全文获取类型
收费全文 | 8378篇 |
免费 | 208篇 |
国内免费 | 42篇 |
专业分类
化学 | 5833篇 |
晶体学 | 40篇 |
力学 | 209篇 |
数学 | 1107篇 |
物理学 | 1439篇 |
出版年
2023年 | 46篇 |
2022年 | 56篇 |
2021年 | 66篇 |
2020年 | 93篇 |
2019年 | 99篇 |
2018年 | 72篇 |
2017年 | 61篇 |
2016年 | 184篇 |
2015年 | 152篇 |
2014年 | 174篇 |
2013年 | 370篇 |
2012年 | 460篇 |
2011年 | 532篇 |
2010年 | 284篇 |
2009年 | 233篇 |
2008年 | 516篇 |
2007年 | 546篇 |
2006年 | 548篇 |
2005年 | 474篇 |
2004年 | 427篇 |
2003年 | 367篇 |
2002年 | 346篇 |
2001年 | 149篇 |
2000年 | 106篇 |
1999年 | 66篇 |
1998年 | 82篇 |
1997年 | 100篇 |
1996年 | 133篇 |
1995年 | 126篇 |
1994年 | 105篇 |
1993年 | 145篇 |
1992年 | 96篇 |
1991年 | 78篇 |
1990年 | 96篇 |
1989年 | 74篇 |
1988年 | 64篇 |
1987年 | 65篇 |
1986年 | 52篇 |
1985年 | 90篇 |
1984年 | 81篇 |
1983年 | 57篇 |
1982年 | 87篇 |
1981年 | 90篇 |
1980年 | 69篇 |
1979年 | 70篇 |
1978年 | 68篇 |
1977年 | 50篇 |
1976年 | 69篇 |
1975年 | 47篇 |
1973年 | 36篇 |
排序方式: 共有8628条查询结果,搜索用时 0 毫秒
721.
Simone Manzini Dr. Albert Poater Dr. David J. Nelson Prof. Dr. Luigi Cavallo Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Steven P. Nolan 《Angewandte Chemie (International ed. in English)》2014,53(34):8995-8999
The decomposition of a series of benzylidene, methylidene, and 3‐phenylindenylidene complexes has been probed in alcohol solution in the presence of base. Tricyclohexylphosphane‐containing precatalysts are shown to yield [RuCl(H)(H2)(PCy3)2] in isopropyl alcohol solutions, while 3‐phenylindenylidene complexes lead to η5‐(3‐phenyl)indenyl products. The potential‐energy surfaces for the formation of the latter species have been probed using density functional theory studies. 相似文献
722.
Dr. Richard D. Adams Dr. Vitaly Rassolov Yuen Onn Wong 《Angewandte Chemie (International ed. in English)》2014,53(41):11006-11009
The electronically unsaturated dirhenium complex [Re2(CO)8(µ‐AuPPh3)(µ‐Ph)] ( 1 ) was obtained from the reaction of [Re2(CO)8{µ‐η2‐C(H)?C(H)nBu}(µ‐H)] with [Au(PPh3)Ph]. The bridging {AuPPh3} group was replaced by a bridging hydrido ligand to yield the unsaturated dirhenium complex [Re2(CO)8(µ‐H)(µ‐Ph)] ( 2 ) by reaction of 1 with HSnPh3. Compound 2 reductively eliminates benzene upon addition of NCMe at 25 °C. The electronic structure of 2 and the mechanism of the reductive elimination of the benzene molecule in its reaction with NCMe were investigated by DFT computational analyses. 相似文献
723.
A Flexible Solution to Anion Transport: Powerful Anionophores Based on a Cyclohexane Scaffold 下载免费PDF全文
James A. Cooper Steven T. G. Street Prof. Anthony P. Davis 《Angewandte Chemie (International ed. in English)》2014,53(22):5609-5613
Transmembrane anion carriers (anionophores) have potential for biological activity, including the treatment of channelopathies such as cystic fibrosis. A new family of anionophores has been synthesized, in which three thiourea groups are mounted on a cyclohexane‐based scaffold. Though conceptually related to earlier polycyclic systems, these molecules are simpler and far more accessible. Preorganization is somewhat reduced compared to earlier systems, and anion affinities are correspondingly lower. However, transport activities set new records. This surprising performance suggests a role for controlled flexibility in the design of transmembrane anion carriers. 相似文献
724.
Jaime Orejas Kevin P. Pfeuffer Steven J. Ray Jorge Pisonero Alfredo Sanz-Medel Gary M. Hieftje 《Analytical and bioanalytical chemistry》2014,406(29):7511-7521
Ambient desorption/ionization (ADI) sources coupled to mass spectrometry (MS) offer outstanding analytical features: direct analysis of real samples without sample pretreatment, combined with the selectivity and sensitivity of MS. Since ADI sources typically work in the open atmosphere, ambient conditions can affect the desorption and ionization processes. Here, the effects of internal source parameters and ambient humidity on the ionization processes of the flowing atmospheric pressure afterglow (FAPA) source are investigated. The interaction of reagent ions with a range of analytes is studied in terms of sensitivity and based upon the processes that occur in the ionization reactions. The results show that internal parameters which lead to higher gas temperatures afforded higher sensitivities, although fragmentation is also affected. In the case of humidity, only extremely dry conditions led to higher sensitivities, while fragmentation remained unaffected. 相似文献
725.
