首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   144篇
  免费   6篇
  国内免费   1篇
化学   123篇
晶体学   2篇
数学   3篇
物理学   23篇
  2022年   6篇
  2020年   1篇
  2018年   1篇
  2017年   3篇
  2016年   3篇
  2015年   5篇
  2014年   5篇
  2013年   8篇
  2012年   15篇
  2011年   10篇
  2010年   9篇
  2009年   4篇
  2008年   11篇
  2007年   6篇
  2006年   9篇
  2005年   7篇
  2004年   12篇
  2003年   8篇
  2002年   4篇
  2001年   7篇
  2000年   4篇
  1999年   2篇
  1997年   2篇
  1994年   1篇
  1992年   4篇
  1991年   2篇
  1989年   1篇
  1975年   1篇
排序方式: 共有151条查询结果,搜索用时 15 毫秒
91.
彭川  Han Q.Le  B.Ishaug  J.Um 《光散射学报》2003,15(3):184-187
本文研究了由InGaAs/InAlAs材料组成,波长为4.6和5.1微米的量子级连中红外半导体激光器的光栅外耦合谐振腔的特性。在温度是80K时波长可调制宽度是激光中心波长的1.5%左右。对于这两个激光器而言,它们的波长可调制宽度随温度升高而减低。被调制的单模激光器的输出光功率是几个毫瓦,激光的谱线宽度是1到2个微米。激光阈值电流随波长缓慢变化,然而激光输出效率在短波长时更加优化。  相似文献   
92.
We purified phytoestrogens from Pueraria root (Pueraria mirifica from Thailand and Pueraria lobata from Korea), which is used as a rejuvenating folk medicine in Thailand and China. Dried, powdered plant material was extracted with 100% ethanol and further separated by concentration, filtration, and thin layer silica gel chromatography. Using the fractions obtained during separation, we first investigated their cytotoxicity in several cancer cell lines from various tissues. The ethanol-extracted components (PE1, PE4) had significant antiproliferative effects on breast cancer cell lines, including MCF-7, ZR-75-1, MDA-MB-231, SK-BR-3, and Hs578T. Second, we compared these results with the cytotoxic effects of known flavonoids, sterols, and coumarins from Pueraria root. The known compounds were not as effective, and occurred in a different polarity region on HPLC. Third, further separation resulted in the isolation of eight different components (Sub PE-A to -H). One of these, PE-D, affected the growth of some breast cancer cell lines (MCF-7, MDA- MB-231) in a dose- and time-dependent manner, as well as the growth of ovarian (2774) and cervical cancer cells (HeLa). Finally, a transfection assay showed that this component had an estrogenic effect similar to 17beta - estradiol, which activates both estrogen receptor alpha (ERalpha) and ERbeta. The NMR analysis determined that spinasterol (stigmasta-7, 22-dien-3beta-ol) is an active cytotoxic component of Pueraria root.  相似文献   
93.
We introduce an energy-momentum density vector which is independent of the affine structure of the manifold and whose conservation is linked to observers. Integrating this quantity over time-like surfaces we can define Hamiltonian and momentum for the system which coincide with the corresponding ADM definitions for the case of irrotational Riemannian manifolds. As a consequence of our formalism, a Weak Equivalence Principle version for manifolds with torsion appears as the natural extension to non-Riemannian geometries from the Equivalence Principle of General Relativity.  相似文献   
94.
Degeneration is one of the limiting factors in butanol fermentation, and it must be monitored and prevented for stable butanol production. In Clostridium acetobutylicum ATCC 824, the most well-known butanol-producing microorganism, degeneration is caused by the loss of the pSOL1 plasmid that carries essential genes involved in solvent production. In this study, we designed two specific primer and probe sets for real-time qPCR (RT-qPCR) detection of C. acetobutylicum ATCC 824 (the C. aceto set) and pSOL1-possessing C. acetobutylicum ATCC 824 (the DGS set). Specific primer and probe sets were designed on the basis of the 16S rDNA sequence and pSOL1 sequence. The number of degenerated C. acetobutylicum could be quantified by subtracting the number of C. acetobutylicum ATCC 824 containing pSOL1 from the total number of C. acetobutylicum ATCC 824. The primer and probe sets permitted the specific detection and quantification of degenerated C. acetobutylicum and total butanol-producing C. acetobutylicum by RT-qPCR.  相似文献   
95.
