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   1619篇
  免费   53篇
  国内免费   2篇
化学   1029篇
晶体学   17篇
力学   50篇
数学   143篇
物理学   435篇
  2023年   13篇
  2022年   24篇
  2021年   28篇
  2020年   30篇
  2019年   35篇
  2018年   25篇
  2017年   26篇
  2016年   47篇
  2015年   41篇
  2014年   38篇
  2013年   125篇
  2012年   83篇
  2011年   110篇
  2010年   76篇
  2009年   63篇
  2008年   86篇
  2007年   72篇
  2006年   87篇
  2005年   55篇
  2004年   44篇
  2003年   57篇
  2002年   48篇
  2001年   36篇
  2000年   15篇
  1999年   21篇
  1998年   13篇
  1997年   11篇
  1996年   16篇
  1995年   18篇
  1994年   19篇
  1993年   22篇
  1992年   17篇
  1991年   16篇
  1990年   13篇
  1989年   11篇
  1988年   6篇
  1987年   8篇
  1986年   8篇
  1985年   10篇
  1984年   17篇
  1983年   16篇
  1982年   18篇
  1981年   16篇
  1980年   18篇
  1979年   11篇
  1978年   10篇
  1977年   15篇
  1976年   10篇
  1975年   10篇
  1973年   6篇
排序方式: 共有1674条查询结果,搜索用时 93 毫秒
41.
Extracellular fluid protein (ECFP) of Streptomyces species SS07 has been used to reduce water soluble azo dyes and the carcinogenic amines released have been compared with that from chemical reduction. The effect of temperature, pH and contact time on the recovery of amines using ECFP was studied. The ECFP releases carcinogenic amines at a pH of 9.2 and a temperature of 37 degrees C for a contact period of 24 h. The reduction products were analyzed with HPLC and their structures confirmed by LC-MS and GC-MS. It was observed that both the ECFP and chemical reduction methods released similar type of amine products. In the case of dye samples, compared to chemical reduction, 5-20% increase in the release of carcinogenic amines by ECFP was observed. The percentage of amine products released by chemical reduction was higher for leather garment samples compared to ECFP treatment.  相似文献   
42.
Abundant n → π* interactions between adjacent backbone carbonyl groups, identified by statistical analysis of protein structures, are predicted to play an important role in dictating the structure of proteins. However, experimentally testing the prediction in proteins has been challenging due to the weak nature of this interaction. By amplifying the strength of the n → π* interaction via amino acid substitution and thioamide incorporation at a solvent exposed β-turn within the GB1 proteins and Pin 1 WW domain, we demonstrate that an n → π* interaction increases the structural stability of proteins by restricting the ϕ torsion angle. Our results also suggest that amino acid side-chain identity and its rotameric conformation play an important and decisive role in dictating the strength of an n → π* interaction.

Amino acid residues adopt a right-handed α-helical conformation with increasing strength of the n → π* interaction. We also demonstrate a direct consequence of n → π* interactions on enhancing the structural stability of proteins.  相似文献   
43.
Xylidines are important precursors for the production of dyes, drugs, and various other products. Because of the high carcinogenic nature of some xylidine isomers it becomes very essential and relevant to develop suitable analytical procedures to separate isomers as well as enhance detection at very low concentrations. Micellar electrokinetic chromatography has been standardized at various influencing parameters such as pH, ionic strength, and micelle modifiers, and the optimum conditions have been ascertained for the best separation and sensitivity of standard mixtures. The applicability of the procedure in environmental samples is studied.  相似文献   
44.
A theoretical model for the multiline TEA CO2 laser has been developed which takes into account the overlap of the P(20) line of (0001) (1000) regular band transition with the R(23) line of (0111) (1110) hot band transition. The model is used for the study of the influence of different parameters like laser gas temperature, gas mixture and pump rates on laser intensities of different rotational lines. This study explains the experimental results of the high power multiline TEA CO2 laser very well.  相似文献   
45.
Schiff-base (SB) derivatives of Ni(II) and Cu(II) porphyrins endowed with various amine functions (R−NH2),n-butylamine,p-anisidine andm-nitroaniline have been prepared from corresponding formyl porphyrins. Protonation studies of these SB derivatives reveal a marked red shift of the optical absorption bands in the visible region relative to the unprotonated imines. The magnitude of the observed red shifts in the protonated derivatives, (SBH+) are found to depend on the electron-withdrawing or electron-donating nature of the R group of the amines. The results of the optical absorption,1H NMR, EPR, and cyclicovoltammetric studies are illustrative of the fact that protonation of the SB derivatives results in a localized positive charge, in the periphery of the porphyrin (p) system. The dibenzo-18-crown-6 interspersedbisporphyrin schiff bases have been prepared fromtrans 4,4′-diamino dibenzo-18-crown-6 and formyl porphyrins. The protonation of these SB derivatives is found to proceed in a concerted fashion. The cation complexation studies by the crown ether entity in thebisporphyrin systems have been investigated using optical absorption, magnetic resonance and electrochemical methods. The redox characteristics of the protonated dimeric SB porphyrins reveal that the first oxidation step involves a two-electron transfer reaction. This is important in view of their possible usage in multielectron transfer reactions of biological and catalytic interest.  相似文献   
46.
