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   74980篇
  免费   14051篇
  国内免费   5236篇
化学   74553篇
晶体学   1303篇
力学   2531篇
综合类   137篇
数学   5882篇
物理学   9861篇
  2024年   60篇
  2023年   250篇
  2022年   767篇
  2021年   944篇
  2020年   1511篇
  2019年   3041篇
  2018年   2853篇
  2017年   3395篇
  2016年   3893篇
  2015年   6042篇
  2014年   5907篇
  2013年   8395篇
  2012年   6581篇
  2011年   6311篇
  2010年   5138篇
  2009年   5006篇
  2008年   5267篇
  2007年   4638篇
  2006年   4261篇
  2005年   3972篇
  2004年   3376篇
  2003年   3053篇
  2002年   3500篇
  2001年   1946篇
  2000年   1687篇
  1999年   856篇
  1998年   269篇
  1997年   242篇
  1996年   214篇
  1995年   190篇
  1994年   126篇
  1993年   137篇
  1992年   74篇
  1991年   73篇
  1990年   46篇
  1989年   31篇
  1988年   33篇
  1987年   33篇
  1986年   24篇
  1985年   22篇
  1984年   17篇
  1983年   16篇
  1982年   13篇
  1981年   13篇
  1980年   10篇
  1979年   11篇
  1978年   5篇
  1977年   3篇
  1973年   4篇
  1972年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
IntroductionMethaneandcarbondioxidearetWomaincompositionsforthegreenhouseeffectandtheworldglobewanningll].ItisbeneficialtoourlivingenviroIUnenttocontrolthereleaseofthesetwogases.Theconversionofmethanetothecommonfeedstocksynthesisgas(carbonmonoxideandhydro…  相似文献   
992.
A chiral stationary phase (CSP) based on (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was evaluated for the direct resolution of the enantiomers of dipeptides and tripeptides. The type and concentration of the acid and the methanol content were optimized with regard to retention time and resolution using Ala-Phe as model peptide. A mobile phase consisting of 10 mM sulfuric acid in 70% aqueous methanol was applied to the separation of a set of 16 structurally diverse dipeptides and tripeptides. Generally, the configuration of the amino acid at the N-terminus determined the enantiomer elution order. With a few exceptions the LL- and LD-enantiomers interacted stronger with the CSP compared to the corresponding DD- or DL-enantiomers. The experimental conditions also allowed the simultaneous separation of all four stereoisomers of Ala-Phe. Addition of ammonium sulfate generally reduced retention times and enantiomer resolution. Addition of triethylamine as modifier led to an overall increase of the retention times while the resolution did not show a general trend, increasing in the case of Ala-Ala but decreasing in the case of Ala-Phe.  相似文献   
993.
Spherical, smooth-surfaced and mechanically stable alginate-poly(L-histidine) (PLHis) microcapsules with narrow particle size distributions were prepared by incubating calcium alginate beads in aqueous solutions of PLHis. The in vitro release characteristics, drug loading and encapsulation efficiency of the microcapsules were investigated using bovine erythrocytes hemoglobin (Hb) as a model drug. The results showed that the concentration of Ca(2+) ions had a considerable effect on the drug loading, encapsulation efficiency and in vitro release behavior of the microcapsules. When the concentration of CaCl(2) in the PLHis solution was increased from 0 to 3.0% (w/v), the drug loading and encapsulation efficiency decreased significantly from 38.0 to 4.3% and from 92.9 to 8.0%, respectively, while the total cumulative release of Hb from microcapsules in phosphate buffered saline solution (PBS, pH 6.8) decreased from 96.2 to 72.8% in 24 h. No significant protein release was observed during 70 h of incubation in hydrochloric acid solution (pH 1.2). However, under neutral conditions (PBS, pH 6.8), the Hb was completely and stably released within 24-70 h. An explosion test showed that the stability of alginate-PLHis microcapsules depended strongly on the concentration of PLHis and the calcium ions in solution. [Diagram: see text] Microscopy photo of Hb-loaded alginate-PLHis microcapsules.  相似文献   
994.
Some triplet energy-transfer reactions initiated by photoexcitation of the triplet excited state of dibenz[a,h]anthracene to higher triplet excited states (DBA(Tn)) were observed in the presence of the triplet energy quenchers (Q) such as naphthalene, biphenyl, p-dichlorobenzene, and o-dicyanobenzene. In the case of carbon tetrachloride (CCl4) as Q, DBA(Tn)-sensitized decomposition of CCl4 occurred.  相似文献   
995.
