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81.
Bao J Baker RK Doss GA Kayser F Kotliar A Miao S Parsons WH Rupprecht KM 《Organic letters》2002,4(11):1871-1873
[reaction: see text] Pentacyclic triterpenoid natural product correolide (1) was converted to ketone 2 via ozonolysis. An unusual fragmentation reaction of ketone 2 with LiCl was discovered. This reaction is general among several similar substrates examined and appears to be specific for the correolide-type E-ring structure (ketone). A mechanism involving a retroaldol reaction, a nucleophilic opening of the epoxide, and a subsequent acetoxy elimination reaction was proposed. 相似文献
82.
Wei Lun-Cún Bao Shanglian Yang Qixiang Yang Xihong 《Journal of Radioanalytical and Nuclear Chemistry》1991,151(1):75-81
Combining the Charged Particle Activation Analysis (CPAA) and the Channeling Technique, the partial concentrations of the impurity carbon atoms in different crystal lattice locations of GaAs were claculated. The calculated results show that at lower total concentrations (0.3 ppm), carbon atoms occupy principally the octahedral and displaced octahedral interstitial positions, but at higher total concentrations (2 ppm), the substitutional carbon plays a principal role. 相似文献
83.
H. Bao S. Navaratnam B. J. Parsons G. O. Phillips 《Radiation Physics and Chemistry》1993,42(4-6):989-992
One-electron oxidation of the ferrous tris-PQ complex, a model for lipoxygenase, was attempted using oxidants such as •OH, N•3, Br•-2, Tl2+ and TlOH+. •OH was found to react with the complex with a bimolecular rate constant of (3.9±0.6)x109dm3mol-1s-1, a rate which is not very dissimilar to that for the reaction with the ligand PQ. However the product of the reaction was found to be a OH-adduct rather than a cation radical. No reaction was found to occur with N•3 or Br•-2. Both Tl2+ and TlOH+ reacted with the complex to form its oxidised species with rate constants of (7.0±1)x108dm3mol-1s-1 and (4.0±0.8)x108dm3mol-1s-1, respectively. From a comparison of the rate constants and the transient spectra it was concluded that the centre of oxidation is the ligand rather than the metal. 相似文献
84.
Qin Ren Hong Jin Zhang Xiao Kang Zhang Bao Tong Huang 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):847-851
To get hydrogenated polybutadiene-polymethyl methacrylate (HPB-b-PMMA) block copolymer to be used as a compatibilizer for blends of polyolefin/polar polymer, PB-b-PMMA was synthesized by anionic-free radical mechanism transformation polymerization. Selective extraction, gradient elution thin layer chromatography, and oil-oil emulsion separation techniques were tried to attempt to separate the copolymerization products. Hydrogenation of the PB sequence in PB-b-PMMA yielded HPB-b-PMMA. The compatibilizing function of PB-b-PMMA was shown in blending experiments. © 1993 John Wiley & Sons, Inc. 相似文献
85.
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87.
Inchul Shin Ian Davis Karinel Nieves-Merced Yifan Wang Stanton McHardy Aimin Liu 《Chemical science》2021,12(11):3984
SfmD is a heme-dependent enzyme in the biosynthetic pathway of saframycin A. Here, we present a 1.78 Å resolution de novo crystal structure of SfmD, which unveils a novel heme cofactor attached to the protein with an unusual HxnHxxxC motif (n ∼ 38). This heme cofactor is unique in two respects. It contains a single thioether bond in a cysteine–vinyl link with Cys317, and the ferric heme has two axial protein ligands, i.e., His274 and His313. We demonstrated that SfmD heme is catalytically active and can utilize dioxygen and ascorbate for a single-oxygen insertion into 3-methyl-l-tyrosine. Catalytic assays using ascorbate derivatives revealed the functional groups of ascorbate essential to its function as a cosubstrate. Abolishing the thioether linkage through mutation of Cys317 resulted in catalytically inactive SfmD variants. EPR and optical data revealed that the heme center undergoes a substantial conformational change with one axial histidine ligand dissociating from the iron ion in response to substrate 3-methyl-l-tyrosine binding or chemical reduction by a reducing agent, such as the cosubstrate ascorbate. The labile axial ligand was identified as His274 through redox-linked structural determinations. Together, identifying an unusual heme cofactor with a previously unknown heme-binding motif for a monooxygenase activity and the structural similarity of SfmD to the members of the heme-based tryptophan dioxygenase superfamily will broaden understanding of heme chemistry.The de novo crystal structure of SfmD reveals a novel c-type heme cofactor for promoting a monooxygenation reaction in the biosynthetic pathway of saframycin A. 相似文献
88.
A new study of the enzymatic hydrolysis of carboxymethyl cellulose with a bulk acoustic wave sensor 总被引:4,自引:0,他引:4
A new bulk acoustic wave (BAW) cellulase sensing technique, which is based on the enzymatic hydrolysis process of sodium carboxymethylcellulose (CMC) by cellulase, was established. The frequency shift curves of BAW sensor indicated that the viscosity of the tested solutions decreased during the hydrolysis process. The hydrolysis rate of CMC by cellulase was calculated from the frequency shift curves. The hydrolysis rate of CMC under different pH conditions at 30°C showed that cellulase had high hydrolysis ability approximately at pH 5.0. Kinetic parameters (the Michaelis constant Km and the maximum rate Vmax) of the process were estimated by using a linear method of Lineweaver–Burk plot. Km is 1.95±0.25 mg ml−1 and Vmax is −(4.25±0.58)×10−3 g1/2 cm−3/2 cP1/2 min−1. Also the activation energy (Ea) of the enzymatic hydrolysis, with a value of 51.99±1.26 kJ mol−1, was estimated in this work. 相似文献
89.
A new sensing method (BAW-TAL technique), which combined the bulk acoustic wave (BAW) technique with the gelation reaction of Tachypleus amebocyte lysate (TAL), was used for viscosity and density measurement and applied to the detection of Escherichia coliform (E. coli). This method depended on the fact that the viscosity and density of the mixture increased, and as a result, the resonance frequency decreased correspondingly after TAL was mixed with the heated E. coli solution that contained endotoxin. Results showed that the frequency shift was linearly related to the logarithm of E. coli concentration in the range of 2.7x10(4)-2.7x10(8) cells/ml. The correlation coefficient was 0.996. This BAW-TAL method was compared with the standard pour plate counts (PPC) method. The proposed method was much more rapid and simpler for detection of E. coli than the traditional methods. 相似文献
90.
研究了用高效液相色谱 /安培检测法测定蜂蜜中苯酚残留量。考察了试验参数对测定结果的影响。在所选试验条件下 ,苯酚保留时间约为 12min ,检出限为 2 .0ng·g- 1。三组不同水平的加样回收率为 91.6 10 1.9% ,相对标准偏差 2 .812 .8%。测定结果满意 相似文献