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   19184篇
  免费   3304篇
  国内免费   1687篇
化学   13267篇
晶体学   179篇
力学   1040篇
综合类   67篇
数学   2034篇
物理学   7588篇
  2024年   63篇
  2023年   402篇
  2022年   712篇
  2021年   744篇
  2020年   741篇
  2019年   757篇
  2018年   738篇
  2017年   589篇
  2016年   987篇
  2015年   877篇
  2014年   1092篇
  2013年   1425篇
  2012年   1736篇
  2011年   1770篇
  2010年   1162篇
  2009年   1086篇
  2008年   1206篇
  2007年   1046篇
  2006年   1001篇
  2005年   795篇
  2004年   605篇
  2003年   431篇
  2002年   440篇
  2001年   336篇
  2000年   283篇
  1999年   389篇
  1998年   279篇
  1997年   293篇
  1996年   288篇
  1995年   247篇
  1994年   211篇
  1993年   216篇
  1992年   152篇
  1991年   161篇
  1990年   137篇
  1989年   103篇
  1988年   88篇
  1987年   72篇
  1986年   71篇
  1985年   57篇
  1984年   58篇
  1983年   32篇
  1982年   33篇
  1981年   24篇
  1980年   27篇
  1976年   18篇
  1975年   16篇
  1974年   14篇
  1973年   18篇
  1968年   15篇
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
101.
To obtain new materials with synergetic or complementary behaviors, polyaniline composite filled with ZnO rods in ramification-like structure was prepared by a hydrothermal approach. Comparative experiments of ZnO preparation in the presence of some metal ions were also carried out. The results indicated that the morphology of ZnO was strongly affected by the preparation condition. The method to grow ZnO rods in the presence of polyaniline offers a simple approach to obtain polyaniline composite filled with linear ZnO structure. The results of X-ray photoelectron spectroscopy show that the strong interaction between ZnO and polyaniline possibly exists to cause the charge transfer.  相似文献   
102.
Poly(amide imide) (PAI) was synthesized using 1,2,4-benzenetricarboxylic anhydride (BTBA) and 4,4′-methylenebis(phenyl isocyanate) (MBPI). SPEEK/PAI blend membranes were prepared and investigated by NMR, GPC, FT-IR and AFM. The chemical structures of PAI and SPEEK were characterized by using NMR and FT-IR. The adsorption of the SPEEK/PAI blend membrane of water or methanol solution was also characterized. The significant swelling of the blend membrane in concentrated methanol solution was explained by the solubility parameter. The water diffusion coefficient (DH2O) was related to the lambda value of the membrane. The SPEEK/PAI blend membrane had a lower proton conductivity and methanol permeability than Nafion. However, the relative selectivity (proton conductivity divided by methanol permeability) of the SPEEK/PAI 70/30 (w/w) blend membrane was 3.46 × 104 S s cm−3, which is closed to that of Nafion (3.30 S s cm−3).  相似文献   
103.
Simple complexes connected through C-H...S and C-H...N interactions are investigated: CH4...NH3, C2H4...NH3, C2H2...NH3, CH4...SH2, C2H4...SH2, and C2H2...SH2. Ab initio and DFT calculations are performed (SCF, MP2, B3LYP) using different basis sets up to the MP2/aug-cc-pVQZ//MP2/aug-cc-pVDZ level of approximation. The Bader theory is applied since MP2/6-311++G(d,p) wave functions are used to find and to characterize bond critical points in terms of electron densities and their Laplacians. The influence of hybridization on the properties of C-H...S and C-H...N systems is also studied showing that the strength of such interactions increases in the following order: C(sp3)-H...Y, C(sp2)-H...Y, C(sp)-H...Y, where Y = S, N--it is in line with the previous findings on C-H...O hydrogen bonds. The results also show that CH4...SH2 and C2H4...SH2 complexes should be rather classified as van der Waals interactions and not as hydrogen bonds. The frequency associated with the C-H stretch of C(sp3)-H...S is blue-shifted.  相似文献   
104.
Polyvinyl alcohol (PVA)-capped CdSe nanoparticles were successfully prepared by a one-step solution growth technique at room temperature and ambient pressure. X-ray diffraction, transmission electron microscopy, infrared spectra, and X-ray photoelectron spectra were used to characterize the final product. The as-prepared CdSe nanocrystals were well dispersed and uniform in shape and the diameter of the particles was confined within 8 nm. Ultraviolet-visible absorption spectra were used to study the confined growth process of PVA-capped CdSe nanoparticles. Photoluminescence measurement showed the near band-edge luminescence of the final product.  相似文献   
105.
