全文获取类型
收费全文 | 1524篇 |
免费 | 61篇 |
国内免费 | 4篇 |
专业分类
化学 | 1080篇 |
晶体学 | 5篇 |
力学 | 19篇 |
数学 | 143篇 |
物理学 | 342篇 |
出版年
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 25篇 |
2020年 | 24篇 |
2019年 | 26篇 |
2018年 | 21篇 |
2017年 | 12篇 |
2016年 | 34篇 |
2015年 | 33篇 |
2014年 | 38篇 |
2013年 | 86篇 |
2012年 | 101篇 |
2011年 | 113篇 |
2010年 | 74篇 |
2009年 | 57篇 |
2008年 | 75篇 |
2007年 | 71篇 |
2006年 | 83篇 |
2005年 | 85篇 |
2004年 | 68篇 |
2003年 | 50篇 |
2002年 | 50篇 |
2001年 | 47篇 |
2000年 | 36篇 |
1999年 | 31篇 |
1998年 | 17篇 |
1997年 | 11篇 |
1996年 | 19篇 |
1995年 | 18篇 |
1994年 | 22篇 |
1993年 | 27篇 |
1992年 | 20篇 |
1991年 | 13篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 18篇 |
1987年 | 11篇 |
1986年 | 12篇 |
1985年 | 19篇 |
1984年 | 13篇 |
1983年 | 15篇 |
1982年 | 8篇 |
1981年 | 15篇 |
1980年 | 9篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1975年 | 3篇 |
1970年 | 3篇 |
1967年 | 2篇 |
排序方式: 共有1589条查询结果,搜索用时 20 毫秒
71.
A Chiral Thioxanthone as an Organocatalyst for Enantioselective [2+2] Photocycloaddition Reactions Induced by Visible Light
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Rafael Alonso Prof. Dr. Thorsten Bach 《Angewandte Chemie (International ed. in English)》2014,53(17):4368-4371
Thioxanthone 1 , which was synthesized in a concise fashion from methyl thiosalicylate, exhibits a significant absorption in the visible light region. It allows for an efficient enantioselective catalysis of intramolecular [2+2] photocycloaddition reactions presumably by triplet energy transfer. 相似文献
72.
73.
Alma Viso Roberto Fernández de la Pradilla Ana García Carlos Guerrero-Strachan Marta Alonso Mariola Tortosa 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1229-1234
Abstract Readily available p-tolylsulfinimines undergo highly stereoselective [3 + 2] cycloadditions with azomethine ylides generated from α -iminoesters and LDA to produce N-sulfinylimidazolidines. In the presence of Lewis acids, p-tolylsulfinimines react with glycine iminoester enolates to produce N-sulfinylimidazolidines, after cyclization of open chain intermediates. These mechanistically diverse processes take place with excellent regio-, stereo-, and facial selectivities, and the latter is opposite to most known reactions involving sulfinimines. Some of the resulting imidazolidines have been transformed into examples of a novel class of nonsymmetrical vicinal diamines using reductive and/or hydrolytic protocols. 相似文献
74.
Elena O. Alonso Maria E. R. Marcondes Vicente G. Toscano 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract As part of our continuing interest in the mechanistic photochemistry of phosphonium salts (Toscano et al., Chez. Commun., 567 (1973); J. Phys. Chem., 83(9), 1213 (1979)) we have investigated the photodecomposition (313 nm irradiation) of (1-naphthyl-methyl) triphenylphosphonium (I) chloride and tetrafluoroborate in deaerated isopropanol: 相似文献
75.
M. Amélia Santos Adelino Afonso M. Matilde Marques Craig Wilcox 《Supramolecular chemistry》2013,25(3):201-215
Abstract New receptors based upon a carboxamidonaphthyridine unit derivatized with the polyaromatic segments [4-(1-pyrenyl)butyroylamino] and [3-(9-anthracenyl)propanoylamino] have been synthesized and studied by 1H NMR titration in their binding interaction to the guanosine-C8 adducts from the carcinogens 2-acetylaminofluorene and 2-aminofluorene. The high binding energy, in comparison with that of the non-derivatized analogues, is rationalized in terms of a bi-site interaction (hydrogen bonding and aromatic stacking). Although many factors may contribute to the strength of the host-guest complexes described herein, it appears that in some cases π-π interaction may induce a concomitant bending in the hydrogen bond system. 相似文献
76.
This work presents an automatic system, based on an electronic tongue, for resolution of mixtures of three pesticides. Inhibition detections were performed during the steady state of biosensors response. Three biosensors were built using two enzymes, electric eel (EE), genetically-modified Drosophila melanogaster (B131), and electric eel co-immobilized with drosophila melanogaster (BH). Calibrations curves for paraoxon, dichorlvos, and carbofuran were performed in the ranges 0.4–50.4 µM, 0.01–1.01 µM, 0.01–0.41 µM with LOD of 3.91 × 10?8, 6.30 × 10?11, and 5.84 × 10?10, respectively. An artificial neural network (ANN) was used to model the combined response of three pesticides. A set of 19 mixtures were prepared in order to train the artificial neural network, the modeling was validated with a set of 6 spiked samples of river water. The error and recovery yields were found in consistent with expected values. 相似文献
77.
