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171.
芳香叔胺引发丙烯腈光聚合的引发机理 总被引:1,自引:0,他引:1
芳香叔胺引发丙烯腈(AN)光聚合是通过形成激基复合物(exciPlex)进行的。紫外光谱和荧光光谱表明,芳香叔胺在基态可以和AN形成电荷转移复合物(CTC),而在激发态可和AN形成exciplc(称定域激发)。CTC经光照亦可激发(称CTC激发)。 定域激发引起光聚合速率为CH_3C_6H_4N(CH_3)_2>C_6H_5N(CH_3)_2>HOCH_2·C_6H_4N(CH_3)_2>CH_3C_6H_4N(CH_2CH_2OH)_2,与芳胺荧光被AN淬灭的Stern-Vo-lmer常数顺序一致。CTC激发引起的光聚合顺序为:CH_3C_6H_4N(CH_3)_2>CH_3C_6H_4N(CH_2CH_2OH)_2>HOCH_2C_6H_4N(CH_3)_2>C_6H_5N(CH_3)_2,与芳胺上取代基推电子能力一致。端基分析表明聚合物有芳胺端基。 相似文献
172.
Yibin Pan Lili Yan Qiaoqiao Chen Cheng Wei Yongdong Dai Xiaomei Tong Haiyan Zhu Meifei Lu Yanling Zhang Xiaoying Jin Tai Zhang Xiaona Lin Feng Zhou Songying Zhang 《Experimental & molecular medicine》2021,53(1):52
In early pregnancy, the placenta anchors the conceptus and supports embryonic development and survival. This study aimed to investigate the underlying functions of Shh signaling in recurrent miscarriage (RM), a serious disorder of pregnancy. In the present study, Shh and Gli2 were mainly observed in cytotrophoblasts (CTBs), Ptch was mainly observed in syncytiotrophoblasts (STBs), and Smo and Gli3 were expressed in both CTBs and STBs. Shh signaling was significantly impaired in human placenta tissue from recurrent miscarriage patients compared to that of gestational age-matched normal controls. VEGF-A and CD31 protein levels were also significantly decreased in recurrent miscarriage patients. Furthermore, inhibition of Shh signaling impaired the motility of JAR cells by regulating the expression of Gli2 and Gli3. Intriguingly, inhibition of Shh signaling also triggered autophagy and autolysosome accumulation. Additionally, knockdown of BECN1 reversed Gant61-induced motility inhibition. In conclusion, our results showed that dysfunction of Shh signaling activated autophagy to inhibit trophoblast motility, which suggests the Shh pathway and autophagy as potential targets for RM therapy.Subject terms: Embryology, Endocrine reproductive disorders, Autophagosomes 相似文献
173.
The mass spectra of neopentyl alcohol, bromide and chloride and some 13C and 2H labelled analogues have been studied. Most fragmentations of the molecular ions of these compounds occur by simple bond cleavages and do not involve rearrangement before fragmentation. We propose that in the [M ? CH3]+ fragment ions, seven of the eight hydrogen atoms and all four carbon atoms are involved in randomisation when an ethylene molecule is ejected. The eighth hydrogen atom (which comes from a methyl group) is probably associated with the heteroatom. The neopentylcation, observed only in the mass spectrum of the bromide, fragments mainly by loss of an ethylene molecule, also containing randomly selected hydrogen and carbon atoms. The [C4H7]+ ion also was observed to undergo complete atom scrambling. 相似文献
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175.
N-phosphorylamino acids are chemically active species that have many biomimic activities. alpha-COOH in amino acids and peptides behaviors rather differently than beta-COOH in many biochemical processes and takes a more important role in the origin of life. Activity differences between alpha-COOH and beta-COOH in the peptide formation of phosphoryl amino acids are studied by 1D, 2D NMR techniques and by ab initio and density functional theory (DFT) calculations in this paper. Phosphoryl dipeptide is formed directly from phosphoryl aspartic acids without any coupling reagents. Only the alpha-dipeptide ester is observed by 1D (1)H, (13)C, and (31)P NMR and 2D NMR. In the ab initio and DFT calculations, the pentacoordinate phosphorane intermediates containing five-membered rings are predicted to be more favored than those with six-membered rings. Both the experimental results and the theoretical calculations suggest that only the alpha-COOH group is activated by N-phosphorylation in N-phosphorylaspartic acid under mild conditions. 相似文献
176.
Changyuan Lu Side Yao Wenfeng Wang Yongpeng Tong Weizhen Lin Tingwen Rong Nianyun Lin 《中国科学B辑(英文版)》1998,41(3):259-265
Fullerols of C60 and of C70 [C60(OH)n, C70(OH)m], water-soluble fullerene derivatives, unlike some other fullerene derivatives (such as C60 (C4H6O), C60 (C3H7N) and C60 [C(COOEt)2]x), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser.
The quantum yields of formation of hydrated electron (Φe
−) are determined to be 0.08 and 0.11 for fullerols of C60 and of C70 respectively at room temperature (ca. 15°C) with KI solution used as reference. By laser flash photolysis and oxidation of
sulfate radical anion SO4
−, the fullerol radical cation or neutral radical of C60 is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C70 are observed for the first time.
Project supported by the National Natural Science Foundation of China 相似文献
177.
T. L. Wang H. W. Tong X. Y. Yan L. Q. Sheng J. Yang S. M. Liu 《Chromatographia》2005,62(11-12):631-636
An effective and rapid method, use of a 2,4-dinitrophenylhydrazine (DNPH)-treated Cambridge filter and high-performance liquid chromatography (HPLC) with diode-array detection (DAD), has been used for determination of low-molecular-mass carbonyl compounds in cigarette smoke. Different chromatographic mobile phases were investigated and the optimized mobile phase was a gradient prepared from water–acetonitrile–tetrahydrofuran (THF)–iso-propanol, 59:30:10:1 (v/v) (mixture A) and acetonitrile–water, 65:35 (v/v) (mixture B). Under the optimized chromatographic conditions, the 2,4-dinitrophenylhydrazones of formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, 2-butanone, and iso-butyraldehyde were separated completely in an 18 min chromatographic run. The concentration of acid, which has large effect on carbonyl-DNPH derivatization, was investigated by adding different volumes of perchloric acid. The DNPH-treated Cambridge filter was convenient and effective compared with conventional methods used to collect and derivatize the carbonyl compounds present in cigarette smoke. Validation of the method showed it to be effective, precise, accurate, and linear over the range of concentrations of analyzed. 相似文献
178.
Cu以其优异的导电性、导热性和易加工性广泛用于工农业生产中.自然Cu的腐蚀和防腐成为人们很关注的问题.人们已经注意到,Cl-对Cu的腐蚀有影响,并进行过一些研究.但目前使用光电化学方法研究这一问题的文章尚不多见,特别是利用测量开路光电压及其瞬态波形这一现场的、无损的、灵敏的监测方法研究户对Cu电极腐蚀全过程的文章尚未见到.本文正是利用如上方法及XPS,AES方法,研究了Cl-对Cu电极腐蚀的全过程,取得了一些有意义的结果.1实验方法Cu电极用99.99%(质量分数)的Cu制成,面积约为39mm2;电极底部由Cu导线焊接引出,… 相似文献
179.
180.