全文获取类型
收费全文 | 8382篇 |
免费 | 305篇 |
国内免费 | 47篇 |
专业分类
化学 | 5449篇 |
晶体学 | 78篇 |
力学 | 257篇 |
数学 | 1489篇 |
物理学 | 1461篇 |
出版年
2023年 | 50篇 |
2022年 | 91篇 |
2021年 | 135篇 |
2020年 | 143篇 |
2019年 | 157篇 |
2018年 | 162篇 |
2017年 | 155篇 |
2016年 | 259篇 |
2015年 | 256篇 |
2014年 | 257篇 |
2013年 | 521篇 |
2012年 | 603篇 |
2011年 | 620篇 |
2010年 | 372篇 |
2009年 | 326篇 |
2008年 | 480篇 |
2007年 | 460篇 |
2006年 | 425篇 |
2005年 | 395篇 |
2004年 | 340篇 |
2003年 | 296篇 |
2002年 | 232篇 |
2001年 | 133篇 |
2000年 | 123篇 |
1999年 | 101篇 |
1998年 | 75篇 |
1997年 | 68篇 |
1996年 | 74篇 |
1995年 | 56篇 |
1994年 | 66篇 |
1993年 | 48篇 |
1992年 | 54篇 |
1991年 | 73篇 |
1990年 | 71篇 |
1989年 | 64篇 |
1988年 | 50篇 |
1987年 | 40篇 |
1985年 | 52篇 |
1984年 | 78篇 |
1983年 | 40篇 |
1982年 | 56篇 |
1981年 | 49篇 |
1980年 | 50篇 |
1979年 | 40篇 |
1978年 | 42篇 |
1977年 | 55篇 |
1976年 | 40篇 |
1975年 | 39篇 |
1974年 | 37篇 |
1973年 | 37篇 |
排序方式: 共有8734条查询结果,搜索用时 31 毫秒
141.
142.
Melinda Fekete Pál Kolonits Ngo Thi Hien Lajos Novák 《Central European Journal of Chemistry》2005,3(4):792-802
New tryptamine 5, 7 and β-carboline derivatives 3 were preparated by palladium-catalyzed coupling reaction of 5-bromotryptamine 1 with aryl boronic acids.
Dedicated to Professor András Lipták on his 70th birthday. 相似文献
143.
[reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction. 相似文献
144.
Marie-Noelle Avettand-Fènoël N. David G. Reumont J. -M. Fiorani M. Vilasi P. Perrot 《Journal of Thermal Analysis and Calorimetry》2007,90(2):329-332
The Fe-Sn-Zn system is of interest because Sn is one element added to the Zn galvanizing bath to overcome the drawbacks due
to the presence of Si in semi-killed steels. This work has been undertaken with the aim to understand the tin effect on the
microstructure and the layers growth in batch galvanized coatings on low alloyed steels.
Various experimental techniques such as metallography, scanning electron microscopy (SEM) coupled with X-ray energy dispersive
spectroscopy (EDX) are used in order to characterize the microstructure and the properties of such coatings elaborated in
a zinc bath enriched with tin.
Solidification phenomena and layers growth mechanisms during galvanization are explained by means of the ternary phase diagram
Fe-Sn-Zn at 450°C. The Calphad method allows to obtain this phase diagram from the three optimized binary phase diagrams Fe-Sn,
Fe-Zn and Sn-Zn and some experimental data inside the ternary Fe-Sn-Zn system. 相似文献
145.
Two new hydrolytically stable analogues of β-d-arabinofuranosyl-1-monophosphoryldecaprenol, the donor substrate for mycobacterial arabinosyltransferase, have been prepared. Biological evaluation of these compounds in vitro against Mycobacterium tuberculosis H37Rv strain revealed a promising activity. 相似文献
146.
