全文获取类型
收费全文 | 1413篇 |
免费 | 42篇 |
国内免费 | 21篇 |
专业分类
化学 | 994篇 |
晶体学 | 9篇 |
力学 | 43篇 |
数学 | 242篇 |
物理学 | 188篇 |
出版年
2022年 | 15篇 |
2021年 | 26篇 |
2020年 | 28篇 |
2019年 | 26篇 |
2018年 | 12篇 |
2017年 | 15篇 |
2016年 | 39篇 |
2015年 | 25篇 |
2014年 | 27篇 |
2013年 | 62篇 |
2012年 | 72篇 |
2011年 | 94篇 |
2010年 | 70篇 |
2009年 | 43篇 |
2008年 | 74篇 |
2007年 | 96篇 |
2006年 | 103篇 |
2005年 | 100篇 |
2004年 | 85篇 |
2003年 | 64篇 |
2002年 | 65篇 |
2001年 | 25篇 |
2000年 | 16篇 |
1999年 | 17篇 |
1998年 | 9篇 |
1997年 | 16篇 |
1996年 | 16篇 |
1995年 | 5篇 |
1994年 | 12篇 |
1993年 | 16篇 |
1992年 | 8篇 |
1991年 | 13篇 |
1990年 | 9篇 |
1988年 | 12篇 |
1987年 | 5篇 |
1986年 | 9篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 8篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 6篇 |
1979年 | 15篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1976年 | 9篇 |
1975年 | 5篇 |
1974年 | 9篇 |
1973年 | 11篇 |
1972年 | 5篇 |
排序方式: 共有1476条查询结果,搜索用时 10 毫秒
121.
This work develops models for calculating the disjoining pressures of a cylindrical fluid "plug", specifically in submicrometer cylindrical pores. This modeling produces closed-form, cylindrical-pore disjoining pressures for London/van der Waals and solute/pore-wall adsorption interactions, which are the slit-pore models with the characteristic pore size replaced by the radius and multiplied by 6, resulting in a 48-fold or more increase in magnitude. In addition, this work contains a numerical solution for electrostatic interactions. The result of the numerical solution was a 9-fold increase in the modeled disjoining pressure compared to that in the slit-pore model. The cylindrical models may apply to the chemical coating of the interior walls of cylindrical pores or to the thermodynamics within droplets after the breakup of a fluid coating a surface. However, the application used as the base case in this paper is the extension of transport and thermodynamic laws for porous media, previously developed with capillary pressure models, to fully saturated porous media with submicrometer-sized pores. As such, the models could apply to mass transport in ultrafiltration, nanofiltration, and reverse-osmosis membranes. Copyright 2001 Academic Press. 相似文献
122.
We obtain upper bounds for mixed exponential sums of the type
where pm is a prime power with m⩾ 2 and X is a multiplicative character (mod pm). If X is primitive or p⫮(a, b) then we obtain |S(χ,f,p
m)| ⩽2np
2/3 m. If X is of conductor p and p⫮( a, b) then we get the stronger bound |S(χ,f,p
m)|⩽np
m/2.
This paper is dedicated to Prof. Wang Yuan on the occasion of his 70th birthday. 相似文献
123.
Todd D. Vance 《Designs, Codes and Cryptography》2000,19(1):27-43
The weight distribution of GRM (generalized Reed-Muller) codes is unknown in general. This article describes and applies some new techniques to the codes over F3. Specifically, we decompose GRM codewords into words from smaller codes and use this decomposition, along with a projective geometry technique, to relate weights occurring in one code with weights occurring in simpler codes. In doing so, we discover a new gap in the weight distribution of many codes. In particular, we show there is no word of weight 3m–2 in GRM3(4,m) for m>6, and for even-order codes over the ternary field, we show that under certain conditions, there is no word of weight d+, where d is the minimum distance and is the largest integer dividing all weights occurring in the code. 相似文献
124.
(Quasi‐)Racemic X‐ray Structures of Glycosylated and Non‐Glycosylated Forms of the Chemokine Ser‐CCL1 Prepared by Total Chemical Synthesis 下载免费PDF全文
Prof. Dr. Ryo Okamoto Dr. Kalyaneswar Mandal Dr. Michael R. Sawaya Prof. Dr. Yasuhiro Kajihara Prof. Dr. Todd O. Yeates Prof. Dr. Stephen B. H. Kent 《Angewandte Chemie (International ed. in English)》2014,53(20):5194-5198
Our goal was to obtain the X‐ray crystal structure of the glycosylated chemokine Ser‐CCL1. Glycoproteins can be hard to crystallize because of the heterogeneity of the oligosaccharide (glycan) moiety. We used glycosylated Ser‐CCL1 that had been prepared by total chemical synthesis as a homogeneous compound containing an N‐linked asialo biantennary nonasaccharide glycan moiety of defined covalent structure. Facile crystal formation occurred from a quasi‐racemic mixture consisting of glycosylated L ‐protein and non‐glycosylated‐D ‐protein, while no crystals were obtained from the glycosylated L ‐protein alone. The structure was solved at a resolution of 2.6–2.1 Å. However, the glycan moiety was disordered: only the N‐linked GlcNAc sugar was well‐defined in the electron density map. A racemic mixture of the protein enantiomers L ‐Ser‐CCL1 and D ‐Ser‐CCL1 was also crystallized, and the structure of the true racemate was solved at a resolution of 2.7–2.15 Å. Superimposition of the structures of the protein moieties of L ‐Ser‐CCL1 and glycosylated‐L ‐Ser‐CCL1 revealed there was no significant alteration of the protein structure by N‐glycosylation. 相似文献
125.
