全文获取类型
收费全文 | 2512篇 |
免费 | 821篇 |
国内免费 | 474篇 |
专业分类
化学 | 1902篇 |
晶体学 | 8篇 |
力学 | 119篇 |
综合类 | 24篇 |
数学 | 158篇 |
物理学 | 1596篇 |
出版年
2024年 | 3篇 |
2023年 | 19篇 |
2022年 | 52篇 |
2021年 | 37篇 |
2020年 | 60篇 |
2019年 | 88篇 |
2018年 | 83篇 |
2017年 | 102篇 |
2016年 | 103篇 |
2015年 | 236篇 |
2014年 | 239篇 |
2013年 | 319篇 |
2012年 | 254篇 |
2011年 | 273篇 |
2010年 | 233篇 |
2009年 | 221篇 |
2008年 | 246篇 |
2007年 | 167篇 |
2006年 | 149篇 |
2005年 | 126篇 |
2004年 | 112篇 |
2003年 | 120篇 |
2002年 | 86篇 |
2001年 | 87篇 |
2000年 | 68篇 |
1999年 | 50篇 |
1998年 | 61篇 |
1997年 | 39篇 |
1996年 | 37篇 |
1995年 | 33篇 |
1994年 | 29篇 |
1993年 | 23篇 |
1992年 | 12篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有3807条查询结果,搜索用时 15 毫秒
61.
The introduction of sulfur atoms onto target molecules is an important area in organic synthesis, in particular in the synthesis of pharmaceutical compounds, and a wide variety of sulfuration agents have been developed for thionation reactions over the past few decades. In this Focus Review, we collect and summarize the C? S bond‐formation reactions that have been used to construct C? S bonds in natural products and pharmaceutical compounds. 相似文献
62.
An improved, mild procedure for the CuI‐catalyzed coupling reactions of aryl iodides with aliphatic and aromatic thiols, using L ‐proline as the ligand, is reported. This procedure is noteworthy given its high generality and exceptional level of functional group toleration. 相似文献
63.
A highly effective, convenient, and reproducible industrial process for palladium‐catalyzed carbon–nitrogen cross coupling has been developed and applied on a large scale. Thus various functionalized N‐arylhydrazones have been easily prepared and well characterized by conventional spectroscopic methods. 相似文献
64.
Peptides bearing an acryloyl residue at their N‐terminus were coupled with various C‐glycosides in an equimolar ratio via cross‐metathesis. The newly formed olefin was obtained with high E/Z selectivity in satisfying to high yields with low homodimerization of the starting materials. The posttranslational cross‐metathesis approach was shown to be suitable for the combinatorial synthesis of a small library of C‐glycopeptides. 相似文献
65.
Yu Liu Lei Zhao Wentao Li Dongyu Zhao Miao Song Yongliang Yang 《Journal of computational chemistry》2013,34(1):67-75
The accurate prediction of protein–ligand binding is of great importance for rational drug design. We present herein a novel docking algorithm called as FIPSDock, which implements a variant of the Fully Informed Particle Swarm (FIPS) optimization method and adopts the newly developed energy function of AutoDock 4.20 suite for solving flexible protein–ligand docking problems. The search ability and docking accuracy of FIPSDock were first evaluated by multiple cognate docking experiments. In a benchmarking test for 77 protein/ligand complex structures derived from GOLD benchmark set, FIPSDock has obtained a successful predicting rate of 93.5% and outperformed a few docking programs including particle swarm optimization (PSO)@AutoDock, SODOCK, AutoDock, DOCK, Glide, GOLD, FlexX, Surflex, and MolDock. More importantly, FIPSDock was evaluated against PSO@AutoDock, SODOCK, and AutoDock 4.20 suite by cross‐docking experiments of 74 protein–ligand complexes among eight protein targets (CDK2, ESR1, F2, MAPK14, MMP8, MMP13, PDE4B, and PDE5A) derived from Sutherland‐crossdock‐set. Remarkably, FIPSDock is superior to PSO@AutoDock, SODOCK, and AutoDock in seven out of eight cross‐docking experiments. The results reveal that FIPS algorithm might be more suitable than the conventional genetic algorithm‐based algorithms in dealing with highly flexible docking problems. © 2012 Wiley Periodicals, Inc. 相似文献
66.
