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   6977篇
  免费   168篇
  国内免费   505篇
化学   6568篇
晶体学   61篇
力学   79篇
综合类   19篇
数学   566篇
物理学   357篇
  2024年   11篇
  2023年   51篇
  2022年   170篇
  2021年   156篇
  2020年   144篇
  2019年   159篇
  2018年   136篇
  2017年   173篇
  2016年   153篇
  2015年   125篇
  2014年   179篇
  2013年   575篇
  2012年   238篇
  2011年   226篇
  2010年   179篇
  2009年   246篇
  2008年   274篇
  2007年   302篇
  2006年   246篇
  2005年   259篇
  2004年   260篇
  2003年   249篇
  2002年   1741篇
  2001年   211篇
  2000年   135篇
  1999年   111篇
  1998年   88篇
  1997年   100篇
  1996年   94篇
  1995年   109篇
  1994年   75篇
  1993年   75篇
  1992年   70篇
  1991年   42篇
  1990年   28篇
  1989年   22篇
  1988年   33篇
  1987年   27篇
  1986年   17篇
  1985年   21篇
  1984年   25篇
  1983年   6篇
  1982年   15篇
  1981年   9篇
  1980年   13篇
  1979年   6篇
  1978年   8篇
  1973年   3篇
  1971年   32篇
  1970年   16篇
排序方式: 共有7650条查询结果,搜索用时 0 毫秒
71.
The interaction of DNA polymerase Tte from Thermus thermophilus B35 with dUTP analog containing a fluorescein residue bound to C(5) of the base (Flu-dUTP) was studied by fluorescence titration. The dissociation constants of the enzyme—substrate complexes in the absence and in the presence of a DNA duplex containing an extended template and bivalent metal ions and the kinetic parameters of polymerization by DNA polymerase Tte in the presence of Flu-dUTP were determined. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1268–1272, May, 2005.  相似文献   
72.
Summary A rapid and simple method for the determination of both lysinoalanine (LAL) and protein hydrolysate amino acids after derivatization with dansyl chloride (5-dimethylaminoaphtalene-1sulfonyl chloride) and separation with RP-HPLC (UV detection) is presented. LAL is analysed in less than 15 minutes and complete separation of 22 amino acids is achieved in less than 30 minutes using single linear gradients of solvents (phosphate buffer and acetonitrile). Quantitative results obtained by HPLC compare well with results of the ion-exchange chromatography (amino acid analyser). The importance of the duration of the derivatization reaction and of the excess of reagent is discussed. As examples, the results of the determination of LAL in two samples of base treated α-casein and 22 samples of soy protein and the results of the analysis of amino acids in two balanced diet mixtures are presented. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984  相似文献   
73.
In this investigation, a mixed convective nanoparticles fluid flow over an inclined plate is deliberated. The effects of slip boundary wall and magnetic field are also considered. The dimensionless governing system for the considered problem is attained by implementing recent definitions of fractional derivatives (FD). The generalized solution is obtained through the Laplace Transformation Scheme (LTS) for the momentum and thermal expressions. To improve the novelty and to demonstrate some more physical perception of the stated research work, some remarkable special cases of velocity distribution through CF and AB-fractional derivative concept are addressed, whose daily life implication is well known in the existing literature. Moreover, to evaluate the physical interest of the stated problem, the outcomes of the obtained system graphical illustrations are made by utilizing MATHEMATICA. As a result, we concluded that the aluminium oxide Al2O3 nanoparticles show more decaying behavior as compared to titanium oxide TiO2 nanoparticles for temperature and velocity profile. Furthermore, both fields i.e., momentum and thermal distributions are increased with the help of rising estimations parameter. Current results report novel applications in enhancement of heat transfer, thermal engineering, chemical processes, engineering and electronics devices, solar systems, extrusion processes, fission reactions etc.  相似文献   
74.
An improved method for the preparation and purification of ethyl 2-hydroxy-4-oxo-4H-pyrido[1,2-a]-pyrimidine-3-carboxylates is proposed. According to 1H and 13C NMR spectroscopic data the synthesized compounds exist in DMSO solution in the 2-hydroxy-4-oxo form while in the crystal (at least for the case of the unsubstituted derivative) X-ray analysis shows that it occurs in the bipolar 2,4-dioxo form. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 864–876, June, 2007.  相似文献   
75.
