全文获取类型
收费全文 | 6755篇 |
免费 | 704篇 |
国内免费 | 758篇 |
专业分类
化学 | 3100篇 |
晶体学 | 27篇 |
力学 | 443篇 |
综合类 | 182篇 |
数学 | 2883篇 |
物理学 | 1582篇 |
出版年
2024年 | 9篇 |
2023年 | 89篇 |
2022年 | 168篇 |
2021年 | 214篇 |
2020年 | 198篇 |
2019年 | 229篇 |
2018年 | 173篇 |
2017年 | 244篇 |
2016年 | 316篇 |
2015年 | 207篇 |
2014年 | 369篇 |
2013年 | 472篇 |
2012年 | 370篇 |
2011年 | 372篇 |
2010年 | 295篇 |
2009年 | 401篇 |
2008年 | 411篇 |
2007年 | 425篇 |
2006年 | 439篇 |
2005年 | 359篇 |
2004年 | 323篇 |
2003年 | 322篇 |
2002年 | 262篇 |
2001年 | 234篇 |
2000年 | 220篇 |
1999年 | 158篇 |
1998年 | 150篇 |
1997年 | 150篇 |
1996年 | 112篇 |
1995年 | 93篇 |
1994年 | 86篇 |
1993年 | 48篇 |
1992年 | 49篇 |
1991年 | 42篇 |
1990年 | 32篇 |
1989年 | 28篇 |
1988年 | 18篇 |
1987年 | 14篇 |
1986年 | 17篇 |
1985年 | 24篇 |
1984年 | 14篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 8篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1972年 | 3篇 |
排序方式: 共有8217条查询结果,搜索用时 15 毫秒
1.
2.
3.
Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport
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)
B. Sc. Eduard Puig Prof. Dr. Beat Ernst Prof. Dr. Horst Kessler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8023-8027
Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (Papp) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature. 相似文献
4.
Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities
下载免费PDF全文
![点击此处可从《Journal of polymer science. Part A, Polymer chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
5.
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
6.
Here, we report a new strategy for rapid synthesis of branched peptide by side-chain hydrazide ligation at Asn. The hydrazide was converted to thioester at Asn side chain by NaNO2 and thiol reagent, and sequential ligation with an N-terminus Cys-peptide efficiently afforded the branched peptide. A branched cyclic peptide was successfully synthesized by side-chain ligation with a two-Cys-peptide and formation of a disulfide bond. This approach provides a new way for expeditious synthesis of branched peptides and facilitates the design of neopeptides as functional bio-mimics. 相似文献
7.
HIRONOBU Ishihara 《Geometriae Dedicata》1997,67(3):309-336
Several classification results for ample vector bundles of rank 2 on Hirzebruch surfaces, and on Del Pezzo surfaces, are obtained. In particular, we classify rank 2 ample vector bundles with c2 less than seven on Hirzebruch surfaces, and with c2 less than four on Del Pezzo surfaces. 相似文献
8.
We examine two criteria for balance of a gain graph, one based on binary cycles and one on circles. The graphs for which each criterion is valid depend on the set of allowed gain groups. The binary cycle test is invalid, except for forests, if any possible gain group has an element of odd order. Assuming all groups are allowed, or all abelian groups, or merely the cyclic group of order 3, we characterize, both constructively and by forbidden minors, the graphs for which the circle test is valid. It turns out that these three classes of groups have the same set of forbidden minors. The exact reason for the importance of the ternary cyclic group is not clear. © 2005 Wiley Periodicals, Inc. J Graph Theory 相似文献
9.
An Improved Gradient Projection-based Decomposition Technique for Support Vector Machines 总被引:2,自引:0,他引:2
Luca Zanni 《Computational Management Science》2006,3(2):131-145
In this paper we propose some improvements to a recent decomposition technique for the large quadratic program arising in
training support vector machines. As standard decomposition approaches, the technique we consider is based on the idea to
optimize, at each iteration, a subset of the variables through the solution of a quadratic programming subproblem. The innovative
features of this approach consist in using a very effective gradient projection method for the inner subproblems and a special
rule for selecting the variables to be optimized at each step. These features allow to obtain promising performance by decomposing
the problem into few large subproblems instead of many small subproblems as usually done by other decomposition schemes. We
improve this technique by introducing a new inner solver and a simple strategy for reducing the computational cost of each
iteration. We evaluate the effectiveness of these improvements by solving large-scale benchmark problems and by comparison
with a widely used decomposition package. 相似文献
10.
Formalization for problems of multicriteria decision making under uncertainty is constructed in terms of guaranteed and weak
estimates. A relevant definition of the vector maximinimax value is given. Parameterization and approximation of maximum,
minimax, and maximinimax values based on the inverse logical convolution are suggested. An application for multicommodity
networks is considered.
Received: December 13, 2000 / Accepted: August 21, 2001?Published online May 8, 2002 相似文献