Dr. Umesh A. Kshirsagar Regev Parnes Hagit Goldshtein Dr. Rivka Ofir Dr. Raz Zarivach Dr. Doron Pappo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13575-13583
An iron‐based cross‐dehydrogenative coupling (CDC) approach was applied for the diversity‐oriented synthesis of coumestrol‐based selective estrogen receptor modulators (SERMs), representing the first application of CDC chemistry in natural product synthesis. The first stage of the two‐step synthesis of coumestrol involved a modified aerobic oxidative cross‐coupling between ethyl 2‐(2,4‐dimethoxybenzoyl)acetate and 3‐methoxyphenol, with FeCl3 (10 mol %) as the catalyst. The benzofuran coupling product was then subjected to sequential deprotection and lactonization steps, affording the natural product in 59 % overall yield. Based on this new methodology other coumestrol analogues were prepared, and their effects on the proliferation of the estrogen receptor (ER)‐dependent MCF‐7 and of the ER‐independent MDA‐MB‐231 breast cancer cells were tested. As a result, new types of estrogen receptor ligands having an acetamide group instead of the 9‐hydroxyl group of coumestrol were discovered. Both 9‐acetamido‐coumestrol and 8‐acetamidocoumestrol were found more active than the natural product against estrogen‐dependent MCF‐7 breast cancer cells, with IC50 values of 30 and 9 nM , respectively. 相似文献
67.
A Rapid and Efficient Way to Dynamic Creation of Cross‐Reactive Sensor Arrays Based on Ionic Liquids
Wei Zhu Weina Li Haowei Yang Yin Jiang Chen Wang Prof. Dr. Yu Chen Prof. Dr. Guangtao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11603-11612
Based on the simple counterion exchange of ionic liquids, a rapid, facile, and efficient strategy to create a cross‐reactive sensor array with a dynamic tunable feature was developed, and exemplified by the construction of a sensor array for the identification and classification of nitroaromatics and explosives mimics. To achieve a good sensing system with fast response, good sensitivity, and low detection limit, the synthesized ionic liquid receptors were tethered onto a silica matrix with a macro‐mesoporous hierarchical structure. Through the facile anion exchange approach, abundant ionic‐liquid‐based individual receptors with diversiform properties, such as different micro‐environments, diverse molecular interactions, and distinctive physico‐chemical properties, were easily and quickly synthesized to generate a distinct fingerprint of explosives for pattern recognition. The reversible anion exchange ability further endowed the sensor array with a dynamic tunable feature as well as good controllability and practicality for real‐world application. With the assistance of statistical analysis, such as principal component analysis (PCA) and linear discrimination analysis (LDA), an optimized‐size array with a good resolution was rationally established from a large number of IL‐based receptors. The performed experiments suggested that the ionic‐liquid‐based sensing protocol is a general and powerful strategy for creating a cross‐reactive sensor array that could find a wide range of applications for sensing various analytes or complex mixtures. 相似文献
68.
Amanda S. Santana Diego B. Carvalho Nadla S. Cassemiro Luiz H. Viana Gabriela R. Hurtado Marcos S. Amaral Najla M. Kassab Palimécio G. Guerrero Jr. Sandro L. Barbosa Miguel J. Dabdoub Adriano C.M. Baroni 《Tetrahedron letters》2014
A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophenes were used as substrates in Sonogashira cross-coupling reactions to obtain thiophene acetylenes. 相似文献
69.
Ligand‐Free Palladium‐Catalyzed Aerobic Oxidative Coupling of Carboxylic Anhydrides with Arylboronic Acids 下载免费PDF全文
We report a new, effective and environmentally friendly protocol for selective aerobic oxidative coupling of arylboronic acids with carboxylic anhydrides in the presence of ligand‐free palladium catalyst. The aryl benzoates are obtained in good to excellent yields. 相似文献
70.
Yusuke Shiraki Kazuhiro Tsuruta Junpei Morimoto Chihiro Ohba Akifumi Kawamura Ryo Yoshida Ryuji Kawano Tadashi Uragami Takashi Miyata 《Macromolecular rapid communications》2015,36(6):515-519
Microdevices designed for practical environmental pollution monitoring need to detect specific pollutants such as dioxins. Bisphenol A (BPA) has been widely used as a monomer for the synthesis of polycarbonate and epoxy resins. However, the recent discovery of its high potential ability to disrupt human endocrine systems has made the development of smart systems and microdevices for its detection and removal necessary. Molecule‐responsive microsized hydrogels with β‐cycrodextrin (β‐CD) as ligands are prepared by photopolymerization using a fluorescence microscope. The molecule‐responsive micro‐hydrogels show ultra‐quick shrinkage in response to target BPA. Furthermore, the flow rate of a microchannel is autonomously regulated by the molecule‐responsive shrinking of their hydrogels as smart microvalves.