P. Alonso F. Argüeso R. Cortina J. Ranilla A. M. Vidal 《Journal of mathematical chemistry》2013,51(4):1153-1163
In this work we present a suitable computational tool to deal with large matrices and solve systems of non-linear equations. This technique is applied to a very interesting problem: the detection and flux estimation of point sources in Cosmic Microwave Background (CMB) maps, which allows a good determination of CMB primordial fluctuations and leads to a better knowledge of the chemistry at the early stages of the Universe. The method uses previous information about the statistical properties of the sources, so that this knowledge is incorporated in a Bayesian scheme. Simulations show that our approach allows the detection of more sources than previous non-Bayesian techniques, with a small computation time. 相似文献
78.
Joaquin Barbera Mercedes Marcos Ana Omenat Jose-Luis Serrano Jesus I. Martinez Pablo J. Alonso 《Liquid crystals》2013,40(2):255-262
The synthesis and liquid crystalline behaviour of the first and second generations of a dendrimeric structure based on poly(propyleneimine)(DAB-dendr(NH2)x) are reported. 4-(4-n-Alkoxybenzoyloxy)salicylaldehydes are used as mesogenic moieties attached at the peripheral amino groups of the dendrimers giving rise to dendromesogens with four and eight mesogenic branches. From these dendromesogens, considered as organic ligands, were prepared six metal-containing dendrimers which incorporate two or four copper atoms in their structures. All the dendrimeric ligands and three of the metal-containing dendrimers exhibit liquid crystalline properties which were studied by optical microscopy, DSC, X-ray diffraction and EPR spectroscopy. 相似文献
79.
Mohamed Fatnassi Corine Tourné-Péteilh Pradial Peralta Thomas Cacciaguerra Philippe Dieudonné Jean-Marie Devoisselle Bruno Alonso 《Journal of Sol-Gel Science and Technology》2013,68(2):307-316
Two model drugs of different physico-chemical and pharmaceutical properties (ibuprofen, acetaminophen) have been incorporated together or separately in silica-based microspheres using sol–gel and spray-drying processes. A variable amount of a neutral surfactant Brij-56© has also been added. The properties of the microspheres vary significantly depending on their composition. Three kinds of texture are identified: (1) silica containing spheroid nano-domains (formed by ibuprofen; diameters between 20 and 100 nm), (2) silica containing worm-like mesophases (formed by Brij-56© and both model drugs, typical correlation distances ~6 nm), (3) silica intimately mixed with the drug (acetaminophen) without visible phase-separation. The kinetics of drug release in simulated intestinal fluid strongly depend on these textures. The association of ibuprofen and acetaminophen in a single type of microsphere and without surfactant favours a concomitant release. Possible mechanisms of materials’ formation are discussed. 相似文献
80.
Núria Mas Alessandro Agostini Dr. Laura Mondragón Dr. Andrea Bernardos Dr. Félix Sancenón Dr. M. Dolores Marcos Prof. Ramón Martínez‐Máñez Prof. Ana M. Costero Prof. Salvador Gil Prof. Matilde Merino‐Sanjuán Prof. Pedro Amorós Dr. Mar Orzáez Prof. Enrique Pérez‐Payá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1346-1356
The preparation of a new capped silica mesoporous material, Rh‐Azo‐S , for on‐command delivery applications in the presence of target enzymes is described. The material consists of nanometric mesoporous MCM‐41‐like supports loaded with Rhodamine B and capped with an azopyridine derivative. The material was designed to show “zero delivery” and to display a cargo release in the presence of reductases and esterases, which are usually present in the colon, mainly due to intestinal microflora. The opening and cargo release of Rh‐Azo‐S in vitro studies were assessed and seen to occur in the presence of these enzymes, whereas no delivery was noted in the presence of pepsine. Moreover, Rh‐Azo‐S nanoparticles were used to study controlled Rhodamine B dye delivery in intracellular media. HeLa cells were employed for testing the “non”‐toxicity of nanoparticles. Moreover, delivery of the dye in these cells, through internalization and enzyme‐mediated gate opening, was confirmed by confocal microscopy. Furthermore, the nanoparticles capped with the Azo group and loaded with a cytotoxic camptothecin ( CPT ) were also prepared (solid CPT‐Azo‐S ) and used as delivery nanodevices in HeLa cells. When this solid was employed, the cell viability decreased significantly due to internalization of the nanoparticles and delivery of the cytotoxic agent. 相似文献