A Monte‐Carlo simulation approach has been applied to describe the spatial distribution of characteristic x‐rays in W/Al film targets of different combinations of film thicknesses for the optimal design of a small‐sized x‐ray source having a high x‐ray intensity. The result has led to optimal combinations of W and Al film targets for 100 kV electrons, e.g. W(1 µm)/Al(20 µm), W(3 µm)/Al(15 µm) and W(5 µm)/Al(8 µm). These Al/W targets could be used as x‐ray sources for a medical instrument currently under development. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   
996.
张丽圆  王磊 《中国化学》2006,24(11):1605-1608
Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields. Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity.  相似文献   
997.
The structure of [CoCl2(C6H4N3CH2Ph)2] has been determined by X-ray crystallography. It is also characterized by elemental analysis, IR and electronic spectroscopy, and by thermogravimetric differential thermal analysis. It crystallizes in the monoclinic system, space group C2/c, with lattice parameters a = 16.133(3) , b = 11.355(2) , c = 15.637(3) , = 117.22(3)°, and Z = 8. The crystal structure of the title compound consists of monomeric molecules of [CoCl2(C6H4N3CH2Ph)2] with slightly distorted tetrahedron geometry for the CoCl2N2 chromophore. The thermal gravimetry (TG) data indicate that there are four decomposition steps with five endothermic peaks. The final product of the thermal decomposition is CoCl2. Elemental analysis and the electronic and IR spectra are in agreement with the structural data.Original Russian Text Copyright © 2004 by F. Jian, H. Wang, and H. XiaoTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 723–728, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.  相似文献   
998.
《Chemphyschem》2004,5(8):1171-1177
The primary light‐induced processes of phycocyanobilin were studied by means of transient‐grating spectroscopy, whereby the excitation wavelength was varied over the spectral region of the ground‐state absorption. On the basis of the results obtained, both the rate of the photoreaction in phycocyanobilin and the ratio of the decay of different excited‐state species via two decay channels depend on the excitation wavelength. Furthermore, the formation of the photoreaction product is also dependent on the pump color. These data support a recently established model for the primary photoprocesses in phycocyanobilin. In addition, phycocyanobilin protonated at the basic pyrrolenine‐type nitrogen atom was included in the transient absorption study. The decay behavior was found to be almost unchanged when compared with the unprotonated form, and this suggests that protonation of the tetrapyrrole ring structure has no effect on the overall photochemistry.  相似文献   
999.
程庆彦  钟顺和 《催化学报》2003,24(7):558-562
 采用表面改性法制备了负载型Ni2(OEt)2/SiO2双核金属乙氧基配合物催化剂,利用示差量热、红外光谱和微反技术对催化剂的表面结构、热稳定性、化学吸附性质和催化活性进行了研究.结果表明,负载型双核金属乙氧基配合物Ni2(OEt)2/SiO2中的Ni2+与载体SiO2表面的O2-以双齿配位形式键合;二氧化碳在催化剂表面存在桥式吸附态和碳酸单乙酯基物种两种吸附态,丙烯则只有一种分子吸附态;在适宜的反应条件下,二氧化碳和丙烯在Ni2(OEt)2/SiO2催化剂上的反应产物主要是甲基丙烯酸.根据实验结果,提出了二氧化碳和丙烯在Ni2(OEt)2/SiO2催化剂表面的反应机理,反应物分子共吸附于催化剂表面同一活性单元上,羧酸根和丙烯解离吸附态的形成是反应顺利进行的关键步骤.  相似文献   
1000.
Density functional theory (DFT) and Monte Carlo (MC) simulation with free energy perturbation (FEP) techniques have been used to study the tautomeric proton transfer reaction of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water. Two reaction pathways were considered: the direct and water-assisted transfers. The optimized structures and thermodynamic properties of stationary points for the title reaction system in the gas phase were calculated at the B3LYP/6-311+G(d, p) level of theory. The potential energy profiles along the minimum energy path in the gas phase and in water were obtained. The study of the solvent effect of water on the proton transfer of 2-amino-2-oxozoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline indicates that water as a solvent is favorable for the water-assisted process and slows down the rate of the direct transfer pathway.  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