Jason L. Nyrop Arash Soheili Rong Xiang Fanyu Meng Jacob H. Waldman Xiujuan Jia Rubina Giarre Parmar Benjamin W. Thuronyi J. Michael Williams Lisa DiMichele Michel Journet Bonnie J. Howell Bing Mao Ian W. Davies Steven L. Colletti Laura Sepp‐Lorenzino Erin N. Guidry 《Journal of polymer science. Part A, Polymer chemistry》2014,52(8):1119-1129
Synthetic polymers represent a modifiable class of materials that can serve as adjuvants to address challenges in numerous biomedical and medicinal chemistry applications including the delivery of siRNA. Polymer‐based therapeutics offer unique challenges in both synthesis and characterization as compared to small molecule therapeutics. The ability to control the structure of the polymer is critical in creating a therapeutic. Reported herein, are batch and flow polymerization processes to produce amphiphilic terpolymers through a Lewis acid BF3OEt2‐catalyzed polymerization. These processes focus on controlling reaction variables, which affect polymer structure in this rapid, exothermic, nonliving cationic polymerization. In addition to analytical characterization of the polymers, the in vivo activity of the polymer‐siRNA conjugates is also highlighted—demonstrating that the method of synthesis does affect the in vivo activity of the resulting polymer conjugate. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1119–1129 相似文献
726.
Hsu‐Feng Lee Po‐Hsun Wang Yi‐Chiang Huang Wen‐Hung Su Ram Gopal Chun Che Lee Steven Holdcroft Wen‐Yao Huang 《Journal of polymer science. Part A, Polymer chemistry》2014,52(18):2579-2587
A series of sterically‐encumbered, sulfonated, poly(arylene ether) copolymers were synthesized and their proton conductivity examined. The series was prepared by copolymerizing a novel monomer, 2″,3″,5″,6″‐tetraphenyl‐[1,1′:4',1″:4″,1″':4″',1″″‐quinquephenyl]‐4,4″″‐diol, with 4,4'‐difluorobenzophenone and bisphenol A. Subsequent sulfonation and solution casting provided membranes possessing ion exchange capacities of 1.9 to 2.7 mmol/g and excellent mechanical properties (Young's modulus, 0.2–1.2 GPa; tensile strength, 35–70 MPa; elongation at break, 62–231%). Water uptake ranged from 34 to 98 wt% at 80 °C/100% RH. Proton conductivities ranged between 0.24 to 16 mS/cm at 80 °C/60% RH, and 3 to 167 mS/cm at 80 °C/95% RH. TEM analysis of the polymers, in the dehydrated state, revealed isolated spherical aggregates of ions, which presumably coalesce when hydrated to provide highly conductive pathways. The strategy of using highly‐encumbered polymer frameworks for the design of mechanically‐robust and dimensionally‐stable proton conducting membranes is demonstrated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2579‐2587 相似文献
727.
Li Yuan Sidi Huang Yinhui Hu Yuzheng Zhang Aijuan Gu Guozheng Liang Guoqiang Chen Yongming Gao Steven Nutt 《先进技术聚合物》2014,25(7):752-759
Self‐healing cyanate ester resins (CE) were developed by adding low molecular weight poly(phenylene oxide) (PPO) resin, yielding a high performance CE/PPO system via a low‐temperature process. The addition of PPO improved the flexural strength and fracture toughness of the CE matrix without sacrificing thermal properties. CE/PPO formulations with 5, 10, and 15 wt.% PPO showed 43%, 65%, and 105% increase in fracture toughness due to a combination of crack deflection, crack pinning, and matrix cavitation around second‐phase particles. When PPO was introduced into the CE, dielectric properties were either unchanged or declined. During thermal treatment to heal damaged CE, liquid PPO flowed into cracks, and during subsequent cooling, solidified to bond the crack surfaces. The self‐healing efficiency for CE with 15 wt.% PPO after heating to 220°C for 1 h exhibited a recovery of 73% in toughness and 81% in microtensile strength. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
728.
The first nickel catalyzed deprotonative cross coupling between C(sp3)–H bonds and aryl chlorides is reported, allowing the challenging arylation of benzylimines in the absence of directing group or stoichiometric metal activation. This methodology represents a convenient access to the (diarylmethyl)amine moiety, which is widespread in pharmaceutically relevant compounds. 相似文献
729.
730.
Robin B. Bedford Steven J. Durrant Michelle Montgomery 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(30):8911-8914
The regiodivergent palladium‐catalyzed C H arylation of pyrazolo[1,5‐a]pyrimidine has been achieved, wherein the switch in regioselectivity between positions C3 and C7 is under complete catalyst control. A phosphine‐containing palladium catalyst promotes the direct arylation at the most acidic position (C7), whereas a phosphine‐free catalyst targets the most electron‐rich position (C3). 相似文献