全文获取类型
收费全文 | 16435篇 |
免费 | 420篇 |
国内免费 | 117篇 |
专业分类
化学 | 11559篇 |
晶体学 | 98篇 |
力学 | 324篇 |
数学 | 2919篇 |
物理学 | 2072篇 |
出版年
2021年 | 124篇 |
2020年 | 167篇 |
2019年 | 169篇 |
2018年 | 137篇 |
2017年 | 130篇 |
2016年 | 278篇 |
2015年 | 303篇 |
2014年 | 309篇 |
2013年 | 716篇 |
2012年 | 726篇 |
2011年 | 948篇 |
2010年 | 474篇 |
2009年 | 419篇 |
2008年 | 868篇 |
2007年 | 889篇 |
2006年 | 911篇 |
2005年 | 974篇 |
2004年 | 864篇 |
2003年 | 707篇 |
2002年 | 535篇 |
2001年 | 163篇 |
2000年 | 160篇 |
1999年 | 115篇 |
1998年 | 118篇 |
1997年 | 191篇 |
1996年 | 246篇 |
1995年 | 168篇 |
1994年 | 172篇 |
1993年 | 161篇 |
1992年 | 163篇 |
1991年 | 152篇 |
1990年 | 148篇 |
1989年 | 132篇 |
1988年 | 147篇 |
1987年 | 151篇 |
1986年 | 121篇 |
1985年 | 265篇 |
1984年 | 236篇 |
1983年 | 182篇 |
1982年 | 254篇 |
1981年 | 207篇 |
1980年 | 265篇 |
1979年 | 231篇 |
1978年 | 234篇 |
1977年 | 243篇 |
1976年 | 206篇 |
1975年 | 167篇 |
1974年 | 160篇 |
1973年 | 153篇 |
1971年 | 84篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Biofunctionalization of Polyoxometalates with DNA Primers,Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products 下载免费PDF全文
Dr. Ahmed M. Debela Dr. Mayreli Ortiz Dr. Valerio Beni Prof. Serge Thorimbert Dr. Denis Lesage Prof. Richard B. Cole Prof. Ciara K. O'Sullivan Prof. Bernold Hasenknopf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17721-17727
The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW11O39{Sn(CH2)2CO}]8? and [P2W17O61{Sn(CH2)2CO}]6? have been used to link to a 5′‐NH2 terminated 21‐mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM‐labeled primers was demonstrated through hybridization with a surface‐immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis. 相似文献
82.
83.
Catalyst‐Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multistep Synthesis Design: A Concise Route to (+)‐Neopeltolide 下载免费PDF全文
Miao Yu Prof. Richard R. Schrock Prof. Amir H. Hoveyda 《Angewandte Chemie (International ed. in English)》2015,54(1):215-220
Molybdenum‐, tungsten‐, and ruthenium‐based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated. A concise diastereo‐ and enantioselective route that furnishes the anti‐proliferative natural product neopeltolide is now disclosed. Catalytic transformations are employed to address every stereochemical issue. Among the featured processes are an enantioselective ring‐opening/cross‐metathesis promoted by a Mo monoaryloxide pyrrolide (MAP) complex and a macrocyclic ring‐closing metathesis that affords a trisubstituted alkene and is catalyzed by a Mo bis(aryloxide) species. Furthermore, Z‐selective cross‐metathesis reactions, facilitated by Mo and Ru complexes, have been employed in the stereoselective synthesis of the acyclic dienyl moiety of the target molecule. 相似文献
84.
Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides 下载免费PDF全文
Bardia Soltanzadeh Dr. Arvind Jaganathan Dr. Richard J. Staples Prof. Dr. Babak Borhan 《Angewandte Chemie (International ed. in English)》2015,54(33):9517-9522
An organocatalytic and highly regio‐, diastereo‐, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio‐ and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. 相似文献
85.
The Role of Substituent Effects in Tuning Metallophilic Interactions and Emission Energy of Bis‐4‐(2‐pyridyl)‐1,2,3‐triazolatoplatinum(II) Complexes 下载免费PDF全文
M. R. Ranga Prabhath Dr. Julia Romanova Prof. Richard J. Curry Prof. S. Ravi P. Silva Dr. Peter D. Jarowski 《Angewandte Chemie (International ed. in English)》2015,54(27):7949-7953
The photoluminescence spectra of a series of 5‐substituted pyridyl‐1,2,3‐triazolato PtII homoleptic complexes show weak emission tunability (ranging from λ=397–408 nm) in dilute (10?6 M ) ethanolic solutions at the monomer level and strong tunability in concentrated solutions (10?4 M ) and thin films (ranging from λ=487–625 nm) from dimeric excited states (excimers). The results of density functional calculations (PBE0) attribute this “turn‐on” sensitivity and intensity in the excimer to strong Pt–Pt metallophilic interactions and a change in the excited‐state character from singlet metal‐to‐ligand charge transfer (1MLCT) to singlet metal‐metal‐to‐ligand charge transfer (1MMLCT) emissions in agreement with lifetime measurements. 相似文献
86.
