全文获取类型
收费全文 | 4825篇 |
免费 | 840篇 |
国内免费 | 1099篇 |
专业分类
化学 | 4104篇 |
晶体学 | 59篇 |
力学 | 320篇 |
综合类 | 81篇 |
数学 | 532篇 |
物理学 | 1668篇 |
出版年
2024年 | 13篇 |
2023年 | 86篇 |
2022年 | 120篇 |
2021年 | 178篇 |
2020年 | 191篇 |
2019年 | 217篇 |
2018年 | 160篇 |
2017年 | 172篇 |
2016年 | 231篇 |
2015年 | 256篇 |
2014年 | 264篇 |
2013年 | 378篇 |
2012年 | 417篇 |
2011年 | 467篇 |
2010年 | 355篇 |
2009年 | 328篇 |
2008年 | 372篇 |
2007年 | 315篇 |
2006年 | 285篇 |
2005年 | 264篇 |
2004年 | 181篇 |
2003年 | 166篇 |
2002年 | 232篇 |
2001年 | 205篇 |
2000年 | 153篇 |
1999年 | 131篇 |
1998年 | 106篇 |
1997年 | 81篇 |
1996年 | 46篇 |
1995年 | 56篇 |
1994年 | 61篇 |
1993年 | 48篇 |
1992年 | 52篇 |
1991年 | 53篇 |
1990年 | 27篇 |
1989年 | 19篇 |
1988年 | 17篇 |
1987年 | 11篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 9篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1957年 | 1篇 |
1943年 | 1篇 |
排序方式: 共有6764条查询结果,搜索用时 156 毫秒
151.
The development and certification of a coal fly ash certified reference material (CRM) for polycyclic aromatic hydrocarbons (PAH) is described; this is the first natural matrix CRM for organic environmental analysis in China. The homogeneity and stability of this material have been tested by HPLC. The concentrations of several PAH were determined by use of two independent, different methods--solvent extraction-HPLC analysis with UV detection coupled with fluorescence detection (FLD) and solvent extraction, isolation with a silica column, and GC analysis with flame ionization detection (FID). Five certified values were determined: phenanthrene 7.1 +/- 2.6 microg g(-1), anthracene 2.0 +/- 0.8 microg g(-1), fluoranthene 7.4 +/- 1.9 microg g(-1), pyrene 7 +/- 2 microg g(-1), and benzo[a]pyrene 1.3 +/- 0.3 microg g(-1). Reference values for several other PAH are also suggested. 相似文献
152.
Influences of permeation of vanadium ions through PVDF-g-PSSA membranes on performances of vanadium redox flow batteries 总被引:6,自引:0,他引:6
Luo X Lu Z Xi J Wu Z Zhu W Chen L Qiu X 《The journal of physical chemistry. B》2005,109(43):20310-20314
The preparation and physical characterization of a poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) membrane prepared by a solution-grafting method were described. These membranes exhibited high conductivity with a value 3.22 x 10(-2) S/cm at 30 degrees C. ICP studies revealed that the PVDF-g-PSSA membrane showed dramatically lower vanadium ion permeability compared to Nafion 117. Trivalent vanadium ions had the highest permeability through all these membranes in contrast to pentavalent vanadium ions with the lowest. The VRB with the low-cost PVDF-g-PSSA membrane exhibited a higher performance than that with Nafion 117 under the same operating conditions, and its energy efficiency reached 75.8% at 30 mA/cm(2). The performance of VRB with the PVDF-g-PSSA membrane can be maintained after more than 200 cycles at a current density of 60 mA/cm(2). 相似文献
153.
(C2H10N2)[BPO4F2] — Strukturbeziehungen zwischen [BPO4F2]2— und [Si2O6]4— Colourless crystals of (C2H10N2)[BPO4F2] were prepared from mixture of ethylendiamine, H3BO3, BF3 · C2H5NH2, H3PO4 and HCl under mild hydrothermal conditions (220 °C). The crystal structure was determined by single crystal methods (triclinic, P1¯ (no. 2), a = 451.85(5) pm, b = 710.20(8) pm, c = 1210.2(2) pm, α = 86.08(1)°, β = 88.52(2)°, γ = 71.74(1)°, Z = 2) and contains infinite tetrahedral zweier‐single‐chains {[BPO4F2]2—} which are isoelectronic (48e—) with the polyanions {[Si2O6]4—} of the pyroxene family. 相似文献
154.
