全文获取类型
收费全文 | 3402篇 |
免费 | 188篇 |
国内免费 | 268篇 |
专业分类
化学 | 3129篇 |
晶体学 | 29篇 |
力学 | 8篇 |
综合类 | 14篇 |
数学 | 3篇 |
物理学 | 168篇 |
综合类 | 507篇 |
出版年
2023年 | 28篇 |
2022年 | 64篇 |
2021年 | 52篇 |
2020年 | 83篇 |
2019年 | 81篇 |
2018年 | 72篇 |
2017年 | 100篇 |
2016年 | 80篇 |
2015年 | 97篇 |
2014年 | 157篇 |
2013年 | 335篇 |
2012年 | 161篇 |
2011年 | 146篇 |
2010年 | 121篇 |
2009年 | 151篇 |
2008年 | 159篇 |
2007年 | 171篇 |
2006年 | 185篇 |
2005年 | 167篇 |
2004年 | 172篇 |
2003年 | 172篇 |
2002年 | 208篇 |
2001年 | 94篇 |
2000年 | 74篇 |
1999年 | 76篇 |
1998年 | 53篇 |
1997年 | 66篇 |
1996年 | 66篇 |
1995年 | 58篇 |
1994年 | 70篇 |
1993年 | 50篇 |
1992年 | 47篇 |
1991年 | 36篇 |
1990年 | 32篇 |
1989年 | 31篇 |
1988年 | 27篇 |
1987年 | 18篇 |
1986年 | 14篇 |
1985年 | 7篇 |
1984年 | 14篇 |
1983年 | 7篇 |
1982年 | 12篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 9篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1972年 | 4篇 |
1966年 | 1篇 |
排序方式: 共有3858条查询结果,搜索用时 15 毫秒
1.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
2.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
3.
Vanessa R. Machado Louis P. Sandjo Giovanni L. Pinheiro Milene H. Moraes Mario Steindel Moacir G. Pizzolatti 《Natural product research》2018,32(3):275-281
The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by 1H NMR, 13C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC50 = 12.48 μg/mL) and the lowest cytotoxic derivative (CC50 = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase. 相似文献
4.
In this study, stoichiometric protonation constants of L-tyrosine, L-cysteine, L-tryptophane, L-lysine, and L-histidine, and
their methyl and ethyl esters in water and ethanol–water mixtures of 30, 50, and 70% ethanol (v/v), were determined potentiometrically
using a combined pH electrode system calibrated as the concentration of hydrogen ion. Titrations were performed at 25∘C and the ionic strength of the medium was maintained at 0.10 mol⋅L−1 using sodium chloride. Protonation constants were calculated by using the BEST computer program. The effect of solvent composition
on the protonation constants is discussed. The log10 K2 values of esters generally decreased with increasing ethanol content. However, the log10 K1 values of the esters of L-tyrosine, L-cysteine, and L-tryptophane were found to increase with increasing ethanol content
in contrast those of L-lysine and L-histidine esters. 相似文献
5.
6.
Guanidinium nitrate: a novel reagent for aryl nitrations 总被引:1,自引:0,他引:1
Nitration of various aromatic compounds utilising guanidinium nitrate in 85% sulfuric acid as a nitrating agent has been studied. 相似文献
7.
A. A. Zazhogin A. P. Zazhogin A. I. Komyak A. I. Serafimovich 《Journal of Applied Spectroscopy》2003,70(6):827-831
Based on the analysis of electronic absorption and luminescence spectra, the processes of complexing in an aqueous solution of uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) on gradual addition of small amounts of acetone have been investigated. In a pure aqueous solution, uranyl exists as the UO2·5H2O complex. It is shown that addition of acetone to the solution leads to displacement of some water molecules from the first coordination sphere of uranyl and formation of uranyl nitrate dihydrate complexes, UO2(NO3)2·2H2O. It has been established that the stability of these complexes is determined by the decrease in both the water activity and the degree of hydration of uranyl and nitrate. This is the result of the local increase in the concentration of the molecules of acetone (due to its hydrophobicity) in those regions of the solution in which there are uranyl and nitrate ions. The experimental facts supporting the proposed mechanism are given. 相似文献
8.
M. V. Veselovskaya S. V. Shilin M. M. Garazd V. P. Khilya 《Chemistry of Natural Compounds》2003,39(2):177-181
Furocoumarins modified by amino acids were prepared by condensation of the N-hydroxysuccinimide ester of 3-(2,3,5-trimethyl-7-oxofuro[3,2-g]chromen-6-yl)propanoic acid with amino acids. 相似文献
9.
This research extends previous work with dynamic models to manage groundwater quality by using the consumptive nitrate use rate instead of the nitrate application rate. The analysis indicates that misspecification results in overestimation of economic benefits, and supra-optimum nitrogen fertilizer application rates and groundwater nitrate stocks at a steady state. 相似文献
10.
The treatment of tertiary esters with triphenylphosphine and iodine under mild conditions gives the most stable alkene in good yield. Formates, acetates and trifluoroacetates were studied. 相似文献