全文获取类型
收费全文 | 14907篇 |
免费 | 2664篇 |
国内免费 | 1815篇 |
专业分类
化学 | 18517篇 |
晶体学 | 35篇 |
力学 | 11篇 |
综合类 | 30篇 |
数学 | 8篇 |
物理学 | 785篇 |
出版年
2024年 | 34篇 |
2023年 | 276篇 |
2022年 | 395篇 |
2021年 | 550篇 |
2020年 | 1018篇 |
2019年 | 716篇 |
2018年 | 682篇 |
2017年 | 508篇 |
2016年 | 882篇 |
2015年 | 982篇 |
2014年 | 1090篇 |
2013年 | 1248篇 |
2012年 | 1042篇 |
2011年 | 1107篇 |
2010年 | 883篇 |
2009年 | 961篇 |
2008年 | 969篇 |
2007年 | 839篇 |
2006年 | 801篇 |
2005年 | 705篇 |
2004年 | 712篇 |
2003年 | 587篇 |
2002年 | 439篇 |
2001年 | 248篇 |
2000年 | 207篇 |
1999年 | 224篇 |
1998年 | 212篇 |
1997年 | 193篇 |
1996年 | 163篇 |
1995年 | 165篇 |
1994年 | 114篇 |
1993年 | 83篇 |
1992年 | 84篇 |
1991年 | 45篇 |
1990年 | 36篇 |
1989年 | 43篇 |
1988年 | 37篇 |
1987年 | 21篇 |
1986年 | 17篇 |
1985年 | 17篇 |
1984年 | 10篇 |
1983年 | 13篇 |
1982年 | 9篇 |
1980年 | 5篇 |
1978年 | 1篇 |
1977年 | 4篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
21.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters
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)
Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
22.
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
23.
24.
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
25.
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
26.
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.
Juzo Oyamada 《Tetrahedron》2006,62(29):6918-6925
Synthesis of coumarins from phenols and propiolic acids was examined by using a Pt catalyst such as PtCl2/AgOTf, K2PtCl4/AgOTf, and K2PtCl4/AgOAc. Propiolic acid reacted even with less reactive phenols in trifluoroacetic acid to give coumarins and dihydrocoumarins. In the case of substituted propiolic acids, phenylpropiolic acid and 2-octynoic acid, the reactions proceeded selectively to afford coumarins in good to high yields. 相似文献
29.
Teresa uczak Radosaw Pankiewicz Bogusawa ska Grzegorz Schroeder Maria Betowska-Brzezinska Bogumil Brzezinski 《Journal of Molecular Structure》2006,800(1-3):140-145
Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li+ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods. 相似文献
30.
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