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61.
Gervais C Dupree R Pike KJ Bonhomme C Profeta M Pickard CJ Mauri F 《The journal of physical chemistry. A》2005,109(31):6960-6969
13C, 14N, 15N, 17O, and 35Cl NMR parameters, including chemical shift tensors and quadrupolar tensors for 14N, 17O, and 35Cl, are calculated for the crystalline forms of various amino acids under periodic boundary conditions and complemented by experiment where necessary. The 13C shift tensors and 14N electric field gradient (EFG) tensors are in excellent agreement with experiment. Similarly, static 17O NMR spectra could be precisely simulated using the calculation of the full chemical shift (CS) tensors and their relative orientation with the EFG tensors. This study allows correlations to be found between hydrogen bonding in the crystal structures and the 17O NMR shielding parameters and the 35Cl quadrupolar parameters, respectively. Calculations using the two experimental structures for L-alanine have shown that, while the calculated isotropic chemical shift values of 13C and 15N are relatively insensitive to small differences in the experimental structure, the 17O shift is markedly affected. 相似文献
62.
Narayani Ramakrishnan Nancy L. Oleinick Marian E. Clay Min-Fen Horng Antonio R. Antunez Helen H. Evans 《Photochemistry and photobiology》1989,50(3):373-378
Two closely related strains of mouse lymphoma L5178Y cells, LY-R and LY-S, have been found to differ in their sensitivity to the cytotoxic effects of photodynamic treatment (PDT) with chloroaluminum phthalocyanine (CAPC) and red light. Strain LY-R is more sensitive to photodynamic cell killing than strain LY-S. Differences in uptake of CAPC could not account for the differences in cytotoxic effects. There was no marked difference between the two strains in the induction of single-strand breaks (which includes frank single-strand breaks and alkali-labile lesions), but substantially more DNA-protein cross-links were formed in strain LY-R by CAPC and light. Repair of single-strand breaks proceeded with similar kinetics in both strains for the first 30 min post-irradiation, suggesting that these lesions are not responsible for the differential sensitivity of the two strains to the lethal effects of photodynamic treatment. Thereafter, alkaline elution revealed the presence of increasing DNA strand breakage in strain LY-R. DNA degradation, as measured by the conversion of prelabeled [14C] DNA to acid-soluble radioactivity, was more rapid and extensive in strain LY-R. 相似文献
63.
Storr T Obata M Fisher CL Bayly SR Green DE Brudziñska I Mikata Y Patrick BO Adam MJ Yano S Orvig C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):195-203
Seven discrete sugar-pendant diamines were complexed to the {M(CO)(3)}(+) ((99m)Tc/Re) core: 1,3-diamino-2-propyl beta-D-glucopyranoside (L(1)), 1,3-diamino-2-propyl beta-D-xylopyranoside (L(2)), 1,3-diamino-2-propyl alpha-D-mannopyranoside (L(3)), 1,3-diamino-2-propyl alpha-D-galactopyranoside (L(4)), 1,3-diamino-2-propyl beta-D-galactopyranoside (L(5)), 1,3-diamino-2-propyl beta-(alpha-D-glucopyranosyl-(1,4)-D-glucopyranoside) (L(6)), and bis(aminomethyl)bis[(beta-D-glucopyranosyloxy)methyl]methane (L(7)). The Re complexes [Re(L(1)-L(7))(Br)(CO)(3)] were characterized by (1)H and (13)C 1D/2D NMR spectroscopy which confirmed the pendant nature of the carbohydrate moieties in solution. Additional characterization was provided by IR spectroscopy, elemental analysis, and mass spectrometry. Two analogues, [Re(L(2))(CO)(3)Br] and [Re(L(3))(CO)(3)Br], were characterized in the solid state by X-ray crystallography and represent the first reported structures of Re organometallic carbohydrate compounds. Conductivity measurements in H(2)O established that the complexes exist as [Re(L(1)-L(7))(H(2)O)(CO)(3)]Br in aqueous conditions. Radiolabelling of L(1)-L(7) with [(99m)Tc(H(2)O)(3)(CO)(3)](+) afforded in high yield compounds of identical character to the Re analogues. The radiolabelled compounds were determined to exhibit high in vitro stability towards ligand exchange in the presence of an excess of either cysteine or histidine over a 24 h period. 相似文献
64.
