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191.
The synthesis of 16a'-homo-leurosidine was achieved through enantioselective generation of a ring D'-seco-precursor 33 (without requirement of a chiral auxiliary). Its cyclization provided the N(b')-quaternary salt 35 with a configuration corresponding to the atropisomeric form 8a rather than 8b of the target product. On debenzylation, the amine 8a was obtained and found not to isomerize thermally to the anticipated atropisomer 8b (in contrast to its lower homologue, with its formation of natural leurosidine). However, on protonation, a 1:1 mixture of atropisomers of 16a'-homo-leurosidine was obtained. A synthesis of 16a'-homo-vinblastine provided two atropisomers 5a and 5b for the free base at equilibrium (1:2.3 at room temperature in CDCl(3)), with a shift to the major conformer 5b with increasing solvent acidity or decreasing temperature. The synthesis was achieved through a stereoselective inversion of the tertiary hydroxyl function in the enantioselectively generated C-20' progenitor 39. 相似文献
192.
Zou Q Bennion BJ Daggett V Murphy KP 《Journal of the American Chemical Society》2002,124(7):1192-1202
Trimethylamine n-oxide (TMAO) is a naturally occurring osmolyte that stabilizes proteins and offsets the destabilizing effects of urea. To investigate the molecular mechanism of these effects, we have studied the thermodynamics of interaction between TMAO and protein functional groups. The solubilities of a homologous series of cyclic dipeptides were measured by differential refractive index and the dissolution heats were determined calorimetrically as a function of TMAO concentration at 25 degrees C. The transfer free energy of the amide unit (-CONH-) from water to 1 M TMAO is large and positive, indicating an unfavorable interaction between the TMAO solution and the amide unit. This unfavorable interaction is enthalpic in origin. The interaction between TMAO and apolar groups is slightly favorable. The transfer free energy of apolar groups from water to TMAO consists of favorable enthalpic and unfavorable entropic contributions. This is in contrast to the contributions for the interaction between urea and apolar groups. Molecular dynamics simulations were performed to provide a structural framework for the interpretation of these results. The simulations show enhancement of water structure by TMAO in the form of a slight increase in the number of hydrogen bonds per water molecule, stronger water hydrogen bonds, and long-range spatial ordering of the solvent. These findings suggest that TMAO stabilizes proteins via enhancement of water structure, such that interactions with the amide unit are discouraged. 相似文献
193.
194.
195.
微波等离子体炬发射光谱法去溶系统性能的研究 总被引:7,自引:0,他引:7
用微波等离子体矩(MPT)作激发光源,等离子体的工作气体为氩气,研究了气动雾化进样去溶系统的工作参数对分析性能的影响,探讨了水冷凝与浓硫酸吸收二者协同去溶的相关性,结果表明,OH (Q1带,带头谱线为308.520nm)的发射强度即可判别样品去溶效果。 相似文献
196.
A novel chemiluminescence (CL) flow system has been developed for the sequential determination of Fe(II) and Fe(III) in water.
Fe(II) was detected by its catalytic effect on the CL reaction between luminol immobilized on an anion exchange resin column
and dissolved oxygen; Fe(III) was determined by difference measurement after on-line conversion to Fe(II) in a reducing mini-column
packed with Cu plated Zn granules. For both ions, the calibration graph was linear in the range 1 × 10–9 to 1 × 10–6 g/mL, and the detection limit was 4 × 10–10 g/mL. A complete analysis could be performed in 1.5 min with a relative standard deviation of less than 5%. The system could
be reused for over 200 times and has been applied successfully to the determination of Fe(II) and Fe(III) in natural water
samples.
Received: 13 March 1997 / Revised: 3 June 1997 / Accepted: 6 June 1997 相似文献
197.
Qin B Lin J Lin Z Ren H Xue Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(4):717-720
The vibration spectrum and FAB mass spectrum of (+/-)-1-[3-(2-methoxyphenoxy)-2-hydroxypropyl]-4-[(2,6-dimethylphenyl)aminocarbonylmethyl]piperazine dihydrochloride salt was studied. By comparing with the spectra of free base, different bands of IR were found in the NH+ stretching, the NH+ deformation motion, the CH2 of NCH2 group symmetric stretching, the CH2 of N-CH2 group twisting and the CN stretching. FAB shows the basic peak is M + H. Other m/e peaks are consistent with the structure. 相似文献
198.
高效液相色谱-串联质谱法结合多糖衍生物手性固定相拆分氰戊菊酯 总被引:1,自引:0,他引:1
建立了以多糖衍生物为手性固定相的高效液相色谱-串联质谱(HPLC-MS/MS)直接拆分氰戊菊酯对映体的方法。在反相液相色谱条件下,考察了手性固定相的种类、流动相组成、柱温、流速对氰戊菊酯4个立体异构体分离的影响。同时,利用热力学方法对氰戊菊酯的立体异构体与固定相之间的色谱保留和分离的热力学机理进行了探讨。结果表明:采用Lux Cellulose-3(纤维素-三(4-甲基苯甲酸酯))手性色谱柱,在以流动相为乙腈-水(5 mmol/L甲酸铵)=(55:45,V:V)流速0.4 mL/min,柱温30℃的条件下,可在14 mins内实现氰戊菊酯4个立体异构体的基线分离。拓展了HPLC-MS/MS在菊酯类手性农药对映体分离及检测上的应用。 相似文献
199.
Chuanguang Qin 《Tetrahedron letters》2004,45(1):217-220
Total synthesis of decapeptide antibiotics streptocidins A-D from Streptomyces sp. Tü 6071 was accomplished for the first time by solid-phase peptide synthesis followed by traceless cyclization of the activated linear precursors, without protection of nucleophilic side chain. Synthetic products were equally active as the natural products isolated from the bacterial source and found to possess similar bacterial selectivity as other members in the amphipathic antimicrobial cyclic decapeptide family. 相似文献
200.