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Unambiguous Determination (unambiguous + determination)
Selected AbstractsUnambiguous determination of H-atom positions: comparing results from neutron and high-resolution X-ray crystallographyACTA CRYSTALLOGRAPHICA SECTION D, Issue 5 2010Anna S. Gardberg The locations of H atoms in biological structures can be difficult to determine using X-ray diffraction methods. Neutron diffraction offers a relatively greater scattering magnitude from H and D atoms. Here, 1.65,Å resolution neutron diffraction studies of fully perdeuterated and selectively CH3 -protonated perdeuterated crystals of Pyrococcus furiosus rubredoxin (D-rubredoxin and HD-rubredoxin, respectively) at room temperature (RT) are described, as well as 1.1,Å resolution X-ray diffraction studies of the same protein at both RT and 100,K. The two techniques are quantitatively compared in terms of their power to directly provide atomic positions for D atoms and analyze the role played by atomic thermal motion by computing the , level at the D-atom coordinate in simulated-annealing composite D-OMIT maps. It is shown that 1.65,Å resolution RT neutron data for perdeuterated rubredoxin are ,8 times more likely overall to provide high-confidence positions for D atoms than 1.1,Å resolution X-ray data at 100,K or RT. At or above the 1.0, level, the joint X-ray/neutron (XN) structures define 342/378 (90%) and 291/365 (80%) of the D-atom positions for D-rubredoxin and HD-rubredoxin, respectively. The X-ray-only 1.1,Å resolution 100,K structures determine only 19/388 (5%) and 8/388 (2%) of the D-atom positions above the 1.0, level for D-rubredoxin and HD-rubredoxin, respectively. Furthermore, the improved model obtained from joint XN refinement yielded improved electron-density maps, permitting the location of more D atoms than electron-density maps from models refined against X-ray data only. [source] Synthesis, Characterization, and Reaction of Crystalline Fischer's Glucopyranosyl IsocyanateEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2004Yoshiyasu Ichikawa Abstract We have established a simple method for the preparation of crystalline Fischer's glucopyranosyl isocyanate 1. NMR spectroscopic analysis of 1 allowed the unambiguous determination of the stereochemistry at the anomeric position. Synthetic applications of glucopyranosyl isocyanate 1 were examined by its reactions with amines and alcohols to furnish a wide variety of neoglycoconjugates. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] New approach to twin interfaces of modulated martensiteJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 3 2010Zongbin Li In Ni,Mn,Ga ferromagnetic shape memory alloys, the crystallographic nature of martensitic variant interfaces is one of the key factors governing the variant reorientation through field-induced interface motion and hence the shape memory performance. So far, the crystal structure studies of these materials , conducted by means of transmission electron microscopy , have suffered from uncertainties in determining the number of unit cells of modulated superstructure, and consequently improper interpretations of orientation correlations of martensitic variants. In this paper a new approach is presented for comprehensive analysis of crystallographic and morphological information of modulated martensite, using automated electron backscatter diffraction. As a first attempt, it has been applied for the unambiguous determination of the orientation relationships of adjacent martensitic variants and their twin interface characters in an incommensurate 7M modulated Ni,Mn,Ga alloy, from which a clear and full-featured image of the crystallographic nature of constituent twin interfaces is built up. Certainly, this new approach will make it feasible not only to generalize the statistical analysis of martensitic variant distributions for various materials with modulated superstructure, but also to give insight into the crystallographic characteristics of martensitic variant interfaces and the variant reorientation mechanism of new advanced materials for interface engineering. [source] Determination of the molecular weight of proteins in solution from a single small-angle X-ray scattering measurement on a relative scaleJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 1 2010H. Fischer This paper describes a new and simple method to determine the molecular weight of proteins in dilute solution, with an error smaller than ,10%, by using the experimental data of a single small-angle X-ray scattering (SAXS) curve measured on a relative scale. This procedure does not require the measurement of SAXS intensity on an absolute scale and does not involve a comparison with another SAXS curve determined from a known standard protein. The proposed procedure can be applied to monodisperse systems of proteins in dilute solution, either in monomeric or multimeric state, and it has been successfully tested on SAXS data experimentally determined for proteins with known molecular weights. It is shown here that the molecular weights determined by this procedure deviate from the known values by less than 10% in each case and the average error for the test set of 21 proteins was 5.3%. Importantly, this method allows for an unambiguous determination of the multimeric state of proteins with known molecular weights. [source] Determination of cholesterol oxides content in milk products by solid phase extraction and gas chromatography-mass spectrometryJOURNAL OF SEPARATION SCIENCE, JSS, Issue 9-10 2003María V. Calvo Abstract A method for quick and reliable analysis of cholesterol oxidation products (COPs) in dairy products has been developed. After lipid extraction, fat was transesterified under mild conditions to avoid degradation of the target compounds. Isolation of the COPs studied from other components in the lipid fraction was carried out on an aminopropyl SPE cartridge. Finally, analytes were analysed by GC-MS without derivatisation. The method developed provides high specificity and good sensitivity, allowing the direct and unambiguous determination of the underivatized COPs investigated. Application of the method to dairy food analysis revealed the presence of COPs in powder milks and milk-based infant formulas commercially available in Spain, showing that attention should be focused on reduction of cholesterol oxidation levels during both the processing and the storage of these types of foodstuffs. [source] Absolute configurations of chiral herbicides determined from vibrational circular dichroismCHIRALITY, Issue S1 2005Jiangtao He Abstract Enantiopure herbicides (+)-2-(4-chloro-2-methylphenoxy) propanoic acid, (+)- 1 and (+)-2-(2,4-dichlorophenoxy) propanoic acid, (+)- 2 were investigated using vibrational circular dichroism (VCD). Experimental absorption and VCD spectra of (+)- 1 and (+)- 2 in CDCl3 solution in the 2000,900 cm,1 region were compared with the ab initio predictions of absorption and VCD spectra obtained with density functional theory using the B3LYP/6-31G* basis set for different conformers of (R)- 1 and (R)- 2. Due to the intermolecular hydrogen bonding, this comparison did not provide unambiguous conclusions. To eliminate intermolecular hydrogen bonding influence, the two acids 1 and 2 were converted to the corresponding methyl esters, namely, (+)-methyl 2-(4-chloro-2-methylphenoxy) propanoate, (+)- 3 and (+)-methyl 2-(2,4-dichlorophenoxy) propanoate, (+)- 4. The experimental VCD spectra were measured for these esters and ab initio calculations for different conformers of (R)- 3 and (R)- 4 were carried out. The experimental VCD spectra and corresponding population-weighted theoretical VCD spectra were found to be in excellent agreement, which allowed unambiguous determination of absolute configuration of 3 and 4 as (+)-(R). Since esterification does not invert the configuration, the absolute configuration of the parent acids 1 and 2 is the same as that of corresponding methyl esters. Chirality 17:S1,S8, 2005. © 2004 Wiley-Liss, Inc. [source] | ||||||||||||||||||||||