Improved ion optics for introduction of ions into a 9.4‐T Fourier transform ion cyclotron resonance mass spectrometer 下载免费PDF全文
Yu Chen Nathan K. Kaiser Xibei Dang Yehia M. Ibrahim Randolph V. Norheim Gordon A. Anderson Richard D. Smith Alan G. Marshall 《Journal of mass spectrometry : JMS》2015,50(1):280-284
Enhancements to the ion source and transfer optics of our 9.4 T Fourier transform ion cyclotron resonance (ICR) mass spectrometer have resulted in improved ion transmission efficiency for more sensitive mass measurement of complex mixtures at the MS and MS/MS levels. The tube lens/skimmer has been replaced by a dual ion funnel and the following octopole by a quadrupole for reduced ion cloud radial expansion before transmission into a mass‐selective quadrupole. The number of ions that reach the ICR cell is increased by an order of magnitude for the funnel/quadrupole relative to the tube lens/skimmer/octopole. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
87.
High Ethene/Ethane Selectivity in 2,2′‐Bipyridine‐Based Silver(I) Complexes by Removal of Coordinated Solvent 下载免费PDF全文
Dr. Matthew G. Cowan William M. McDanel Prof. Hans H. Funke Dr. Yuki Kohno Prof. Douglas L. Gin Prof. Richard D. Noble 《Angewandte Chemie (International ed. in English)》2015,54(19):5740-5743
Following removal of coordinated CH3CN, the resulting complexes [AgI(2,2′‐bipyridine)][BF4] ( 1 ) and [AgI(6,6′‐dimethyl‐2,2′‐bipyridine)][OTf] ( 2 ) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g?1 when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2 , ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes. 相似文献
88.
89.
Acid‐Labile Thermoresponsive Copolymers That Combine Fast pH‐Triggered Hydrolysis and High Stability under Neutral Conditions 下载免费PDF全文
Dr. Qilu Zhang Zhanyao Hou Benoit Louage Dr. Dingying Zhou Nane Vanparijs Prof. Dr. Bruno G. De Geest Prof. Dr. Richard Hoogenboom 《Angewandte Chemie (International ed. in English)》2015,54(37):10879-10883
Biodegradable polymeric materials are intensively used in biomedical applications. Of particular interest for drug‐delivery applications are polymers that are stable at pH 7.4, that is, in the blood stream, but rapidly hydrolyze under acidic conditions, such as those encountered in the endo/lysosome or the tumor microenvironment. However, an increase in the acidic‐degradation rate of acid‐labile groups goes hand in hand with higher instability of the polymer at pH 7.4 or during storage, thus posing an intrinsic limitation on fast degradation under acidic conditions. Herein, we report that a combination of acid‐labile dimethyldioxolane side chains and hydroxyethyl side chains leads to acid‐degradable thermoresponsive polymers that are quickly hydrolyzed under slightly acidic conditions but stable at pH 7.4 or during storage. We ascribe these properties to high hydration of the hydroxy‐containing collapsed polymer globules in conjunction with autocatalytic acceleration of the hydrolysis reactions by the hydroxy groups. 相似文献
90.
Synthesis and Evaluation of GdIII‐Based Magnetic Resonance Contrast Agents for Molecular Imaging of Prostate‐Specific Membrane Antigen 下载免费PDF全文
Dr. Sangeeta Ray Banerjee Dr. Ethel J. Ngen Matthew W. Rotz Dr. Samata Kakkad Ala Lisok Richard Pracitto Mrudula Pullambhatla Dr. Zhengping Chen Dr. Tariq Shah Dr. Dmitri Artemov Dr. Thomas J. Meade Dr. Zaver M. Bhujwalla Dr. Martin G. Pomper 《Angewandte Chemie (International ed. in English)》2015,54(37):10778-10782
Magnetic resonance (MR) imaging is advantageous because it concurrently provides anatomic, functional, and molecular information. MR molecular imaging can combine the high spatial resolution of this established clinical modality with molecular profiling in vivo. However, as a result of the intrinsically low sensitivity of MR imaging, high local concentrations of biological targets are required to generate discernable MR contrast. We hypothesize that the prostate‐specific membrane antigen (PSMA), an attractive target for imaging and therapy of prostate cancer, could serve as a suitable biomarker for MR‐based molecular imaging. We have synthesized three new high‐affinity, low‐molecular‐weight GdIII‐based PSMA‐targeted contrast agents containing one to three GdIII chelates per molecule. We evaluated the relaxometric properties of these agents in solution, in prostate cancer cells, and in an in vivo experimental model to demonstrate the feasibility of PSMA‐based MR molecular imaging. 相似文献