6 resultados para Retro
em Chinese Academy of Sciences Institutional Repositories Grid Portal
Resumo:
The electrochemical properties of a series of structurally related fullerooxazoles, [6,6] cyclic phenylimidate C-60 (1), 1,2-benzal-3-N-4-O-cyclic phenylimidate C-60 (2), and 1,4-dibenzyl-2,3-cyclic phenylimidate C-60 (3), are described, and the spectroscopic characterizations of their anionic species are reported. The results show that compounds I and 2 undergo retro-cycloaddition reactions that lead to the formation of C-60 and C61HPh, respectively, upon two-electron-transfer reduction. However, compound 3 demonstrates much more electrochemical stability as no retro-cycloaddition reaction occurs under similar conditions. Natural bond orbital (NBO) calculations on charge distribution show there is no significant difference among the dianions of 1, 2, and 3, indicating that the electrochemical stability of 3 is unlikely to be caused by the charge distribution difference of the dianions of three compounds. Examination on the crystal structure of compound 3 reveals close contacts of the C-H group with the heteroatoms (N and O) of cyclic phenylimidate, suggesting the existence of C-H center dot center dot center dot X (X = N, O) intramolecular hydrogen bonding among the addends, which is further confirmed by NBO analysis.
Resumo:
High-resolution Sustained off resonance irradiation (SORI) CID was employed to distinguish four pairs of isomeric diglycosyl flavonoids in the negative mode using the electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). All of these isomers can be distinguished via MS/MS data. For these diglycosyl flavones and flavanones, the deprotonated alpha 1-->6 linkage diglycosyl flavonoids produce fewer fragments than the alpha 1-->2 linkage type compounds and the Retro-Diels-Alder (RDA) reaction in MS/MS only takes place when the aglycone is a flavanone and glycosylated with an alpha 1-->2 intersaccharide linkage disaccharide. The deprotonation sites after collisional activation are discussed according to the high mass accuracy and high-resolution data of tandem spectrometry. Some of these high-resolution SORI CID product ions from alpha 1-->2 linkage diglycosyl flavonoids involve multibond cleavages; the possible mechanism is discussed based on the computer modeling using Gaussian 03 program package at the B3LYP/6-31G level of theory. Unambiguous elementary composition data provides fragmentation information that has not been reported previously.
Resumo:
Seven structure analogical flavonoid aglycones have been analyzed using electrospray ionization tandem mass spectrometry (ESI-MSn) in the negative-ion mode. The spectra obtained ESI-MSn allowed us to propose plausible schemes for their fragmentation mechanism. By analyzing the product ions spectra of deprotonated molecule ions [M-H](-), some neutral diagnostic losses and specific retro Diels-Alder fragments were obtained. By using all of these characteristic fragment ions we can specially differentiate the flavone isomer.
Studies on the flavones using liquid chromatography-electrospray ionization tandem mass spectrometry
Resumo:
Fragmentation pathways of nine flavone compounds have been studied by using electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn). Analyzing the product ion spectra of flavonoids and aglycones, we observed some diagnostic neutral losses, such as *CH3, H2O, residue of glucose and gluconic acid, which are very useful for the identification of the functional groups in the structures. Furthermore, specific retro Diels-Alder (RDA) fragments for flavones with different hydroxyl substitution have also been discussed. The information is helpful for the rapid identification of the location site of hydroxyl substitution on flavones. Fragmentation pathways of C-glycosidic flavonoid have also been discussed using ESI-MSn, demonstrating ions [M-H-60](-), [M-H-90](-), [M-H-120](-) are characteristic ions of C-glycosidic flavonoid. According to the fragmentation mechanism of mass spectrometry and HPLC-MS data, the structures of seven flavones in Scutellaria baicalensis Georgi have been identified on-line without time-consuming isolation. The HPLC-ESI-MSn method for analyzing constituents in the Scutellaria baicalensis Georgi has been established.