Atmospheric pressure ionization has been used to great effect by mass spectrometrists in widely diverse fields. The aim of this brief review is to set down the advantages of API/MS to fundamental and analytical chemists alike through discussion of the basic processes of ionisation and through its application. 相似文献
126.
Dr. Christopher K. Prier Dr. Todd K. Hyster Dr. Christopher C. Farwell Audrey Huang Prof. Dr. Frances H. Arnold 《Angewandte Chemie (International ed. in English)》2016,55(15):4711-4715
Sigmatropic rearrangements, while rare in biology, offer opportunities for the efficient and selective synthesis of complex chemical motifs. A “P411” serine‐ligated variant of cytochrome P450BM3 has been engineered to initiate a sulfimidation/[2,3]‐sigmatropic rearrangement sequence in whole E. coli cells, a non‐natural function for any enzyme, providing access to enantioenriched, protected allylic amines. Five mutations in the enzyme substantially enhance its activity toward this new function, demonstrating the evolvability of the catalyst toward challenging nitrene transfer reactions. The evolved catalyst additionally performs the highly enantioselective imidation of non‐allylic sulfides. 相似文献
127.
Lin Y Böker A Skaff H Cookson D Dinsmore AD Emrick T Russell TP 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):191-194
The self-assembly of nanoparticles at fluid interfaces, driven by the reduction in interfacial energy, was investigated. With spherical, tri-n-octyl-phosphine-oxide covered cadmium selenide (CdSe) nanoparticles (1-8 nm), thermal fluctuations compete with the interfacial segregation giving rise to a size-dependent self-assembly of the particles. The structure of the nanoparticle assembly was studied using electron microscopy, atomic force microscopy, and X-ray scattering in situ, which indicate that the particles form a densely packed monolayer. The energetics of the adsorption of nanoparticles onto the interface was revealed by time-dependent fluorescence studies on a mixture of two different sized nanoparticles at the interface. The dynamics of the nanoparticles at the fluid interface, probed using fluorescence photobleaching methods, suggests a liquid-like behavior. The results have implications in the design of hierarchical self-assemblies of nanoparticles for the one-step fabrication of devices on multiple length scales. 相似文献
128.
Site‐Selective CH Borylation of Quinolines at the C8 Position Catalyzed by a Silica‐Supported Phosphane–Iridium System 下载免费PDF全文
Shota Konishi Dr. Soichiro Kawamorita Dr. Tomohiro Iwai Prof. Patrick G. Steel Prof. Dr. Todd B. Marder Prof. Dr. Masaya Sawamura 《化学:亚洲杂志》2014,9(2):434-438
Site‐selective C? H borylation of quinoline derivatives at the C8 position has been achieved by using a heterogeneous Ir catalyst system based on a silica‐supported cage‐type monophosphane ligand SMAP. The efficient synthesis of a corticotropin‐releasing factor1 (CRF1) receptor antagonist based on a late‐stage C? H borylation strategy demonstrates the utility of the C8 borylation reaction. 相似文献
129.
Todd B. Vinzant Christine I. Ehrman William S. Adney Steven R. Thomas Michael E. Himmel 《Applied biochemistry and biotechnology》1997,62(1):99-104
A series of correlations was made between the performance of 15 wood species in simultaneous saccharification and fermentation (SSF) and their respective chemical compositions. A compelling inverse trend (p < 0.001) was demonstrated between the percent conversion of glucan to ethanol during SSF and the Klason lignin content of the wood samples before dilute acid pretreatment. No significant relationships were found between the glucan, xylan, and ash compositions of the native wood samples and ethanol yield. This observation is unique and provides a convenient predictor of biomass conversion efficiency. 相似文献
130.
Dr. Carsten Lenczyk Dr. Dipak Kumar Roy Kai Oberdorf Dr. Jörn Nitsch Dr. Rian D. Dewhurst Dr. Krzysztof Radacki Prof. Dr. Jean-François Halet Prof. Dr. Todd B. Marder Prof. Dr. Matthias Bickelhaupt Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16544-16549
The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH2] (Dur=2,3,5,6-Me4C6H) and [(Me3Si)2NBH2] led to the formation of bridging borylene complexes of the form [(Cp*RuH)2BR] (Cp*=C5Me5; 1 a : R=Dur; 1 b : R=N(SiMe3)2) through oxidative addition of the B−H bonds with concomitant hydrogen liberation. Employing the more electron-deficient dihydroborane [3,5-(CF3)2-C6H3BH2] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)4[(Cp*Ru)2B4H5(3,5-(CF3)2C6H3)4] ( 4 ), through an unusual, incomplete threefold dehydrocoupling process. A comparative theoretical investigation of the bonding in a simplified model of 4 and the analogous complex nido-[1,2(Cp*Ru)2(μ-H)B4H9] ( I ) indicates that there appear to be no classical σ-bonds between the boron atoms in complex I , whereas in the case of 4 the B4 chain better resembles a network of three B−B σ bonds, the central bond being significantly weaker than the other two. 相似文献