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31.
[reaction: see text] Psymberin is a sponge-derived natural product that shows striking selectivity as a cytotoxic agent. Conformational mobility has precluded stereochemical assignment for the acyl fragment of this molecule (psymberic acid) by NMR. Herein we report stereoselective syntheses of all four stereoisomers of psymberic acid. A comparison of the acid-mediated cyclization products of these compounds to the product of psymberin's acidic methanolysis showed the stereochemical configuration of this fragment to be 4S,5S. 相似文献
32.
Peter LM Riley DJ Tull EJ Wijayantha KG 《Chemical communications (Cambridge, England)》2002,(10):1030-1031
CdS quantum dots can be self-assembled on high surface area nanocrystalline TiO2 electrodes; spectroscopic and photoelectrochemical studies indicate that the size, and hence the absorption edge, of the CdS particles can be controlled; efficient photosensitization of the TiO2 electrode by the Q-particles has been achieved. 相似文献
33.
The synthesis of 3-pyridyl biaryl systems can be readily achieved by means of palladium-catalyzed Suzuki cross-coupling reactions between aryl halides and 3-pyridylboroxin. A series of cross-couplings were conducted in order to investigate the scope and limitations of this protocol. 相似文献
34.
A dense-phase latex rubber tube and a polyporous propylene hollow-fiber membrane module (HFMM) were investigated for control
of benzene-contaminated gas streams. The abiotic mass flux observed through the latex tube was 3.9–13 mg/(min·m2) for 150 ppm of benzene at various gas and liquid flow rates, while a 100-fold lower mass flux was observed in the HFMM.
After seeding with an aromatic-degrading culture enriched from activated sludge, the observed removal was 80% of 150 ppm,
corresponding toa mass flux of 45 mg/(min·m2). The observed mass flux through the HFMM during biofiltration also rose, to 0.4 mg/(min·m2). Because the HFMM had a 50-fold higher surface area than the latex tube, the observed ben zene removal was 99.8%. Compared
to conventional biofilters, the two reactors had modest elimination capacities, 2.5–18 g/(m3·h) in the latex tube membrane bioreactor and 4.8–58 g/(m3·h) in the HFMM. Although the HFMM had a higher elimination capacity, the gas-phase pressure drop was much greater. 相似文献
35.
Micklefield J 《Chemistry & biology》2005,12(6):611-613
(2S)-4-amino-2-hydroxybutyrate (AHBA) is a side chain that is important for the antibiotic activities of aminoglycosides. The elucidation of the biosynthetic pathway to AHBA, by Spencer et al. in this issue of Chemistry & Biology [1], reveals several surprises and will facilitate biosynthetic engineering of new improved aminoglycoside antibiotics. 相似文献
36.
A computational study has been performed to examine the reactions of a model beta-diketiminatoaluminium (I) complex with the hydrogen atom and with the electron. It was found that the hydrogen atom adds to the metal centre exothermically (DeltaH(rxn)=-202 kJ mol(-1)), and the spin density in the resulting radical resides entirely on the beta-diketiminato ligand. The spin density of the corresponding radical anion is very similar to the H-adduct. 相似文献
37.
The synthesis of indaphyrins, novel meso-tetraarylsecochlorin-derived chromophores incorporating o-phenyl-to-beta-linkages, is described. Oxidative diol cleavage of meso-tetraaryl-2,3-dihydroxy-2,3-chlorins results in the formation of a secochlorin bisaldehyde. Depending on the reaction conditions during the ring cleavage reaction, one or two of the aldehyde groups react with the adjacent o-phenyl positions, leading to an intramolecular electrophilic aromatic substitution of the o-phenyl proton, and the establishment of a direct o-phenyl-to-beta-linkage. The initially formed carbinol is spontaneously oxidized to the corresponding ketone. This modification forces the aryl groups into co-planarity with the macrocycle, allowing for interactions between the pi-electrons of the aryl groups, the ketone linkage, and those of the chromophore, resulting in a significant electronic modulation of the porphyrinic pi-system. The UV-vis spectroscopic properties of the free base, CuII, NiII, and ZnII indaphyrins are discussed. 相似文献
38.
Keiper JS Behles JA Bucholz TL Simhan R DeSimone JM Lynn GW Wignall GD Melnichenko YB Frielinghaus H 《Langmuir : the ACS journal of surfaces and colloids》2004,20(4):1065-1072
Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions. 相似文献
39.
May JP Ting R Lermer L Thomas JM Roupioz Y Perrin DM 《Journal of the American Chemical Society》2004,126(13):4145-4156
A DNAzyme, synthetically modified with both primary amines and imidazoles, is found to act as a M2+ -independent AP lyase-endonuclease. In the course of the cleavage reaction, this DNAzyme forms a covalent Schiff base intermediate with an abasic site on a complementary oligodeoxyribonucleotide. This intermediate, which is inferred from NaCNBH3 trapping as well as cyanide inhibition, does not evidently accumulate because the second step, dehydrophosphorylative elimination, is fast compared to Schiff base formation. The 5'-product that remains linked to the catalyst hydrolyzes slowly to regenerate free catalyst. The use of duly modified DNAzymes to perform Schiff base catalysis demonstrates the value of modified nucleotides for enhancing the catalytic repertoire of nucleic acids. This work suggests that DNAzymes will be capable of catalyzing aldol condensation reactions. 相似文献
40.
Recent analytical innovations for nucleic acid detection have revolutionized the biological sciences. Single nucleic acid sequence detection methods have been expanded to incorporate multiplexed detection strategies. A variety of nucleic acid detection formats are now available that can address high throughput genomic interrogation. Many of these parallel detection platforms or arrays, employ fluorescence as the signaling method. Fluorescence-based assays offer many advantages, including increased sensitivity, safety and multiplexing capabilities, as well as the ability to measure multiple fluorescence properties. Multiplexed microarray platforms provide parallel detection capabilities capable of measuring thousands of simultaneous responses. This review will discuss both single target detection and microarray applications with a focus on gene expression and pathogenic microorganism (PM) detection. 相似文献