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161.
Meyers CY Chan-Yu-King R Hua DH Kolb VM Matthews WS Parady TE Horii T Sandrock PB Hou Y Xie S 《The Journal of organic chemistry》2003,68(2):500-511
Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes. 相似文献
162.
163.
Zhang WW Ren XM Li H Xie JL Lu CS Zou Y Ni ZP Meng QJ 《Journal of colloid and interface science》2003,268(1):173-180
Self-assembled monolayers (SAMs) of functionalized azobenzene thiols (RAzoCnSH, n=3-6 for R=H, abbreviated as AzoCnSH; and n=4 for R=CH(3)CONH, abbreviated as aaAzoC4SH) on different substrates RAzoCnSz.sbnd;z.sfnc;S (S represents substrates of vacuum-deposited gold (Au), silver foil (Ag), HNO(3) etched silver foil (EAg), and silver mirror (mAg)) have been studied by SERS in the near-infrared region. SERS of the SAMs on EAg and/or mAg exhibit SERS effects that vary with etching time and/or deposition time. The most appropriate time is 5 s for etching in 1:1 HNO(3) and 40 s for deposition in 0.1 M Ag(NH(3))(2)NO(3). Further, a layer of Ag mirror was conveniently deposited on the top of the SAMs on different substrates, yielding a more efficient SERS-active system possessing a "sandwiched" structure of mAgz.sfnc;RAzoCnS-z.sfnc;S. An appropriate surface roughness is required for the strongest SERS effect. Scanning electron microscopy (SEM) indicates that there exist a large number of projects around 100 nm on the surface showing the strongest SERS effect. When the surface roughness is decreased or increased, the SERS effect decreases sharply. The relationship between the SERS effect and the structural nature was investigated and showed that the enhancement factor decays exponentially with increasing in distances of the azobenzene group from the underlying substrate or the overlying silver mirror. This result reveals that the SERS effect may be the result of the electromagnetic coupling effect between two metal layers. 相似文献
164.
Peng Chen Xiaojun Luo Guanqi Dai Yuchuan Jiang Yue Luo Shuang Peng Hao Wang Penghui Xie Chen Qu Wenyu Lin Jian Hong Xue Ning Aimin Li 《Experimental & molecular medicine》2020,52(7):1062
Dexmedetomidine (DEX) is an anesthetic that is widely used in the clinic, and it has been reported to exhibit paradoxical effects in the progression of multiple solid tumors. In this study, we sought to explore the mechanism by which DEX regulates hepatocellular carcinoma (HCC) progression underlying liver fibrosis. We determined the effects of DEX on tumor progression in an orthotopic HCC mouse model of fibrotic liver. A coculture system and a subcutaneous xenograft model involving coimplantation of mouse hepatoma cells (H22) and primary activated hepatic stellate cells (aHSCs) were used to study the effects of DEX on HCC progression. We found that in the preclinical mouse model of liver fibrosis, DEX treatment significantly shortened median survival time and promoted tumor growth, intrahepatic metastasis and pulmonary metastasis. The DEX receptor (ADRA2A) was mainly expressed in aHSCs but was barely detected in HCC cells. DEX dramatically reinforced HCC malignant behaviors in the presence of aHSCs in both the coculture system and the coimplantation mouse model, but DEX alone exerted no significant effects on the malignancy of HCC. Mechanistically, DEX induced IL-6 secretion from aHSCs and promoted HCC progression via STAT3 activation. Our findings provide evidence that the clinical application of DEX may cause undesirable side effects in HCC patients with liver fibrosis.Subject terms: Cancer microenvironment, Cell growth 相似文献
165.
167.
研究了一些氧化物的H2-TPR及CO-TPR行为,结果发现,Co3O4/Al2O3,NiO/SiO2,NiO和Pd/NiO的H2-TPR温度要低于它们的CO-TPR温度,特别是Pd/NiO样品,它的H2-TPR温度为598K,而其CO-TPR温度高达949K,差别为351K,因此有可能利用Pd/NiO在一定温度下选择性地与CO中的H2反应而将其除去. 实验结果表明,Pd/NiO可在603K及4000h-1的条件下从H2(0.34%),CO(50%)和N2(余)的混合气中选择性地除去90%以上的H2,吸氢容量为每克样品55mL标准态H2. 相似文献
168.
研究了对象基苯甲酸(ABA)/聚对苯二甲酸乙二酯(PET)液晶共聚酯酰胺的晶体结构,以及热性能、流变学和力学性质。广角X射线衍射研究结果表明ABA链节的引入使PET的晶态结构发生畸变,但大部分结晶衍射峰仍然存在。随着ABA含量的增加,各晶面间距基本不变,微晶尺寸显著增大,结晶度急剧降低。差示扫描量热分析和热失重结果表明共聚酯胺具有优良的热稳定性,并且随着ABA含量的增加,共聚物的热稳定性提高,共聚 相似文献
169.
酞侧基聚芳醚酮的热学性能谢红卫,李滨耀(中国科学院长春应用化学研究所长春130022)关键词酞侧基聚芳醚酮,pvT行为,导热系数,定压比热容酞侧基聚芳醚酮(PEK-C)具有较高的玻璃化转变温度,其流变加工性能和力学性能已被广泛研究[1~3],被证明是... 相似文献
170.