密闭空间空气有机物的色/质谱定性分析研究   总被引:9,自引:0,他引:9  
周升如  马健 《分析化学》1991,19(10):1115-1121
  相似文献   
106.
Yields of NH3 and N2H4 in radiation-catalytic reduction of N2 by means of a hydride complex of WIV with dppe in thf solution and in mixtures of thf with other solvents have been estimated. A mechanism proposed earlier of reduction of coordinated N2 has been confirmed and the role of solvent in reduction of N2 to NH3 and amines has been explained.  相似文献   
107.
Ci YX  Zhai Q  Wang S  Chang WB  Zhang CY  Ma H  Chen DY  Zhao MZ  Hu SW 《Talanta》2001,55(4):693-698
In this paper, the voltammetric method was used for the first time to study the effect of Cisplatin-liposome on Hela cells. The results showed the voltammetric behavior of Hela cells was irreversible and the peak current had linear relationship with the cell number. With both Cisplatin-liposome concentration and treating time increasing, the peak current decreased. The peak current decreasing was in accordance with the nuclear damage and loss of mitochondrial membrane potential revealed by two-photon laser scanning microscopy and confocal laser scanning microscopy. This voltammetric method may provide a simple way to study the electron-transfer mechanism in drug-treating cells.  相似文献   
108.
Aquation of [Cr(pic)3]0 and [Cr(pic)2(OH)]2 0 in aqueous HClO4 solutions leads to formation of the common product – [Cr(pic)2(H2O)2]+. The first, reversible stage, the ring opening via Cr—N bond breaking in [Cr(pic)3]0 is followed by the second, rate-determining step – one-end bonded pic ligand liberation. In the case of the [Cr(pic)2(OH)]2 0 complex, the first faster stage produces the singly bridged dimer, which undergoes cleavage into the parent monomers in the second, much slower step. The subsequent aquation of [Cr(pic)2(H2O)2]+ is extremely slow and leads to [Cr(pic)(H2O)4]2+ formation, which practically does not undergo further ligand substitution under the conditions applied. Kinetics of the first aquation stage for [Cr(pic)3]0 and of the second step for [Cr(pic)2(OH)]2 0 were studied spectrophotometrically in the 0.1–1.0 M HClO4 range at I = 1.0 M. The observed pseudo-first order rate constant for [Cr(pic)3]0 decreases with [H+] increase according to the rate law: k obs = k 1 + k –1 Q 1/[H+], where k 1 and k –1 are the rate constants of the forward and the reverse processes in the unprotonated substrate and Q 1 is the protonation constant of the pyridine nitrogen atom. In the case of the [Cr(pic)2(OH)]2 0 complex, the rate for the singly bridged dimer cleavage does not depend on [H+]. The activation parameters for the chelate-ring opening in [Cr(pic)3]0 and for the singly bridged dimer cleavage have been determined and discussed. Some kinetic data of the slow, second aquation stage for the [Cr(pic)3]0 complex and of the fast, first aquation stage for the doubly bridged dimer have been studied; for both reactions the rate increases linearly with the increase in [H+].  相似文献   
109.
Human adenocarcinoma cells of the line WiDr were incubated with 5-aminolevulinic acid to induce protoporphyrin IX (PpIX) and then exposed to laser light of wavelength 635 nm. The PpIX fluorescence decreased with increasing exposure. The decay rate was slightly dependent on the initial PpIX concentration. The PpIX fluorescence was halved by a fluence of about 40 J/cm2. Several fluorescing photoproducts were formed. The main one, supposedly the chlorine-type photoprotoporphyrin (Ppp), had a fluorescence excitation spectrum stretching out to about 680 nm with a maximum at around 668 nm. The formation kinetics of this product was dependent on the initial PpIX concentration. Moreover, it was selectively bleached by exposure to light at 670 nm. A photoproduct with an emission maximum at 652 nm, different from Ppp, remained after this exposure. Traces of a photoproduct(s) with fluorescence emission slightly blue-shifted compared with that of PpIX, supposedly water-soluble porphyrins, were also detected after light exposure.  相似文献   
110.
用三角波电流代替正弦波电流,进行交流示波极谱滴定,所得示波极谱图与正弦波结果相似。对一些离子的滴定表明,两法所得结果均在定量分析允许误差范围以内。报道了三角波交流示波极谱图的一些性质。  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