全文获取类型
收费全文 | 29444篇 |
免费 | 3178篇 |
国内免费 | 5459篇 |
专业分类
化学 | 28427篇 |
晶体学 | 202篇 |
力学 | 1565篇 |
综合类 | 160篇 |
数学 | 806篇 |
物理学 | 4892篇 |
无线电 | 2029篇 |
出版年
2024年 | 92篇 |
2023年 | 516篇 |
2022年 | 802篇 |
2021年 | 1047篇 |
2020年 | 1472篇 |
2019年 | 1203篇 |
2018年 | 1223篇 |
2017年 | 1168篇 |
2016年 | 1316篇 |
2015年 | 1212篇 |
2014年 | 1825篇 |
2013年 | 2624篇 |
2012年 | 1586篇 |
2011年 | 2020篇 |
2010年 | 1544篇 |
2009年 | 1742篇 |
2008年 | 1813篇 |
2007年 | 2003篇 |
2006年 | 1828篇 |
2005年 | 1626篇 |
2004年 | 1635篇 |
2003年 | 1304篇 |
2002年 | 841篇 |
2001年 | 688篇 |
2000年 | 687篇 |
1999年 | 608篇 |
1998年 | 509篇 |
1997年 | 445篇 |
1996年 | 396篇 |
1995年 | 369篇 |
1994年 | 302篇 |
1993年 | 231篇 |
1992年 | 215篇 |
1991年 | 181篇 |
1990年 | 133篇 |
1989年 | 118篇 |
1988年 | 103篇 |
1987年 | 68篇 |
1986年 | 58篇 |
1985年 | 60篇 |
1984年 | 60篇 |
1983年 | 31篇 |
1982年 | 48篇 |
1981年 | 42篇 |
1980年 | 35篇 |
1979年 | 36篇 |
1977年 | 31篇 |
1976年 | 38篇 |
1974年 | 39篇 |
1973年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
摩擦强度对薄膜表面形态的作用:原子力显微镜下的观察 总被引:2,自引:2,他引:0
展示了摩擦强度对聚酰亚胺薄膜表面形态的影响,原子力显微图像显示,机械摩擦会使聚酰亚胺薄膜表面上形成微沟槽,这些沟槽的表面具有丰富的表面精细构造。原子显微图像还揭示了机械摩擦可以改变被磨擦聚酰亚胺膜的表面形态。 相似文献
22.
Cosmic dust and our origins 总被引:1,自引:0,他引:1
J Mayo Greenberg 《Surface science》2002,500(1-3):793-822
The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized. 相似文献
23.
1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1~4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7~14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- … 相似文献
24.
G.P. Romanelli D. Bennardi D.M. Ruiz G. Baronetti H.J. Thomas 《Tetrahedron letters》2004,45(48):8935-8939
Substituted coumarins are synthesized from phenols and β-ketoesters by the Pechmann reaction, using a Wells-Dawson heteropolyacid (H6P2W18O62·24H2O) as catalyst by a solvent-free procedure. This one requires low reaction times, 130 °C temperature and as little as 1 mol % of Wells-Dawson acid, obtaining good to excellent yields of coumarins. The catalyst showed to be reusable with no differences in the yields. The results are compared with those of the reactions performed in toluene solution. The presented synthetic procedure is a convenient, clean and fast alternative for synthesizing 4-substituted coumarins (17 examples). 相似文献
25.
26.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
27.
K. C. Kumara Swamy E. Balaraman M. Phani Pavan N. N. Bhuvan Kumar K. Praveen Kumar N. Satish Kumar 《Journal of Chemical Sciences》2006,118(6):495-501
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated
acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature
of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction. 相似文献
28.
Yuliya V. Rassukana Kateryna O. Davydova Anatolii D. Sinitsa 《Tetrahedron letters》2004,45(20):3899-3902
Hydrophosphoryl nucleophilic agents add to the CN bond of N-sulfonyltrichloroacetimidoylphosphonates to give unstable C,C-diphosphorylated adducts, which undergo competitive 1,2-C → N phosphorotropic rearrangement and dehydrochlorination with the formation of aza-Perkow reaction products, C,N-diphosphorylated dichlorovinylsulfonamides. This is the first reliably identified case of an aza-Perkow transformation for acid phosphites and their initial nucleophilic attack at the C atom of the azomethine bond in the aza-substrates. 相似文献
29.
Mao‐Chuan Yuan Ping‐I Shih Chen‐Han Chien Ching‐Fong Shu 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2925-2937
We have synthesized a blue‐light‐emitting polyfluorene (PF) derivative ( PF‐CBZ‐OXD ) that presents bulky hole‐transporting carbazole and electron‐transporting oxadiazole pendent groups functionalized at the C‐9 positions of alternating fluorene units. The results from photoluminescence and electrochemical measurements indicate that both the side chains and the PF main chain retain their own electronic characteristics in the copolymer. An electroluminescent device incorporating this polymer as the emitting layer was turned on at 4.5 V; it exhibited a stable blue emission with a maximum external quantum efficiency of 1.1%. Moreover, we doped PF‐CBZ‐OXD and its analogue PF‐TPA‐OXD with a red‐light‐emitting iridium phosphor for use as components of phosphorescent red‐light emitters to investigate the effect of the host's HOMO energy level on the degree of charge trapping and on the electrophosphorescent efficiency. We found that spectral overlap and individual energy level matching between the host and guest were both crucial features affecting the performance of the electroluminescence devices. Atomic force microscopy measurements indicated that the dipolar nature of PF‐CBZ‐OXD , in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment that allowed homogeneous dispersion of the polar iridium triplet dopant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2925–2937, 2007 相似文献
30.
Calculations and detailed first principle and thermodynamic analyses have been performed to understand the formation mechanism of K2Ti6O13 nanowires (NWs) by a hydrothermal reaction between bulk Na2Ti3O7 crystals and a KOH solution. It is found that direct ion exchange between K+ and Na+ plus H+ interactions with [TiO6] octahedra in Na2Ti3O7 promote the formation of an intermediate H2K2Ti6O14 phase. The large lattice mismatch between this intermediate phase and the bulk Na2Ti3O7 structure, and the large energy reduction associated with the formation of this intermediate phase, drive the splitting of the bulk crystal into H2K2Ti6O14 NWs. However, these NWs are not stable because of large [TiO6] octahedra distortion and are subject to a dehydration process, which results in uniform K2Ti6O13 NWs with narrowly distributed diameters of around 10 nm. 相似文献