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991.
Regio- and stereoselective iodinative cleavage of 2′,3′-anhydropurine nucleosides was achieved with samarium diiodide and ethyl bromoacetate to produce the corresponding 3′-iodopurine nucleosides, which were then converted to 3′-deoxypurine nucleosides including the natural product cordycepin. 相似文献
992.
Zhou YanXia Tan HongWei Yang ZuoYin Jia ZongChao Liu RuoZhuang Chen GuangJu 《中国科学B辑(英文版)》2007,50(2):266-271
The insect spruce budworm(Choristoneura fumiferana) produces antifreeze protein(AFP) to assist in the protection of the over-wintering larval stage and contains multiple isoforms. Structures for two isoforms,known as CfAFP-501 and CfAFP-337,show that both possess similar left-handed β-helical structure,although thermal hysteresis activity of the longer isoform CfAFP-501 is three times that of CfAFP-337. The markedly enhanced activity of CfAFP-501 is not proportional to,and cannot be simply accounted for,by the increased ice-binding site resulting from the two extra coils in CfAFP-501. In or-der to investigate the molecular basis for the activity difference and gain better understanding of AFPs in general,we have employed several different computational methods to systematically study the structural properties and ice interactions of the AFPs and their deletion models. In the context of intact AFPs,a majority of the coils in CfAFP-501 has better ice interaction and causes stronger ice lattice disruption than CfAFP-337,strongly suggesting a cooperative or synergistic effect among β-helical coils. The synergistic effect would play a critical role and make significant contributions to the anti-freeze activity β-helical antifreeze proteins. This is the first time that synergistic effect and its implica-tion for antifreeze activity are reported for β-helical antifreeze proteins. 相似文献
993.
The effect of introducing a bridge group into the diamine moiety on the thermal stability of aromatic polyamides substituted with nitro group in the diamine ring at the ortho position to the amide group was studied. Our present work showed that the bridge group, whether it was electron withdrawing or releasing, did not have a significant effect on the activity of the nitro group for the intramolecular cyclization reaction to poly(benzoxazole)s. 相似文献
994.
Preparation of Silver Nanoparticles through Alcohol Reduction with Organoalkoxysilanes 总被引:1,自引:0,他引:1
Hoe Jin Hah Sang Man Koo Sang Hoon Lee 《Journal of Sol-Gel Science and Technology》2003,26(1-3):467-471
Silver nanoparticles of narrow size distribution were prepared through the chemical reduction in an alcohol solution with several organoalkoxysilanes. In this system, organoalkoxysilanes served as a stabilizer, protecting silver nanoparticles from aggregation. The changes in size and morphology of colloidal silver nanoparticles were investigated with the addition of organoalkoxysilanes such as 3-aminopropyltriethoxysilane (APS), methyltriethoxysilane (MTS), phenyltrimethoxysilane (PTS), vinyltriethoxysilane (VTS), and 3-glycidoxypropyltrimethoxysilane (GPS) as stabilizers. The organic functional groups of organoalkoxysilanes interact with silver ions and clusters, which stabilize silver nanoparticles in the system. The silver nanoparticles obtained were characterized with transmission electron microscopy (TEM), UV-vis spectroscopy, etc. 相似文献
995.
Małgorzata Olejnik Teresa Szprengier-Juszkiewicz Piotr Jedziniak Jan Żmudzki 《Accreditation and quality assurance》2007,12(12):637-641
In this paper, the case of FAPAS PT 0270 “Doramectin and Oxfendazole in Sheep Liver” is discussed. During evaluation of the
data received from participants (determination of total, oxidised oxfendazole residue and calculation of the sum of oxfendazole
and oxfendazole sulfone residues), significant differences were observed between the results obtained by use of two analytical
approaches. This phenomenon can be explained by the route of oxfendazole metabolism, which results in the presence of fenbendazole
in the sample. This was not predicted by the provider; consequently, not all the necessary tests on the material were conducted.
Due to the high uncertainty of the z-scores in this test, the results of the PT cannot be used for purposes of evaluation, and the benefits of participation in
PT 0270 are questionable. 相似文献
996.
Zhang B Harb JN Davis RC Kim JW Chu SH Choi S Miller T Watt GD 《Inorganic chemistry》2005,44(10):3738-3745
Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05 +/- 0.10 e/M forming a stable M(OH)(2) mineral core. At pH 9.0, ascorbic acid (AH(2)), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH(2) shifted the reaction to completion with a M(3+)/AH(2) stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(O)OH and excess AH(2) was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74 M(-1) min(-1), respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH(2) concentration, equilibrium constants at pH 9.0 of 5.0 +/- 1.9 for Co-HoSF and 2.9 +/- 0.9 for Mn-HoSF were calculated for 2M(O)OH + AH(2) = 2M(OH)(2) + D, where AH(2) and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH(2). Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron. 相似文献
997.
Dong Won Kim Young Shin Jeon Young Kyu Jeong Moo Yul Suh Kih Soo Joe 《Journal of Radioanalytical and Nuclear Chemistry》1995,189(2):219-227
The chromatographic separation of lithium isotopes was investigated by chemical exchange with the recently synthesized polymer-bound dibenzo pyridino diamide azacrown (DBPDA) and reduced dibenzo pyridino diamide azacrown (RDBPDA). Column chromatography was employed for the determination of the effect of solvents and ligand conformation on the separation coefficients. The maximum separation coefficients, , for the DBPDA and RDBPDA at 20.0±0.02°C with acetonitrile as eluent, were found to be 0.034±0.002 and 0.035±0.002, respectively. The isotope separation coefficient and adsorption capability of the lithium ion on the DBPDA and RDBPDA were only slightly dependent on ligand structure, but strongly dependent on the solvent. DBPDA and RDBPDA appeared to have almost the same value for the isotope separation coefficient of lithium. 相似文献
998.
The use of reduced overlap population (ROP) analysis from EHMO calculations as a means to gauge the presence of metal–metal
bonds in triosmium clusters is examined. A number of triosmium clusters containing bridging ligands have been used as test
cases, including the bis-ethoxy bridged cluster Os3(μ-OEt)2(CO)10, 1b, and some of its group 15 derivatives Os3(μ-OEt)2(CO)9(EPh3), 2. These latter clusters are newly synthesized and have been characterized completely, including by single-crystal X-ray crystallographic
studies.
In honour of Professor Dieter Fenske on his 65th birthday. 相似文献
999.
The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature
of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom
in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net
resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two
junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface.
Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between
the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are
in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation
as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study
of the electrostatic potential at the position of the hydrogen nuclei.
We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive
life. 相似文献
1000.
A multi-wall carbon nanotube (MWNT)/cetyl pyridine bromine (CPB) composite film modified glassy carbon electrode (GCE) was
developed for the electrochemical determination of hymecromone in phosphonate buffer. Electrochemical behaviour of hymecromone
at the composite film electrode was investigated with voltammetry. Compared with an irreversible oxidation of hymecromone
at the bare GCE, the oxidation peak current was enhanced greatly at the film electrode. Some parameters such as pH, scan rate,
accumulation potential and accumulation time were optimized. Under optimal conditions, an oxidation peak at 0.82 V was employed
to determine hymecromone electrochemically. A linearity between the oxidation peak current and the hymecromone concentration
was obtained in the range of 3.0 × 10−7 − 2.0 × 10−5 mol 1−1 with a detection limit of 8.0 × 10−8 mol 1−1. The proposed procedure was successfully applied to assay hymecromone in pharmaceutical formulation with satisfactory results.
The text was submitted by the authors in English. 相似文献