四唑及其衍生物的理论研究Ⅷ: 硝氨四唑衍生物的从头算   总被引:3,自引:0,他引:3  
陈兆旭  肖鹤鸣 《化学学报》1998,56(12):1198-1206
运用从头计算法,在HF/6-31G^*水平下,全优化计算了7种硝氨四唑衍生物的分子几何和电子结构。结果表明,标题物的四唑环近似为平面构型;2H式中性分子的芳香性大于相应的1H式异构体。5-硝氨-1H四唑分子内氢键使硝氨基与环共面;其余标题物中硝氨基与环垂直。不同水平下的总能量计算表明,标题物中电子相关效应显著;1H式中性分子较2H式的能量高,5-硝氨四唑负离子在三个负离子中最稳定。根据电荷分布阐明了四唑环质子化位置和标题物与金属的配位方式。此外还计算了各标题物的红外光谱及热力学性质。  相似文献   
76.
The structure of mono- and di-O-arylmercury-derivatives of quinizarin (1,4-dihydroxy-9, 10-anthraquinone) and anthrarufin (1,5-dihydroxy-9, 10-anthraquinone) and their reactions with Br, Cl, OH, andtBuO anions in the solid state and in aprotic solvents were examined by vibrational and electron spectroscopy. These reactions result in cleavage of the O-Hg bond. The formation of ions or contact ion pairs depends on the size and nature of the counterion; quinizarin dianions give very strong ion pairs with K+ cations, which do not cleave in DMSO. The electronic structure of mono- and dianions of the compounds studied is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2933–2940, December, 1996.  相似文献   
77.
Summary The retention, enantionselectivity and enantiomeric elution order of racemic propranolol (PP) and its ester derivatives (O-acetyl,-propionyl,-butyrul and-valeryl PP) on an 1-acid glycoprotein (AGP)-bonded column have been investigated by changing eluent composition (eluent pH, buffer concentration, type and content of organic modifier). The retention of these cationic solutes, PP and its ester derivatives, was influenced by eluent pH, ionic strength and organic modifier content. The enantioselectivity was dependent on eluent pH and type of organic modifier. Reversal of the enantiomeric elution order of ester derivatives of PP (O-propionyl-butyryl) and-valeryl PP) occurred around eluent pH 6–7. These results suggst that chiral recognition or binding properties may be altered by the change in eluent composition, espeically eluent pH and type of organic modifier.  相似文献   
78.
[(Ph3Sn)3VO4]·CH3CN and [(Ph3Sn)3VO4]·2 DMF, Triphenyltin Vanadates with Novel Chain Structures The reaction of Na3VO4 with Ph3SnCl in a water/CH2Cl2 mixture leads to the formation of [(Ph3Sn)3VO4] ( 1 ). Recrystallization of 1 from toluene/CH3CN gives pale yellow crystals of [(Ph3Sn)3VO4]·CH3CN ( 2 ). 2 crystallizes as coordination polymer which consists of infinite chains composed of corner‐sharing VO4 tetrahedra and Ph3SnO2 trigonal bipyramides. Additionally the VO4 groups are connected to two terminal SnPh3‐Groups containing tin atoms in a tetrahedral environment. [(Ph3Sn)3VO4]·2 DMF ( 3 ) which is obtained from Na3VO4 and Ph3SnCl in a water/DMF mixture contains a polymeric chain structure similar to 2 and additionally one of the terminal SnPh3 groups is coordinated to a DMF solvent molecule.  相似文献   
79.
Synthesis of novel-2,3-bifunctionalised indole regioisomers (2/3 and 6/7) from unsymmetrical dicyanoanilines 1 by regioselective cyclization in two independent ways. Regioisomers 6 are further utilized in synthesis of novel 4,5-dihydro[1,3]oxazino[5,4-b] indole-6-carbonitriles 9.  相似文献   
80.
Summary Reversed (RP-HPLC) and normal phase chromatographic (NP-HPLC) separations have been developed for diastereomers ofN-acyl-1-methyl-1,2,3,4-tetrahydo-β-carbolines which are acylated derivatives of simple natural β-carboline alkaloids. Separations of derivatives having different acyl moieties in theO,O-diacyl-tartaric acid ester subtituent differed remarkably. Little or no resolution in either NP-HPLC or RP-HPLC could be achieved with the diacetyl-tartrate derivative. Base-line separation by RP-HPLC but no separation by NP-HPLC was possible with the bulkier and more apolar dipivaloyl derivative. Retention order of the bis-benzoylated diastereomers was reversed and separation time increased dramatically by RP-HPLC. Good separation of the medium polarity, but rigid,N-camphanyl derivative by NP-HPLC has been achieved, whereas RP-HPLC could not be used for separation of these diastereomers. Separability of different diastereomers was highly dependent on polarity and rigidity of the derivatizingN-acyl moieties. Conformational analysis by molecular mechanics and comparison of the lowest energy conformational states of the diastereomers was applied to rationalise separation-retention behaviour of stereoisomers by RP-HPLC. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001  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