Rondelez Y Rager MN Duprat A Reinaud O 《Journal of the American Chemical Society》2002,124(7):1334-1340
Two calixarene-based model systems (a and b) for monocopper enzymes are compared. Both present a tris(pyridine) coordination site for Cu that mimics the imidazole-rich neutral binding site in enzymes. Upon reaction with 1 equiv of copper(I), the tridentate ligands gave rise to ill-defined unsymmetrical complexes. However, in the presence of an organonitrile RCN (R = Me, Et, Ph), tetrahedral species were obtained, with the nitrilo ligand included in the calixarene hydrophobic cone. System b presents a larger cavity than system a, with a wider opening thanks to the removal of three tBu groups from the calixarene structure. As a result, the recognition pattern for MeCN vs PhCN is inverted, and the relative affinity constants differ by 3 orders of magnitude. The mechanism of the acetonitrile exchange at the cuprous centers was studied by (1)H NMR spectroscopy. Thermodynamic and kinetic data show that it follows a dissociative pathway in both cases. The main differences between systems a and b stem from the presence of a door that entraps the guest in case a. In system b indeed, the removal of three calixarene tBu groups led to a 100-fold acceleration of the MeCN exchange rate. Hence, these supramolecular systems provide a rare and interesting model for the hydrophobic substrate channel giving access to a metalloenzyme active site. 相似文献
147.
A new method has been developed for the determination of the isotope abundance ratios of deuterium, D, and oxygen-18, 18O, in water vapor (and water) using selected ion flow tube mass spectrometry (SIFT-MS). H3O+ ions are injected into the helium carrier gas where they associate with the H2O and HDO molecules in a sample of water introduced into the carrier gas. The D and 18O contents of the product cluster ions H8DO4+ and H9(18)OO3+ at m/e = 74 and 75, respectively, are determined by reference to the majority cluster ion H9O4+ at m/e = 73. Allowance is made for the contribution of the H8(17)OO3+ ions to the m/z = 74 ions. Absolute isotopic ratios are measured within seconds without the need for precalibration of the SIFT-MS instrument, currently to an accuracy of better than 2%. 相似文献
148.
Raif Kurtaran Cengiz Arici Kaan C. Emregül Diner Ülkü Orhan Atakol Mustafa Tatekin 《无机化学与普通化学杂志》2003,629(9):1617-1621
A homo‐dinuclear NiII complex was prepared from 2, 6‐bis(3, 5‐dimethylpyrazolyl)pyridine (Me4‐bpp) and azide ions in nonaqueous media. It was characterized by single crystal X‐ray structural analysis, IR spectroscopy, and elemental analysis. In addition, the electrochemical properties of the compound were determined with cyclic voltammetry in DMF. The title compound crystallizes in the P21/n monoclinic space group, with unit cell parameters a = 8.978(1), b = 12.459(1), c = 17.764(1) Å, ß =100.603(3)°, V = 1953.0(3) Å3, Z = 2. The Ni2+ ion has a distorted octahedral environment involving three nitrogen atoms of the Me4‐bpp ligand, two nitrogen atoms from the bridged azide group, and one nitrogen atom from the terminal azide group. The Ni···Ni distance is 3.273(5) Å. 相似文献
149.
Cremer GA Bureaud N Lelièvre D Piller V Piller F Delmas A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6353-6360
Our goal was to develop mimics of MUC1, highly immunogenic to induce an efficient immune response against the tumor-associated form of MUC1, and sufficiently different from the natural antigen to bypass the tolerance barrier in humans. With the aim of obtaining a well-defined peptide construct as a means of evoking the precise immune responses required in immunotherapy, we synthesized artificial mimics of the MUC1 protein composed of two MUC1 repeat units of inverse orientation and a universal T-helper epitope. To synthesize these heteromeric peptide constructs, we followed a convergent approach using chemoselective ligation based on oxime chemistry. A stem peptide was first synthesized bearing two orthogonally masked aldehydes. After successive deprotection, two oxime bonds can be specifically generated. The proposed strategy proved to be concise and robust, and allowed the synthesis of the tri-branched protein in a very satisfactory yield. The different constructs were tested for their ability to generate antibodies able to recognize the MUC1 protein. 相似文献
150.
de Arquer María Ponte Borja Pino Raúl 《Central European Journal of Operations Research》2022,30(4):1307-1336
Central European Journal of Operations Research - We study a hybrid system where the demand of customers can be satisfied by both manufacturing new products and remanufacturing used products. To... 相似文献