全文获取类型
收费全文 | 13891篇 |
免费 | 2607篇 |
国内免费 | 1646篇 |
专业分类
化学 | 17543篇 |
晶体学 | 58篇 |
力学 | 17篇 |
综合类 | 30篇 |
数学 | 6篇 |
物理学 | 490篇 |
出版年
2024年 | 32篇 |
2023年 | 255篇 |
2022年 | 364篇 |
2021年 | 517篇 |
2020年 | 980篇 |
2019年 | 685篇 |
2018年 | 666篇 |
2017年 | 454篇 |
2016年 | 836篇 |
2015年 | 927篇 |
2014年 | 1025篇 |
2013年 | 1203篇 |
2012年 | 938篇 |
2011年 | 1000篇 |
2010年 | 803篇 |
2009年 | 854篇 |
2008年 | 896篇 |
2007年 | 755篇 |
2006年 | 735篇 |
2005年 | 660篇 |
2004年 | 700篇 |
2003年 | 550篇 |
2002年 | 413篇 |
2001年 | 233篇 |
2000年 | 191篇 |
1999年 | 225篇 |
1998年 | 203篇 |
1997年 | 192篇 |
1996年 | 155篇 |
1995年 | 151篇 |
1994年 | 102篇 |
1993年 | 81篇 |
1992年 | 84篇 |
1991年 | 41篇 |
1990年 | 30篇 |
1989年 | 38篇 |
1988年 | 37篇 |
1987年 | 22篇 |
1986年 | 16篇 |
1985年 | 17篇 |
1984年 | 10篇 |
1983年 | 13篇 |
1982年 | 9篇 |
1981年 | 5篇 |
1980年 | 9篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1972年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Claudia Savelli Riccardo Salvio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5856-5863
Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts. 相似文献
22.
23.
杂多酸催化合成乙酸乙酯 总被引:14,自引:0,他引:14
回流吸附法制备的负载型12-钨磷酸(HPW/C)是合成乙酸乙酯的高效催化剂。最佳反应条件下乙醇转化率达96%,酯化选择性100%。催化剂的高活性是由于HPW在活性炭上高度分散,使活性位增多,有效酸量增大。HPW/C还具有热稳定性高和不易流失等优点。 相似文献
24.
本文用密度泛函理论(DFT)的总能计算研究了一氧化碳和氢原子在Ni(111)表面上p(2×2)共吸附系统的原子结构和电子态,结果表明CO和H原子分别被吸附于两个对角p(1×1)元胞的hcp和fcc位置.以氢分子和CO分子作为能量参考点,总吸附能为2.81 eV,相应的共吸附表面功函数φ为6.28 eV.计算得到的C—O,C—Ni和H—Ni的键长分别是1.19?, 1.96?和 1.71?,并且CO分子以C原子处于hcp的谷位与金属衬底原子结合.衬底Ni(111)的最外两层的晶面间距在吸附后的相对变化分别是
关键词:
Fisher-Tropsch反应
催化作用
Ni(111) p(2×2)/(CO+H)
共吸附 相似文献
25.
26.
Thin Ca films were evaporated on Si(1 1 1) under UHV conditions and subsequently annealed in the temperature range 200–650 °C. The interdiffusion of Ca and Si was examined by ex situ Auger depth profiling. In situ monitoring of the Si 2p core-level shift by X-ray photoemission spectroscopy (XPS) was employed to study the silicide formation process. The formation temperature of CaSi2 films on Si(1 1 1) was found to be about 350 °C. Epitaxial growth takes place at T≥400 °C. The morphology of the films, measured by atomic force microscopy (AFM), was correlated with their crystallinity as analyzed by X-ray diffraction (XRD). According to measurements of temperature-dependent I–V characteristics and internal photoemission the Schottky-barrier height of CaSi2 on Si(1 1 1) amounts to qΦBn=0.25 eV on n-type and to qΦBp=0.82 eV on p-type silicon. 相似文献
27.
A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated. 相似文献
28.
Simonetta Orlandi 《Tetrahedron letters》2004,45(8):1747-1749
A mild, decarboxylative, aldol-type addition of malonic acid hemithioesters to aldehydes has been shown to occur with up to 39% enantioselectivity when the reaction was carried out in the presence of catalytic amounts of a Cu(II) salt, an enantiopure, tartaric acid-derived bis-benzimidazole and an achiral base. 相似文献
29.
Pengbo Jiang Tiexin Cheng Yan Liu Xianghao Cui Yingli Bi Kaiji Zhen 《Reaction Kinetics and Catalysis Letters》2004,82(1):49-56
The novel phase transfer catalysts S-8 [4-(dimethyloctylammonium) propansultan] and DB-X [1,4-bis(triethylmethylammonium)benzene dibromide] were synthesized and employed for high conversion synthesis of dichlorocyclopropane from various olefins.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
30.
A synthetic form of the mineral hewettite was prepared via a new route in aqueous medium, starting either from the crystalline compound Li1.1V3O8, or from its amorphous precursor. The anhydrous, crystalline derivative Ca0.5V3O8 was obtained by heating the synthetic hewettite at 250°C under dynamic vacuum. The diffraction studies show that the 2D structure of Ca0.5V3O8 involves the same V3O8 layers as in the hewettite or in Li1+αV3O8. The stacking of the layers is similar to that in the metahewettite. A structural model is proposed, where the Ca2+ ions occupy octahedral sites in the interlayer space. The electrochemical behavior of Ca0.5V3O8 vs. lithium insertion is presented. It is original and reveals particularly good performances in terms of stability during cycling at C/5 rate. The homologues obtained with Mg or Ba, instead of Ca, are briefly presented. 相似文献