Effects of self-coiling of organic molecules on intramolecular exciplex formation of compound I,in which the carbazole chromophore and terephthalic acid methylester acceptor group are linked by one (CH2)10 chain,and the decrease of the fluorescence intensities of compounds Ⅱ,Ⅲ,and Ⅳ,in which the carbazole chromophore and 3,5-dinitrobenzoate are connected by one aliphatic chain of (CH2)10 (Ⅱ),(CH2)12(Ⅲ),or (CH2)4(Ⅳ),have been studied in the dioxane (DX)-H2O binary system.The results show that self-coiling of organic molecules in DX-H2O facilitates intramolecular exciplex formation of I and induces the decrease of fluorescence intensities of Ⅱ,bacause of the proximity effect brought about by selfcoiling of organic molecules under hydrophobic-lipophilic interaction(HLI) between the excited carbazole chromophore and the acceptor.Since the similar effects are observed even when the concentration of the probes are less than their CAgCs(critical aggregate concentrations )in the DX-H2O mixture with the same φ values,formation of the intermolecular exciplex has been excluded.The effects are found to be strongly depended on φ values,indication that they are mainly driven by HLI.The properties of the acceptors can also affect the intramolecular exciplex formation.With terephthalic acid methylester moiety as the acceptor,the carbazole chromophore exhibits the fluorescence spectra of the exciplex,while with 3,5-dinitrobenzoate moiety as the acceptor,only the fluorescence spectra of excited carbazolyl chromophore are observed. 相似文献
155.
156.
Sn0.5Ti0.5O2催化剂上SO2、NO和CO反应的机理 总被引:7,自引:0,他引:7
Sn0.5Ti0.5O2催化剂对NO+CO反应活性不高, 350 ℃时NO的转化率只有50%,但反应气中含有SO2时, NO的转化率接近100%,说明SO2对Sn0.5Ti0.5O2催化剂上的NO+CO反应具有促进作用. XPS表征发现,SO2+CO、SO2+NO+CO反应后催化剂表面有微量硫存在,而反应前没有检测到硫的存在.结合反应性能测定、瞬变应答实验、XRD、TPD研究等,发现催化剂上的表面硫参与了NO的催化还原反应,是NO+CO反应更重要的活性中心.据此,提出了SO2+NO+CO反应的氧化还原反应机理. 相似文献
157.
Tetsuro Fujita 《中国化学快报》2007,18(2):175-177
A new highly conjugated alkaloid of veratramine type, 225,25S,5α-veratramine-7(8),12(14)-diene-3β,13β,23β-triol-6-one (1), was isolated from the bulbs of Fritillaria hupehensis Hsiao et K.C. Hsia. Its structure was determined on the basis of spectroscopic evidences. 相似文献
158.
Patterned polyelectrolyte multilayer: surface modification for enhancing selective adsorption 总被引:4,自引:0,他引:4
Shi F Wang Z Zhao N Zhang X 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1599-1602
This paper describes the use of surface chemical modification to enhance the difference of the surface charge on a patterned polyelectrolyte multilayer, which can be used for selectively adsorbing functional materials. We fabricated a patterned multilayer by combining the layer-by-layer self-assembly technique and photolithography and taking advantage of the different solubility of polyelectrolyte multilayers of diazo resins (DAR)/poly(acrylic acid) before and after UV irradiation. This patterned surface can be used as a matrix for selective adsorption of small molecular dyes, such as Methylene Blue. However the difference in surface charge on the patterned surface was not enough when we used it to selectively adsorb polystyrene (PS) nanoparticles using electrostatic force as the driving force. Therefore, we modified the patterned surface by interfacial chemistry. After modification, the patterned polyelectrolyte multilayer can be used as a good matrix for selective adsorption of PS nanoparticles with both positive and negative charges. 相似文献
159.
KMnO4-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields. 相似文献
160.