Resumo:
本文研究越野移动机器人驾驶专家系统等有关问题.首先介绍了系统的硬件支持环境,然后阐述了自动驾驶专家系统的总体结构,有关知识库的内容以及使用知识的各功能模块的作用与运行机理.该系统已部分得以应用,能够完全代替驾驶员完成各种驾驶操作,并能进行自主导航、运动规划、自动绕障、动态跟踪目标、原路返回以及示教再现等复杂任务。
Resumo:
To study the relationship between mental-physical health and coping behavior,job stress and job motivation in medical laboratory scientists and technicians. A cross-section survey was conducted,using the anxiety rating scale(SAS), depression rating scale(SDS), coping behavior rating scale,self-rating subhealth scale,self-rating stress scale,and self-rating job motivation scale among 289 medical laboratory scientists and technicians with analysis of ANOVA and Regression. The study was carried out in three steps:step1 is to analyze the general situation of the mental-physical health.Step 2 is to analyze the features of the main influencial facotors.Step 3 is to study the influence of the relative factors on mental-physical health.The following are the results: 1.The anxiety and depression scores of the medical researchers and technicians were 30±6 and 37±8 respectively,both significantly lower than those of the national norm(34±6 and 42±11 respectively,both P<0.01),which are of significant difference. The depression score of the associate chief technician was 42±7, significantly higher than those of the medical researchers and technicians with any other professional titles (all P<0.05), and the anxiety score of the associate chief technicians was 32±7, significantly higher than that of the research fellows(28±4, P<0.05),with no significant difference to the score of the medical researchers and technicians with other professional titles. The depression score,anxiety score and the subhealth score of the age group of 36~49 were 39±9,31±7 and 32±9 respectively, both higher than that of the age group of 20~35 (36±8,29±6 and 29±7 respectively,both P<0.05),while there is much diference among other age groups. And the subhealth status has nothing to do with marital status,education background and professional titles. 2.The coping behaviors,job stress and motivation of the military medical laboratory scientists and technicians. 1)Coping behaviors:The seeking help score of the associate chief technicians was 2.8±0.5,not significantly different from that of the associate research fellows(2.8±0.5),but significantly lower than those of the medical researchers and technicians with other professional titles(all P<0.01),and whose self-blame score was higher than that of the research fellows,which is of significant difference.The self-blame score and the imagination score of the associate research fellows were 2.0±0.5 and 2.4±0.5 respectively, significantly higher than that of the research fellows(1.6±0.4, 2.1±0.4,both P<0.01). The seeking help score of the females was 3.1±0.5, significantly higher than that of the males(2.9±0.5, both P<0.01),and the solving problem score was 3.4±0.6,significantly lower than the male(3.6±0.7, both P<0.01).There is no any significant difference in coping behaviors among researchers and technicians of different marital status,education background and age groups. 2)Job stress: The score of job stress of the age group of 35~49 and 50~60 were 23±8 and 25±6 respectively,significantly higher than that of the 20~35(21±7,both P<0.05). There is no any significant difference in job stress among researchers and technicians of different marital status,gender,professional titles and education background. 3)The score of meeting personal desire for reputation and interests of the males was 19.6±5.4,significantly higher than that of the females(18.4±5.0, both P<0.05), while there is no significant difference in job motivation among researchers and technicians of different titles,education,age and marital status. 3.The relationship of the mental-physical health of the military medical laboratory scientists and technicians with their coping behaviors,job stress and motivations 1) Coping behaviors:Regression analysis showed that, the best predictors of subhealth were anxiety,depression and escaping (β=-0.40,β=0.23, β=0.14, both P<0.01).the best predictors of anxiety and depression were active coping behaviors and negative coping behaviors (β=-0.40,β=0.40, both P<0.01).The moderate(rational) coping behaviors is the best predictor only of anxiety and of significant difference. 2)job stress : Regression analysis demonstrated that anxiety,depression,job stress 2 and job stress 4 are the best predictor for subhealth;job stress 12 is the best retro-predictor for depression; job stress 3 and 8 are the best predictor for depression;and job stress 2 and 9 are the best predictor for anxiety ,which are of significant difference. 3)Motivation:Regression analysis demonstrated that depression is the best predictor for subhealth while motivation itself doesn't predict subhealth;with respect to the specific contents of motivation,"probing unknown rules and making contributions to the human society "is the best retro-predictor for depression and has nothing to do with anxiety prediction. 4) The combined influences of coping behaviors,job stress and motivations: Regression analysis showed that, the best predictors for subhealth were anxiety,depression and job stress(β=0.41,β=0.24, β=0.19, both P<0.01).the best predictors for anxiety and depression were active coping behaviors and negative coping behaviors (β=-0.40,β=0.40, both P<0.01).The moderate(rational) coping behaviors is the best predictor only for anxiety and of significant difference. CONCLUSIONS: Regression analysis showed that the best predictors for anxiety and depression were active coping behaviors and negative coping behaviors, the best predictors for subhealth were anxiety,depression and job stress.Coping behaviors, job stress and motivations have significant influences on the mental-physical health of the military medical researchers and and technicians. Among them,coping behavior is the most important factor while job stress and motivation follow. Seeking help more often,less self-blame ,imagination and job stress could help release the anxiety, depression and improve the subhealth of the medical researchers and technicians. The findings of this study indicate we should address the physical and mental health of the military laboratory researchers and technicians.