been used to identify disorder and (3) circular dichroism (CD) spectroscopy, where whole-protein disorder is identified by a random coil-type CD spectrum. 

Terminal methylene complexes are relatively rare—less than 10 such compounds have been isolated and about as many again have been characterized by spectroscopic techniques only. The methylene complexes previously reported fall into two groups, (i) neutral complexes of the early transition metals (e.g., Ti, Ta) and (ii) cationic complexes of the later transition metals (e.g., Re, Fe). The osmium complex 47 is important, then, as it is a new example extending the neutral group to the later transition metals. Compound 47 is the prototype for the series Os(=CHR)Cl(NO)(PPh3)2 and is one of only three terminal methylene complexes to be structurally characterized by X-ray crystallography (see Section IV,B). 

Adducts that have been characterized by single X-ray crystallography include the dimethylzinc complexes with triazine, [Me2Zn (CH2NMe)3 2],23,2 and TMEDA, [Me2Zn Me2N(CH)2 NMe2 ].23 Other amine adducts that have been structurally characterized, but not used in... 

The flow of information on the highly reactive alkali organometallics in the 1990s is certainly closely connected to the wider availability of low temperature crystallography and advanced crystal mounting techniques,22 allowing the structural characterization of compounds previously deemed too reactive for investigation. 

From structural characterization of 48 by X-ray crystallography [31], it is suggested that formation of stable Ru 11,111- cluster derivative 47 or 48 is involved in substitution of the axially coordinated methanol as well as one of the six bridging acetates in the Ru ni ni precursor 2 by an abpy or abcp, in which formal oxidation state of the triruthenium species is converted from 111,111,111 to III,III,II. 

Tolman (144, 202) and Wieghardt (203, 204) and their co-workers used amine macrocycles with a 1,4,7-triazacyclononane backbone and one, two, or three phenol pendent arms (Table VIII). In all cases, square-base pyramidal (phenolate)copper(II) precursor complexes were isolated and in many instances structurally characterized by X-ray crystallography. Depending on the number of coordinated phenolates, these complexes are reversibly one-electron oxidized yielding the (phenoxyl)copper(II) species that were characterized in solution by UV-vis, EPR, and RR spectroscopy. 

The biogenic amines are the preferred substrates of MAO. The enzyme comes in two flavors, MAO-A and MAO-B, both of which, like FMO, rely on the redox properties of FAD for their oxidative machinery. The two isoforms share a sequence homology of approximately 70% (81) and are found in the outer mitochondrial membrane, but they differ in substrate selectivity and tissue distribution. In mammalian tissues MAO-A is located primarily in the placenta, gut, and liver, while MAO-B is predominant in the brain, liver, and platelets. MAO-A is selective for serotonin and norepinephrine and is selectively inhibited by the mechanism-based inhibitor clorgyline (82). MAO-B is selective for /1-phcncthylaminc and tryptamine, and it is selectively inhibited by the mechanism-based inhibitors, deprenyl and pargyline (82) (Fig. 4.32). Recently, both MAO-A (83) and MAO-B (84) were structurally characterized by x-ray crystallography. 

Two carborane cations, zV/ -2,3,4,5,6-McsC5BBr+ and the tentatively proposed arachno-N ci WX I71, were reported. The identity and pyramidal structure of the pentacarbaborane cation was determined by X-ray crystallography.112 The small arachno-carborane was detected on the basis of ab initio computations and 11B NMR data in the mixture from reaction of the 2-propyl cation with diborane.113 Two neutral adducts based on the pentacarbaborane cation, ///V/9-2,3,4,5,6-McsCsBBKCI2 (R = Cl or SiClj), were made from MesCsSiMe3 or (MesCs Si with B2CI4, respectively.114 The BCI3 adduct was structurally characterized by X-ray crystallography. 

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