全文获取类型
收费全文 | 22675篇 |
免费 | 746篇 |
国内免费 | 370篇 |
专业分类
化学 | 14336篇 |
晶体学 | 152篇 |
力学 | 666篇 |
综合类 | 30篇 |
数学 | 3380篇 |
物理学 | 5227篇 |
出版年
2022年 | 265篇 |
2021年 | 316篇 |
2020年 | 312篇 |
2019年 | 328篇 |
2018年 | 329篇 |
2017年 | 290篇 |
2016年 | 569篇 |
2015年 | 544篇 |
2014年 | 610篇 |
2013年 | 1273篇 |
2012年 | 1192篇 |
2011年 | 1327篇 |
2010年 | 880篇 |
2009年 | 809篇 |
2008年 | 1116篇 |
2007年 | 1136篇 |
2006年 | 983篇 |
2005年 | 972篇 |
2004年 | 905篇 |
2003年 | 869篇 |
2002年 | 847篇 |
2001年 | 575篇 |
2000年 | 519篇 |
1999年 | 395篇 |
1998年 | 299篇 |
1997年 | 268篇 |
1996年 | 290篇 |
1995年 | 288篇 |
1994年 | 293篇 |
1993年 | 223篇 |
1992年 | 220篇 |
1991年 | 244篇 |
1990年 | 251篇 |
1989年 | 209篇 |
1988年 | 187篇 |
1987年 | 174篇 |
1986年 | 154篇 |
1985年 | 269篇 |
1984年 | 308篇 |
1983年 | 197篇 |
1982年 | 234篇 |
1981年 | 190篇 |
1980年 | 206篇 |
1979年 | 177篇 |
1978年 | 153篇 |
1977年 | 216篇 |
1976年 | 181篇 |
1975年 | 157篇 |
1974年 | 145篇 |
1973年 | 146篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
1.
Dominik Vítek Prof. Aleš Růžička Lise Vermeersch Dr. Libor Dostál Dr. Jan Turek Prof. Roman Jambor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202639
Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 ( 1 ; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 ( 2 ) and [LGe⋅BH3]2 ( 3 ) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 ( 4 ) and L(Cl)Ge⋅GaCl3 ( 5 ) without a GeII→B interaction. In 5 , an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed. 相似文献
2.
Peralta Cecilia Mariana Acosta Gimena Henestrosa Cecilia Gil Raúl Andrés Fernández Liliana Patricia 《Journal of Analytical Chemistry》2022,77(3):308-317
Journal of Analytical Chemistry - The present development involved a flow injection strategy using a mini-column of multiwalled carbon nanotubes and fluorescent detection (λex of 283 nm,... 相似文献
3.
Verdecho María-José Alarcón-Valero Faustino Pérez-Perales David Alfaro-Saiz Juan-José Rodríguez-Rodríguez Raúl 《Central European Journal of Operations Research》2021,29(4):1231-1251
Central European Journal of Operations Research - Sustainability practice within supply chains remains in an early development phase. Enterprises still need tools that support the integration of... 相似文献
4.
Reza Kordnezhadian Bing-Yu Li Armir Zogu Dr. Joachim Demaerel Prof. Dr. Wim M. De Borggraeve Dr. Ermal Ismalaj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201491
Pentafluorosulfanyl (SF5)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF5 bond formation as well as the use of SF5-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF5 group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015. 相似文献
5.
Dr. Sabin Llona‐Minguez Dr. Matthieu Desroses Artin Ghassemian Dr. Sylvain A. Jacques Dr. Lars Eriksson Rebecka Isacksson Tobias Koolmeister Dr. Pål Stenmark Dr. Martin Scobie Prof. Thomas Helleday 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7394-7398
A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif. 相似文献
6.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
7.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes 下载免费PDF全文
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
8.
Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells 下载免费PDF全文
Dr. Donatella Diana Anna Russomanno Dr. Lucia De Rosa Dr. Rossella Di Stasi Dr. Domenica Capasso Dr. Sonia Di Gaetano Dr. Alessandra Romanelli Dr. Luigi Russo Dr. Luca D. D'Andrea Prof. Roberto Fattorusso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):91-95
In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast 15N‐edited NMR spectroscopic experiments. To this aim, 15N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including 15N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2. 相似文献
9.
10.