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111.
Synthesis of 1‐silacyclopent‐2‐ene derivatives using 1,2‐hydroboration, 1,1‐organoboration and protodeborylation 下载免费PDF全文
The reaction of di(alkyn‐1‐yl)vinylsilanes R1(H2C═CH)Si(C≡C―R)2 (R1 = Me ( 1 ), Ph ( 2 ); R = Bu (a), Ph (b), Me2HSi (c)) at 25°C with 1 equiv. of 9‐borabicyclo[3.3.1]nonane (9‐BBN) affords 1‐silacyclopent‐2‐ene derivatives ( 3a , 3b , 3c , 4a , 4b ), bearing one Si―C≡C―R function readily available for further transformations. These compounds are formed by consecutive 1,2‐hydroboration followed by intramolecular 1,1‐carboboration. Treated with a further equivalent of 9‐BBN in benzene they are converted at relatively high temperature (80–100°C) into 1‐alkenyl‐1‐silacyclopent‐2‐ene derivatives ( 5a , 5b 6a , 6b ) as a result of 1,2‐hydroboration of the Si―C≡C―R function. Protodeborylation of the 9‐BBN‐substituted 1‐silacyclopent‐2‐ene derivatives 3 , 4 , 5 , 6 , using acetic acid in excess, proceeds smoothly to give the novel 1‐silacyclopent‐2‐ene ( 7 , 8 , 9 , 10 ). The solution‐state structural assignment of all new compounds, i.e. di(alkyn‐1‐yl)vinylsilanes and 1‐silacyclopent‐2‐ene derivatives, was carried out using multinuclear magnetic resonance techniques (1H, 13C, 11B, 29Si NMR). The gas phase structures of some examples were calculated and optimized by density functional theory methods (B3LYP/6‐311+G/(d,p) level of theory), and 29Si NMR parameters were calculated (chemical shifts δ29Si and coupling constants nJ(29Si,13C)). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
112.
Dr. Oleg A. Levitskiy Olga I. Aglamazova Prof. Dr. Vadim A. Soloshonok Dr. Hiroki Moriwaki Prof. Dr. Tatiana V. Magdesieva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(31):7074-7082
The results of extended comparative investigation of nickel(II) Schiff base complexes (containing various auxiliary chiral moieties) commonly used as a methodological platform for the asymmetric synthesis of tailor-made α-amino acids are provided. The following issues are addressed: 1) redox activity (determining the possibility for electrochemically induced reactions); 2) quantitative estimation of the reactivity of deprotonated complexes towards electrophiles; and 3) quantum-chemical estimation of noncovalent interactions in the metal coordination environment (which shed light on the origin of the stereochemical outcome observed for different stereoinductors). Possible mechanisms that determine the relationship between the stereochemical configuration of a molecule and its electronic structure are discussed. The DFT-calculated HOMO–LUMO energies and localization, as well as relative energies for the (S)- and (R)-alanine derivatives, that determine the stereoinduction efficiency in thermodynamically controlled reactions in nickel(II) coordination are provided. The computational data are supported by experimental results on the monobenzylation of glycine derivatives. 相似文献
113.
Back Cover: Single‐Atom Gold Catalysis in the Context of Developments in Parahydrogen‐Induced Polarization (Chem. Eur. J. 19/2015) 下载免费PDF全文
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Shestakova Tatyana S. Deev Sergey L. Khalymbadzha Igor А. Rusinov Vladimir L. Paramonov Alexander S. Arseniev Alexander S. Shenkarev Zakhar O. Charushin Valery N. Chupakhin Oleg N. 《Chemistry of Heterocyclic Compounds》2021,57(4):479-482
Chemistry of Heterocyclic Compounds - Isotope-labeled antiviral drug Triazavirin containing 2H, 13C, and 15N atoms in its structure has been synthesized. 13C2H3I and KS13CN served as donors of 13C... 相似文献
118.
Oleg G. Sinyashin Irina P. Romanova Gulshat G. Yusupova Valery I. Kovalenko Yuri Y. Efremov Irina I. Vandyukova 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Data on the structure of cycloadducts of organophosphorus dipolar reagents and fullerenes arc absent, to our knowledge. We died the reactions and the shucturc of cycloadducts of phosphorylated azidcs and nitrile oxide with [60]fullcrcnc. The cycloaddition of diphcnylphosphinic llzide to fullcrme has bcm determined to lead to the 1 -[(N-diphenylphosphoryl)amino]-2-hydroxy[6O]hllcrme (l), the mixhuc of phosphorylated aziridinofullcrcne (2) and derivative of fullerne (3) with one aziridine fragment and one aminohydmxy-fragment, or to product (4), depending on the conditions of don . 相似文献
119.
Lidiya I. Kursheva Olga N. Kataeva Dmitrii B. Krivolapov Elvira S. Batyeva Oleg G. Sinyashin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1425-1426
Abstract The synthesis and coordination chemistry of ligands bearing PS donor groups in complexes with copper(I) halides, in particular thiophosphites, thiophosphonites, and thiophosphinites, are described. 相似文献
120.
Nimmy R. Mammoottil James F. Reuther Dumindika A. Siriwardane Oleg V. Kulikov Bruce M. Novak 《Journal of polymer science. Part A, Polymer chemistry》2017,55(18):2915-2934
Described herein is a comprehensive survey on the most recent advancements in polycarbodiimide synthetic methodologies, structure determination, property design, and self-assembly. In particular, the 15N-isotopic enrichment of polycarbodiimides is detailed along with the use of 15N NMR to identify the regioregularity and mechanism of chiroptical switching in polycarbodiimides. Furthermore, the new Ni(II) mediated “living” polymerization is explained along with its utilization in the incorporation of polycarbodiimides into block copolymers, graft copolymers, and star polymers. Finally, we review the recent discoveries focusing on the highly tunable self-assembly behaviors of polycarbodiimide homopolymers and copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2915–2934 相似文献