全文获取类型
收费全文 | 2022篇 |
免费 | 57篇 |
国内免费 | 6篇 |
专业分类
化学 | 1302篇 |
晶体学 | 36篇 |
力学 | 40篇 |
数学 | 239篇 |
物理学 | 468篇 |
出版年
2021年 | 15篇 |
2020年 | 28篇 |
2019年 | 13篇 |
2018年 | 17篇 |
2017年 | 16篇 |
2016年 | 41篇 |
2015年 | 41篇 |
2014年 | 41篇 |
2013年 | 127篇 |
2012年 | 119篇 |
2011年 | 141篇 |
2010年 | 64篇 |
2009年 | 35篇 |
2008年 | 110篇 |
2007年 | 134篇 |
2006年 | 136篇 |
2005年 | 131篇 |
2004年 | 98篇 |
2003年 | 65篇 |
2002年 | 61篇 |
2001年 | 29篇 |
2000年 | 21篇 |
1999年 | 21篇 |
1998年 | 17篇 |
1997年 | 15篇 |
1996年 | 27篇 |
1995年 | 26篇 |
1994年 | 24篇 |
1993年 | 31篇 |
1992年 | 22篇 |
1991年 | 19篇 |
1990年 | 16篇 |
1989年 | 21篇 |
1988年 | 12篇 |
1987年 | 20篇 |
1986年 | 28篇 |
1985年 | 30篇 |
1984年 | 14篇 |
1983年 | 15篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 15篇 |
1979年 | 8篇 |
1978年 | 15篇 |
1977年 | 25篇 |
1976年 | 25篇 |
1975年 | 24篇 |
1974年 | 12篇 |
1973年 | 8篇 |
1970年 | 11篇 |
排序方式: 共有2085条查询结果,搜索用时 31 毫秒
1.
Dr. Chenge Li Dr. Alison G. Tebo Marion Thauvin Marie-Aude Plamont Prof. Dr. Michel Volovitch Dr. Xavier Morin Prof. Dr. Sophie Vriz Prof. Dr. Arnaud Gautier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18073-18079
Far-red emitting fluorescent labels are highly desirable for spectral multiplexing and deep tissue imaging. Here, we describe the generation of frFAST (far-red Fluorescence Activating and absorption Shifting Tag), a 14-kDa monomeric protein that forms a bright far-red fluorescent assembly with (4-hydroxy-3-methoxy-phenyl)allylidene rhodanine (HPAR-3OM). As HPAR-3OM is essentially non-fluorescent in solution and in cells, frFAST can be imaged with high contrast in presence of free HPAR-3OM, which allowed the rapid and efficient imaging of frFAST fusions in live cells, zebrafish embryo/larvae, and chicken embryos. Beyond enabling the genetic encoding of far-red fluorescence, frFAST allowed the design of a far-red chemogenetic reporter of protein–protein interactions, demonstrating its great potential for the design of innovative far-red emitting biosensors. 相似文献
2.
3.
N-Heterocyclic carbene catalysed redox isomerisation with reduction about the carbonyl has been developed in the transformation of trienyl esters to tetrasubstituted benzaldehydes. The reaction proceeds in good to excellent yield, and in cases that provide 2,2′-biaryls, enantioselectivity is observed. Mechanistic studies demonstrate the intermediacy of a cyclohexenyl β-lactone, while implicating formation of the homoenolate as turnover limiting. 相似文献
4.
Timothy R. Totsch Victoria L. Stanford Oleksander Klep Mary K. Burdette Benjamin Grant Stephen H. Foulger Gary M. Gray 《Journal of polymer science. Part A, Polymer chemistry》2020,58(13):1825-1842
Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2 and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2) –[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2 with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, TGA, DSC, and SEC. 31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and Tg profiles. The polymers have weight average MWs of up to 3.8 × 104 Da. 相似文献
5.
Liam J. R. McGeachie Cameron L. Carpenter-Warren David B. Cordes Michael Bühl Steven J. Gray Guoxiong Hua Alexandra M. Z. Slawin J. Derek Woollins 《无机化学与普通化学杂志》2020,646(22):1795-1798
An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar3Sb(NSO)2), and copper examples [CuBipy(PPh3)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding. 相似文献
6.