Second-order rate constants have been measured spectrophotometrically for the nucleophilic reactions of three substituted phenyl acetates with butane-2,3-dione monoximate (Ox(-)) as an alpha-nucleophile and p-chlorophenoxide (ClPhO(-)) as corresponding normal nucleophile, in MeCN-H2O mixtures of varying compositions at 25.0 +/- 0.1 degrees C. The reactivity of Ox(-) toward the aryl acetates decreases upon addition of MeCN to the reaction medium up to ca. 30 mol % MeCN, followed by a gradual increase in rate upon further addition of MeCN. A similar result has been obtained for the reaction of ClPhO(-) with the aryl acetates. However, the decrease in rate is more significant for the less reactive ClPhO(-) than for the more reactive Ox(-). Thus, for all the aryl acetates studied, Ox(-) exhibits a sizable alpha-effect (k(Ox)-/k(ClPhO)-) whose magnitude increases as the mol % MeCN in the reaction medium increases. The relative basicities (DeltapK(a)) of Ox(-) and ClPhO(-) have been determined spectrophotometrically using piperazine as a reference base. The DeltapK(a) values increase on increasing the mol % MeCN in the medium for both Ox(-) and ClPhO(-). The difference in the relative basicities of these nucleophiles (DeltaDeltapK(a)) becomes larger with increasing mol % MeCN. The plots of log k(Ox)-/k(ClPhO)- vs DeltaDeltapK(a) for the three substrates are linear with near-unit slope, indicating that the difference in the relative basicity of the nucleophiles is largely responsible for the increasing alpha-effect with medium composition in this system.  相似文献   
96.
This research was done on the basis of prediction that there is a relationship between welding parameters and geometry of the back-bead in arc welding which is a gap. Multiple regression analysis and artificial neural network were used as methods for predicting the geometry of the back-bead. The multiple regression analysis and the artificial neural network were formed, and the analysis data or verification data which were used in the formation process of the multiple regression, and the training data or test data which were used in the formation process of the artificial neural network, were used to perform the prediction of the back-bead. Through this research, it was found that the error rate predicted by the artificial neural network was smaller than that predicted by the multiple regression analysis, in terms of the width and depth of the back-bead. It was also found that between the two predictions, the prediction of the width of the back-bead was superior to the prediction of the depth in both methods.  相似文献   
97.
In a study of the solvent effect on the alpha-effect, second-order rate constants (kNu-) have been determined spectrophotometrically for reactions of a series of substituted phenyl acetates with butan-2,3-dione monoximate (Ox-, alpha-nucleophile) and p-chlorophenoxide (p-ClPhO-, reference nucleophile) in DMSO-H2O (DMSO = dimethyl sulfoxide) mixtures of varying compositions at 25.0 +/- 0.1 degrees C. The magnitude of the alpha-effect, kOx-/kp-ClPhO-, increases as the DMSO content in the medium increases up to 40-50 mol %, reaching 500, one of the largest alpha-effect values, and then decreases on further addition of DMSO, resulting in a bell-shaped alpha-effect profile regardless of the nature of the substrates. The magnitude of the alpha-effect is found to be significantly dependent on the substrates (or, more quantitatively, on beta(nuc)). Thus, beta(nuc) is an important predictor of the magnitude of the alpha-effect. The bell-shaped alpha-effect profile found in the present system is attributed to the differential change in the sensitivity of the medium effect on the Ox- and p-ClPhO- systems but not due to a change in the reaction mechanism or to a drastic change in the basicity of the two nucleophiles on addition of DMSO to the medium. Through application of calorimetric measurements of ground-state solvation combined with the diagnostic beta(nuc) values, it is shown that the transition-state effect is more dominant than the ground-state effect as the origin of the alpha-effect in the present system.  相似文献   
98.
The title reaction has been suggested to proceed through a zwitterionic tetrahedral intermediate with a change in the rate determining step on the basis of the curved Br?nsted-type plots obtained. The curvature center of the curved Br?nsted-type plots is at pKa = 6.4 regardless of the electronic nature of the substituent X in the benzoyl moiety.  相似文献   
99.
A mild, convenient reaction sequence for the synthesis of Nazarov cyclization substrates is described. The [3+2] dipolar cycloaddition of a nitrone and an electron-deficient alkyne gives an isolable isoxazoline intermediate, which upon oxidation undergoes stereoselective extrusion of nitrosomethane to give aryl vinyl or divinyl ketones.  相似文献   
100.
A kinetic study is reported for aminolysis of aryl diphenylphosphinothioates (2a-i). The phosphinothioates 2a-i are less reactive than aryl diphenylphosphinates (1a-i), the oxygen analogues of 2a-i, regardless of the basicity of the leaving aryloxides or the attacking amines. The Yukawa-Tsuno plot for the reactions of 2b-i with piperidine exhibits good linearity with a small r value (r=0.28), indicating that the leaving group departs at the rate-determining step with a small degree of bond fission. Reactions of 2,4-dinitrophenyl diphenylphosphinothioate (2a) with alicyclic secondary amines result in a good linear Br?nsted-type plot with betanuc=0.52, implying that the reactions proceed through a concerted mechanism. The betanuc value determined for the reactions of 2a is slightly larger than that reported for the corresponding reactions of 2,4-dinitrophenyl diphenylphosphinate (1a, i.e., betanuc=0.38), suggesting that reactions of 2a proceed through a tighter transition state (TS) than that of 1a. The reaction of 2a with piperidine exhibits a ca. 0.4 kcal/mol more favorable enthalpy of activation (DeltaH) than that of 1a. On the contrary, the entropy of activation at 25.0 degrees C (TDeltaS) is ca. 1.5 kcal/mol more unfavorable for the reaction of 2a than for that of 1a. This result supports the proposal that the reaction of 2a proceeds through a tighter TS than that of 1a and explains why 2a-i are less reactive than 1a-i.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号