Conformational properties of 3-deazapurine nucleosides (namely, 3-deazaadenosine and 3-deazaguanosine) have been investigated by the PCILO method. Both C(2′)-endo and C(3′)-endo sugar puckers have been considered and the results indicate that the conformational preferences of these nucleoside analogs are quite different from those of their parent nucleosides adenosine and guanosine, respectively. This result has been correlated in terms of the biological inactivity of these nucleoside analogs.  相似文献   
47.
The stability constants of the Ni2+ and Co2+ complexes with 1,5-diazacyclooctane-N,N′-diacetic acid (H2DACODA) have been determined potentiometrically in 0.5M KNO3 at 25°. Only M(DACODA) and M(DACODA)OH? were observed. In addition the formation and dissociation kinetics of the pentacoordinate complexes M(DACODA) has been studied in aqueous solution using a stopped-flow technique. Formation follows the rate law vf = kf [M2+] [HDACODA?]/[H+], which can be interpreted as a bimolecular process either between M2+ and DACODA2? (k) or between MOH+ and HDACODA? (k). The second order rate constants k are much higher than those expected from water exchange and can only be explained by a strong internal conjugate base effect. In the limiting case, however, this is equivalent to the second possible explanation, which assumes MOH+ and HDACODA? as reactive species. The dissociation rate is given by vd = (kML + k [H+]) · [M(DACODA)].  相似文献   
48.
Some three-component random phenolic copolymers were prepared from three typical phenolic monomers; for example, p-chlorophenol, p-aminophenol, and p-cresol. Several samples of the copolymer were prepared by changing the feed composition and the composition of the copolymers was established by estimating ? NH2 and ? OH groups by electrometric titration techniques in nonaqueous media. Halogen was estimated by Volhard's method. The average degree of polymerization (DP) of the copolymers was calculated from the features of the electrometric titration curves, and the effects of monomer functional groups on the composition of the copolymers were interpreted in terms of the electron-donating and electron-attracting nature of the substituents present in the monomers.  相似文献   
49.
Bhaskar SU  Nandakumar NV 《Talanta》1980,27(9):757-758
A simple, sensitive and rapid colorimetric method is described for determining dimethoate [O,O-dimethyl-S-(N-methylcarbanoylmethyl)phosphorodithioate] and omethoate by an enzymatic method using pig liver acetone powder as enzyme source and p-nitrobenzenediazonium fluoroborate as the chromogenic reagent. This colorimetric method is more sensitive than non-enzymatic methods. Inhibition can be detected at ng levels and amounts ranging from 50 to 1000 ng of omethoate and from 1 to 10 mug of dimethoate can be estimated.  相似文献   
50.
The shape of liquid drops on solid surfaces deviates from the spherical as tension decreases and gravity effects start affecting the drop shape. This paper attempts to define this deviation and estimates the dimensionless Eotvos number limits above which the deviation becomes "significant." The use of these limiting values can facilitate estimation of contact angle in the following manner. It is well known that the equilibrium contact angle made by a liquid drop on a solid surface can be estimated from measurements of two drop parameters. These parameters can be any two chosen from the drop volume, height, and wetted radius. In case the effect of gravity on the drop shape is negligible, simple algebraic relations derived from the spherical section assumption exist, from which the contact angle can be estimated. In systems where the "spherical section" assumption is invalid, the Laplace equation for the drop shape has been solved numerically with any two of the above parameters as the constraints, to obtain the contact angle. In this paper, Eotvos numbers at which the deviation of the drop profile from the spherical is significant enough to result in contact angle deviation of 1 degrees are estimated. The limiting values of Eotvos number, expressed as a function of the original contact angle made by the spherical profile, are obtained by solving the Laplace equation for the drop shape with the drop volume and wetted radius constraints for decreasing values of Interfacial tension. These limiting values are also estimated for different drop sizes and for cases where the drop phase is heavier (sessile) and lighter (buoyant) than the surrounding fluid. The independence of the Eotvos number estimates from the sign of the density difference as well as the drop size is shown. These Eotvos number limits can be used to check if the spherical section assumption, with the resulting simple algebraic relations, can be used for contact angle estimation and other shape-related analysis for a system.  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