Fereshteh K. Yousefi Ali Jannesari Shahla Pazokifard Mohammad Reza Saeb Alison J. Scott Alexander Penlidis 《大分子反应工程》2019,13(4)
Ternary monomer reactivity ratios of triisopropylsilyl acrylate (SiA), methyl methacrylate (MMA), and n‐butyl acrylate (BA), as common monomers in self‐polishing coatings (SPCs) binders are obtained using experimental data collected from free radical bulk polymerization at 70 °C. Different terpolymerizations at low and medium‐high conversions are performed at optimized feed compositions. Estimations are made using the error‐in‐variables model (EVM) framework, applying the recast form of the Alfrey–Goldfinger (AG) model and a direct numerical integration (DNI) approach to the collected data. Estimations from individual low and medium‐high conversion data are compared to those found with the combined data (full conversion range data). The highest certainty in point estimates are obtained with analysis of the full conversion range data. Furthermore, the reactivity ratios determined from the combined data fall between those found with analysis of individual low and medium‐high conversion data, another corroboration of reliable data collection. Reactivity ratios determined from analysis of the combined data (rSiA/MMA = 0.4185, rMMA/SiA = 1.3754, rSiA/BA = 0.8739, rBA/SiA = 0.5736, rBA/MMA = 0.3692, rMMA/BA = 1.7919) are used in the recast AG model to predict cumulative terpolymer composition as a function of conversion. The experimental data and model prediction show satisfactory agreement. 相似文献
7.
π‐Expanded α,β‐Unsaturated Ketones: Synthesis,Optical Properties,and Two‐Photon‐Induced Polymerization 下载免费PDF全文
Rashid Nazir Dr. Florent Bourquard Evaldas Balčiūnas Dr. Sabina Smoleń Dr. David Gray Prof. Dr. Nikolai V. Tkachenko Dr. Maria Farsari Prof. Dr. Daniel T. Gryko 《Chemphyschem》2015,16(3):682-690
A library of π‐expanded α,β‐unsaturated ketones was designed and synthesized. They were prepared by a combination of Wittig reaction, Sonogashira reaction, and aldol condensation. It was further demonstrated that the double aldol condensation can be performed effectively for highly polarized styrene‐ and diphenylacetylene‐derived aldehydes. The strategic placement of two dialkylamino groups at the periphery of D ‐π‐A‐π‐D molecules resulted in dyes with excellent solubility. These ketones absorb light in the region 400–550 nm. Many of them display strong solvatochromism so that the emission ranges from 530–580 nm in toluene to the near‐IR region in benzonitrile. Ketones based on cyclobutanone as central moieties display very high fluorescence quantum yields in nonpolar solvents, which decrease drastically in polar media. Photophysical studies of these new functional dyes revealed that they possess an enhanced two‐photon absorption cross section when compared with simpler ketone derivatives. Due to strong polarization of the resulting dyes, values of two‐photon absorption cross sections on the level of 200–300 GM at 800 nm were achieved, and thanks to that as well as the presence of the keto group, these new two‐photon initiators display excellent performance so that the operating region is 5–75 mW in some cases. 相似文献
8.
Intramolecular Fluorocyclizations of Unsaturated Carboxylic Acids with a Stable Hypervalent Fluoroiodane Reagent 下载免费PDF全文
Gemma C. Geary Prof. Eric G. Hope Dr. Alison M. Stuart 《Angewandte Chemie (International ed. in English)》2015,54(49):14911-14914
A new class of fluorinated lactones was prepared by the intramolecular fluorocyclizations of unsaturated carboxylic acids by using the stable fluoroiodane reagent in combination with AgBF4. This unique reaction incorporates a cyclization, an aryl migration, and a fluorination all in one step. The fluoroiodane reagent, prepared easily from fluoride, can also be used without a metal catalyst to give moderate yields within just 1 hour, thus demonstrating that it is a suitable reagent for developing new 18F‐labelled radiotracers for PET imaging. 相似文献
9.
Inside Cover: Benzoxazolone Carboxamides: Potent and Systemically Active Inhibitors of Intracellular Acid Ceramidase (Angew. Chem. Int. Ed. 2/2015) 下载免费PDF全文
10.
Reversible Modulation of Surface Plasmons in Gold Nanoparticles Enabled by Surface Redox Chemistry 下载免费PDF全文
Dr. Zheng Li Dr. Jonathan J. Foley IV Dr. Sheng Peng Dr. Cheng‐Jun Sun Dr. Yang Ren Dr. Gary P. Wiederrecht Dr. Stephen K. Gray Dr. Yugang Sun 《Angewandte Chemie (International ed. in English)》2015,54(31):8948-8951
Switchable surface redox chemistry is demonstrated in gold@iron/iron oxide core–shell nanoparticles with ambient oxidation and plasmon‐mediated reduction to modulate the oxidation state of shell layers. The iron shell can be oxidized to iron oxide through ambient oxidation, leading to an enhancement and red‐shift of the gold surface plasmon resonance (SPR). This enhanced gold SPR can drive reduction of the iron oxide shell under broadband illumination to reversibly blue‐shift and significantly dampen gold SPR absorption. The observed phenomena provide a unique mechanism for controlling the plasmonic properties and surface chemistry of small metal nanoparticles. 相似文献