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901.
Haines TJ Bionta RM Blewitt G Bratton CB Casper D Claus R Cortez BG Errede S Foster GW Gajewski W Ganezer KS Goldhaber M Jones TW Kielczewska D Kropp WR Learned JG Lehmann E LoSecco JM Matthews J Park HS Price LR Reines F Schultz J Seidel S Shumard E Sinclair D Sobel HW Stone JL Sulak L Svoboda R van der Velde JC Wuest C 《Physical review letters》1986,57(16):1986-1989
902.
Salicylidene-o-aminophenol provides a sensitive spectrofluorimetric reagent for the determination of aluminium down to 27 ng (or 2.7 x 10(-4) ppm in the final solution). The most suitable conditions of pH (5.6), reagent concentration and development time (>20 min) have been established. Extraction with sodium diethyldithiocarbamate into ethyl acetate at the pH of the determination renders the method highly selective; out of 46 foreign cations examined only chromium(III), scandium and thorium interfere. Anions which form complexes with aluminium, such as citrate, tartrate and fluoride, also cause interference, but none of the common anions interferes. A 1:1 stoichiometry of the complex has been established and some conclusions have been drawn concerning its nature. 相似文献
903.
The translational and orientation order of arg-cysteamine molecules chemiabsorbed on the Au(111) crystal surface is considered. Couplings between carbon, nitrogen, and hydrogen atoms of the n-alkanethiols are approximated by the Lennard-Jones potential. Moreover, hydrogen bonds between oxygen and nitrogen and dipole-dipole interactions of the dipole moments of different atomic groups are taken into account. It is found that molecules are arranged in a 2 x 2 lattice and have the total symmetry C6 x Z2. The critical temperature of the phase transition to the tilted state Tc1, which breaks the symmetry C6, is estimated to be extremely high. The spontaneous breakdown of the remaining symmetry Z2 leads to the twisted state of the molecules and has the critical temperature Tc2=340 K. 相似文献
904.
Mack ET Carle AB Liang JT Coyle W Wilson RM 《Journal of the American Chemical Society》2004,126(47):15324-15325
Pyrene dihydrodioxins (1 and 2) have been synthesized and shown to be effective photochemical blocking groups for pyrene-4,5-dione (3). The mechanism of quinone release proceeds through the formation of a remarkably stable radical cation. Direct evidence is provided that this radical cation is not only thermally labile but also photochemically labile, and that both pathways lead to quinone extrusion. Once initiated with UV light, the pyrene quinone product serves as an electron-transfer photosensitizer for the further release of quinone with visible light. 相似文献
905.
A simple and rapid titrimetric method is described for the microdetermination of Ag(+), Cd(2+) and Pb(2+), based on their formation of mercaptides with a measured excess of 2-mercaptopropanoic acid, and similar determination of Hg(2+) with thioglycollic acid. Univalent and bivalent metal ions release one and two thiol protons respectively, which along with the carboxyl protons of the thiol reagent are titrated with standard alkali. The difference from the blank titration gives the increase in acidity which is a function of the metal-ion concentration. The proposed procedure is applicable to samples containing 0.025-0.25 mmole of these ions, the average deviation being in the range 0.2-0.5%. 相似文献
906.
The equilibrium dynamics of the acetyl and amino amide-I groups of the alanine dipeptide were examined separately using (13)C isotopic selection and 2D IR. The population relaxation times of the amide transitions were measured to be in the range 500 fs by means of heterodyne transient grating methods. The vibrational frequency correlation functions consisted in all cases of a motionally narrowed part, a component near 800 fs, and a constant part representing a distribution of structures that is static on the few ps time scale. The intermediate time scale is attributed to fluctuations in the stretching and bending of hydrogen bonds between the carbonyl and water. 相似文献
907.
The synthesis of taxa-4(20),11(12)-diene-2alpha,5alpha-diol is described. An improved procedure for the intramolecular Diels-Alder cycloaddition previously reported in our synthesis of taxa-4(5), 11(12)-diene has been utilized to prepare a taxoid with oxygenation in the B and C rings. It has been established previously that taxa-4(20),11(12)-dien-5alpha-ol is the first oxygenated intermediate on the biosynthetic pathway to Taxol. Taxa-4(20), 11(12)-diene-2alpha,5alpha-diol (5), which has been observed in a biosynthetic conversion, is a potential candidate as the second oxygenated intermediate on the Taxol biosynthetic pathway, has been prepared to probe the intermediacy of this substance. 相似文献
908.
Wang W Rusin O Xu X Kim KK Escobedo JO Fakayode SO Fletcher KA Lowry M Schowalter CM Lawrence CM Fronczek FR Warner IM Strongin RM 《Journal of the American Chemical Society》2005,127(45):15949-15958
At elevated levels, homocysteine (Hcy, 1) is a risk factor for cardiovascular diseases, Alzheimer's disease, neural tube defects, and osteoporosis. Both 1 and cysteine (Cys, 3) are linked to neurotoxicity. The biochemical mechanisms by which 1 and 3 are involved in disease states are relatively unclear. Herein, we describe simple methods for detecting either Hcy or Cys in the visible spectral region with the highest selectivity reported to date without using biochemical techniques or preparative separations. Simple methods and readily available reagents allow for the detection of Cys and Hcy in the range of their physiologically relevant levels. New HPLC postcolumn detection methods for biological thiols are reported. The potential biomedical relevance of the chemical mechanisms involved in the detection of 1 is described. 相似文献
909.
The viability of tandem photochemical reaction-chemiluminescence detection was studied for a heterogeneous family of nitro compounds using chloramphenicol as a test substance. The 'on-line' chemical photodegradation of chloramphenicol was performed in a flow injection assembly by using a photoreactor consisting of a 725 cm x 0.5 mm id piece of PTFE tubing coiled around an 8 W low-pressure mercury lamp. Photodegraded chloramphenicol was detected by oxidizing photo-fragments from the parent compound and their subsequent reaction with a luminol-Co(II) system. The calibration graph was linear up to 3 x 10(-5) mol l-1 chloramphenicol, the limit of detection was 3 x 10(-9) mol l-1, the relative standard deviation was 1.8% for 2 x 10(-6) mol l-1 of the drug and the sample throughput was 60 h-1. The proposed method was used to determine chloramphenicol in pharmaceutical formulations and its application to other related nitro compounds was studied. 相似文献
910.
Paterson I Coster MJ Chen DY Oballa RM Wallace DJ Norcross RD 《Organic & biomolecular chemistry》2005,3(13):2399-2409
The convergent synthesis of the C1-C15 AB-spiroacetal subunit of altohyrtin A/spongistatin 1 is described. This highly stereocontrolled synthesis relies on matched boron aldol reactions of chiral methyl ketones, under Ipc(2)BCl mediation, to establish the C5, C9 and C11 stereocentres, and formation of the desired thermodynamic spiroacetal under acidic conditions. The scalable synthetic sequence developed provided access to multi-gram quantities of , thus enabling the successful completion of the total synthesis of altohyrtin A/spongistatin 1, as reported in Part 4. 相似文献