Chris McDonald 《Analytica chimica acta》2005,534(1):3-10
Studies of protein-protein and protein-ligand interactions are important for understanding biological functions of proteins. A new technique based on the partial proteolysis of proteins combined with quantitative mass spectrometry is developed as a means of tracking structural changes after the formation of a protein-ligand complex. In this technique, a protein of interest with and without the binding of a ligand is digested with an enzyme to generate a set of peptides, followed by separation of the peptides by liquid chromatography. Matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) is used to identify chromatographically separated peptides, and locate their sequence alignments in the parent protein. Using an isotopically labeled protein as a sample against an unlabeled protein standard, quantitative information can be gathered. This overcomes the inherent lack of quantitative capability of MALDI MS. The utility of the technique to investigate protein-ligand interactions is demonstrated in a model system involving calcium binding to cardiac Troponin C (cTnC). Using this technique, the general location of the three calcium-binding sites of cTnC can be determined by using several different enzymes to generate overlapping peptide maps of cTnC. 相似文献
65.
66.
Varrot A Tarling CA Macdonald JM Stick RV Zechel DL Withers SG Davies GJ 《Journal of the American Chemical Society》2003,125(25):7496-7497
Glycosidases are some of the most ubiquitous enzyme in nature. Their biological significance, coupled to their enormous catalytic prowess derived from tight binding of the transition state, is reflected in their importance as therapeutic targets. Many glycosidase inhibitors are known. Imino sugars are often potent inhibitors, yet many facets of their mode of action, such as their degree, if any, of transition-state "mimicry" and their protonation state when bound to the target glycosidase remain unclear. Atomic resolution analysis of the endoglucanase, Cel5A, in complex with a cellobio-derived isofagomine in conjunction with the pH dependence of Ki and kcat/KM reveals that this compound binds as a protonated sugar. Surprisingly, both the enzymatic nucleophile and the acid/base are unprotonated in the complex. 相似文献
67.
68.
Asymmetric hydrogenation of ketone 1 using trans-RuCl(2)[(R)-xylbinap][(R)-daipen] (3) as a catalyst afforded secondary alcohol 2 quantitatively and in 99.4% ee. Further exploration of the effect of the thiazole ring substitution revealed that the catalyst was highly effective for the enantioselective hydrogenation of 5-benzoyl thiazoles, which afforded corresponding alcohols in 92-99% ee. The same protocol was applicable to a variety of aromatic-heteroaromatic ketones to generate secondary alcohols in excellent enantioselectivities. [reaction: see text] 相似文献
69.
In this paper we present an automated system for simultaneous measurement of CO(2) concentration, delta(13)C and delta(18)O from small (<1 mL) air samples in a short period of time (approximately 1 hour). This system combines continuous-flow isotope ratio mass spectrometry (CF-IRMS) and gas chromatography (GC) with an inlet system similar to conventional dual-inlet methods permitting several measurement cycles of standard and sample air. Analogous to the dual-inlet method, the precision of this system increases with the number of replicate cycles measured. The standard error of the mean for a measurement with this system is 0.7 ppm for the CO(2) concentration and 0.05 per thousand for the delta(13)C and delta(18)O with four replicate cycles and 0.4 ppm and 0.03 per thousand respectively with nine replicate cycles. The mean offset of our measurements from NOAA/CMDL analyzed air samples was 0.08 ppm for the CO(2) concentration, 0.01 per thousand for delta(13)C and 0.00 per thousand for delta(18)O. A specific list of the parts and operation of the system is detailed as well as some of the applications for micrometeorological and ecophysiological applications. 相似文献
70.
Rapid deposition of triangular silver nanoplates on planar surfaces: application to metal-enhanced fluorescence 总被引:6,自引:0,他引:6
A simple and rapid wet-chemical technique for the deposition of silver triangles on conventional glass substrates, which alleviates the need for lithography, has been developed. The technique is based on the seed-mediated cetyltrimethylammonium-bromide-directed growth of silver triangles on glass surfaces, where smaller spherical silver seeds that were attached to the surface were subsequently converted and grown into silver triangles in the presence of a cationic surfactant and silver ions. The size of the silver triangles was controlled by sequential immersion of silver seed-coated glass substrates into a growth solution and by the duration time of immersion. Atomic force microscopy studies revealed that the size of the silver triangles ranged between 100 and 500 nm. Interestingly, these new surfaces are a significant improvement over traditional silver island films for applications in metal-enhanced fluorescence. A routine 16-fold enhancement in emission intensity was typically observed, for protein-immobilized indocyanine green, with a relatively very low loading density of silver triangles on the glass surface. 相似文献