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   19125篇
  免费   868篇
  国内免费   99篇
化学   13194篇
晶体学   123篇
力学   426篇
数学   2909篇
物理学   3440篇
  2023年   117篇
  2022年   140篇
  2021年   270篇
  2020年   381篇
  2019年   399篇
  2018年   240篇
  2017年   239篇
  2016年   603篇
  2015年   560篇
  2014年   657篇
  2013年   1036篇
  2012年   1126篇
  2011年   1258篇
  2010年   748篇
  2009年   662篇
  2008年   1048篇
  2007年   1025篇
  2006年   959篇
  2005年   890篇
  2004年   785篇
  2003年   644篇
  2002年   616篇
  2001年   320篇
  2000年   294篇
  1999年   277篇
  1998年   244篇
  1997年   231篇
  1996年   266篇
  1995年   252篇
  1994年   221篇
  1993年   211篇
  1992年   200篇
  1991年   176篇
  1990年   180篇
  1989年   174篇
  1988年   150篇
  1987年   125篇
  1986年   115篇
  1985年   168篇
  1984年   166篇
  1983年   129篇
  1982年   156篇
  1981年   160篇
  1980年   134篇
  1979年   142篇
  1978年   160篇
  1977年   117篇
  1976年   102篇
  1975年   117篇
  1974年   92篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
161.
This work highlights four different topics in modeling of DNA: (i) the importance of water and ions together with the structure and function of DNA; the hydration structure around the ions appears to be the determining factor in the ion coordination to DNA, as demonstrated in the results of our MD simulations; (ii) how MD simulations can be used to simulate single molecule manipulation experiments as a complement to reveal the structural dynamics of the studied biomolecules; (iii) how damaged DNA can be studied in computer simulations; and (iv) how repair of damaged DNA can be studied theoretically. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007  相似文献   
162.
163.
The racemic cis-anti-trans-steroids 9 to 11 have been synthesized in a highly stereoselective manner starting from 4-methoxybenzocyclobutene carboxylic acid via the key step 8 → 9 . (cf. Scheme 2).  相似文献   
164.
It is shown that essentially incoherent, stepwise one-photon transitions arising in dense multilevel structures of polyatomic molecules irradiated with monochromatic coherent infrared radiation can give rise (under specified conditions) to a more than proportional intensity dependence of the steady-state rate coefficient in unimolecular reactions induced by monochromatic infrared radiation.  相似文献   
165.
13C-nmr spectral assignments for asperdiol are made with the aid of model compounds and T1 relaxation behavior. Overall isotropic tumbling was inferred from the latter providing a supplemental means of multiplicity determination. Utilization of the T1 relaxation times as an assignment criterion for select resonances in asperdiol is also described.  相似文献   
166.
Lipophilic neutral carriers were synthesized which show Li+/Na+ selectivities of up to ca. 80 in highly lipophilic liquid membranes. The sensor membranes exhibit improved response times and increased lifetimes as compared to systems described earlier. They allow reliable measurements of Li+ in blood serum within the clinical concentration range. A 1:1 Li+/ionophore complex of one representative (N,N,N′,N′-tetracyclohexyl-5,5-dimethyl-3,7-dioxaazelaamide) has been prepared, and its structure was elucidated by X-ray analysis.  相似文献   
167.
HMQC-TOCSY spectra provide a convenient means of establishing proton-proton connectivities in congested spectra of complex aromatic heterocycles. Advantage is taken of the greater dispersion of the 13C nmr spectrum to circumvent overlap which would preclude spectral interpretation through the usual COSY spectrum. A recently reported method for inverting direct responses (IDR) in HMQC-TOCSY spectra is demonstrated for [1]benzothieno[2,3-c]naphtho[2,1-g]quinoline. A modification of the IDR-HMQC-TOCSY method is also demonstrated which is capable of fully suppressing direct responses (SDR) without resorting to the timing of the onset of decoupling as in the original report of the HMQC-TOCSY experiment. SDR-HMQC-TOCSY has the further advantage of allowing the use of higher levels of digitization in F2 than can be attained when broadband heteronuclear decoupling is employed.  相似文献   
168.
A highly sensitive and selective liquid chromatography-mass spectrometry (LC-MS) method has been developed for the determination of epirubicin in serum and cell specimens using daunorubicin as an internal standard. Using atmospheric pressure chemical ionisation (APCI), the epirubicin metabolites were readily distinguishable by their fragmentation pattern in the mass spectrometer. Selected reaction monitoring (SRM) mode was employed for quantitation of epirubicin and the metabolites. Following extraction, chromatography was performed on a C18 column with a mobile phase consisting of water-acetonitrile-formic acid, pH 3.2, with a flow rate of 200 μl/min. The limit of detection (LOD) and the limit of quantitation (LOQ) of this method in serum were determined to be 1.0 and 2.5 ng/ml, respectively. Linearity of the method was verified over the concentration range of 2.5-2000 ng/ml, with a high correlation coefficient (R2 ≥ 0.998). For the extraction procedure, an aliquot of 500 μl serum, spiked with internal standard, was extracted using a chloroform-2-isopropanol (2:1, v/v) mixture. The method has been applied to the analysis of epirubicin in cancer cell samples and the identification of known and unknown metabolites in clinical trial patient serum samples.  相似文献   
169.
170.
The reactions of K[Fe{Si(OMe)3}(CO)3(PY)][PY=Ph2PCH2C(O)Ph, Ph2PCH2C(O)[(-C5H4)FeCp] (Cp=5-C5H5), Ph2P(CH2)2CN] with CdCl2·2.5H2O, ZnX 2 (X=Cl, I) or InCl3 afforded Fe-Cd-Fe or Fe-M(-X)2 M-Fe (M=Cd, Zn, In;X=Cl, I) and Fe-InCl2 complexes. Some of them contain an unusual and labile -2-SiO alkoxysilyl bridge which may be associated with a bridging mode for the ketophosphine ligand (first such example structurally established), thus providing original results in bimetallic chemistry on the intramolecular coordination of oxygendonor functions ofchemically different hemilabile ligands firmly attached to a neighboring metal center. The structures of the trinuclear complex (3), of the chlorobenzene solvate of the tetranuclear complex (4a·C6H5Cl) and of [mer-(OC)3{(EtO)3Si} (4e) have been determined by X-ray diffraction. Crystals of 3 are orthorhombic, space groupPbcn, witha=19.010(4),b=11.766(5),c=26.998(7)Å, andZ=4. Crystals of4a·C6H5Cl are monoclinic, space groupC2/c witha=22.455(3),b=17.680(2),c=16.627(4)Å, =90.80(4)°, andZ=4. Crystals of4e are monoclinic, space groupC2/c witha=25.392(5),b=18.554(6),c=16.28(1)Å, =120.73(3)°, andZ=4. The structures were solved using direct methods and Fourier difference techniques and refined by blocked full-matrix least squares toR=0.035 (R w =0.049) for 2719 observed reflections, toR=0.042 (R w =0.056) for 3082 observed reflections, and toR=0.057 (R w =0.075) for 1850 observed reflections for3, 4a·C6H5Cl and4e, respectively. The Fe-Zn complexes (9a), (9b) and (9c) were prepared and characterized by spectroscopic methods.Part 21 in the Series: Complexes with Functional Phosphines. Part 20: P. Braunstein, S. Coco Cea, A. DeCian, and J. Fischer (1992).Inorg. Chem. 31, 4203.  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