全文获取类型
收费全文 | 1228篇 |
免费 | 60篇 |
国内免费 | 4篇 |
专业分类
化学 | 907篇 |
晶体学 | 7篇 |
力学 | 27篇 |
数学 | 76篇 |
物理学 | 275篇 |
出版年
2023年 | 11篇 |
2022年 | 5篇 |
2021年 | 19篇 |
2020年 | 17篇 |
2019年 | 17篇 |
2018年 | 13篇 |
2017年 | 9篇 |
2016年 | 34篇 |
2015年 | 29篇 |
2014年 | 38篇 |
2013年 | 63篇 |
2012年 | 84篇 |
2011年 | 101篇 |
2010年 | 63篇 |
2009年 | 57篇 |
2008年 | 78篇 |
2007年 | 80篇 |
2006年 | 83篇 |
2005年 | 66篇 |
2004年 | 55篇 |
2003年 | 50篇 |
2002年 | 42篇 |
2001年 | 23篇 |
2000年 | 23篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 9篇 |
1996年 | 20篇 |
1995年 | 7篇 |
1994年 | 12篇 |
1993年 | 11篇 |
1992年 | 15篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 15篇 |
1984年 | 7篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 5篇 |
1974年 | 2篇 |
1973年 | 4篇 |
排序方式: 共有1292条查询结果,搜索用时 62 毫秒
31.
32.
[reactions: see text] [(Ph3P)CuH]6 effectively catalyzes the hydrostannation of activated alkynes with exclusive regioselectivity for alpha-stannation. Syn hydrostannation is observed exclusively for alkynoates. Anti or syn hydrostannation adducts are obtained as products for alkynone substrates. 相似文献
33.
Ging-ho Hsiue Ying-Ling Liu Yie-Shun Chiu 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2155-2159
Novel energetic thermoplastic elastomers (TPEs) based on tetrahydrofuran (THF) and 3,3-bis (azidomethyl) oxetane (BAMO) were prepared in this present study by cationic living polymerization. A bifunctional catalyst, triflic anhydride [(CF3SO2)2)O] was selected to be an initiator for the polymerization THF and BAMO. The resulting polymers were characterized by IR, NMR, and DSC, which demonstrated that triblock copolymers with A-B-A type were formed. The polymers were indicated from thermogravimetric analysis (TGA) to have decomposed at approximately 243°C. The decomposition enthalpies were determined by DSC. These enthalpies were varied with the poly-BAMO contents of the copolymers. The synthesized polymers exhibited relatively good mechanical properties and thermoplastic characteristics at room temperature. © 1994 John Wiley & Sons, Inc. 相似文献
34.
Twenty-two isomers/conformers of C3H6S+√ radical cations have been identified and their heats of formation (ΔHf) at 0 and 298 K have been calculated using the Gaussian-3 (G3) method. Seven of these isomers are known and their ΔHf data are available in the literature for comparison. The least energy isomer is found to be the thioacetone radical cation (4+) with C2v symmetry. In contrast, the least energy C3H6O+√ isomer is the 1-propen-2-ol radical cation. The G3 ΔHf298 of 4+ is calculated to be 859.4 kJ mol−1, ca. 38 kJ mol−1 higher than the literature value, ≤821 kJ mol−1. For allyl mercaptan radical cation (7+), the G3 ΔHf298 is calculated to be 927.8 kJ mol−1, also not in good agreement with the experimental estimate, 956 kJ mol−1. Upon examining the experimental data and carrying out further calculations, it is shown that the G3 ΔHf298 values for 4+ and 7+ should be more reliable than the compiled values. For the five remaining cations with available experimental thermal data, the agreement between the experimental and G3 results ranges from fair to excellent.
Cation CH3CHSCH2+√ (10+) has the least energy among the eleven distonic radical cations identified. Their ΔHf298 values range from 918 to 1151 kJ mol−1. Nevertheless, only one of them, CH2=SCH2CH2+√ (12+), has been observed. Its G3 ΔHf298 value is 980.9 kJ mol−1, in fair agreement with the experimental result, 990 kJ mol−1.
A couple of reactions involving C3H6S+√ isomers CH2=SCH2CH2+√ (12+) and trimethylene sulfide radical cation (13+) have also been studied with the G3 method and the results are consistent with experimental findings. 相似文献
35.
In this study, microemulsion electrokinetic chromatography (MEEKC) and micellar electrokinetic chromatography (MEKC) were compared for their abilities to separate and detect thirteen phenolic compounds (syringic acid, p-coumaric acid, vanillic acid, caffeic acid, gallic acid, 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, (+)-catechin, (-)-epigallocatechin, (-)-epicatechin gallate, (-)-epigallocatechin gallate, (-)-epicatechin, and (-)-gallocatechin), and two other ingredients (caffeine and theophylline) in teas and grapes. Separation of phenolic compounds was improved by changing the SDS concentration for MEEKC, but the SDS concentration rarely affected the resolution for MEKC. Organic modifier (acetonitrile or methanol) was found to markedly influence the resolution and selectivity for both MEEKC and MEKC systems. In addition, a higher voltage and a higher column temperature improved the separation efficiency without any noticeable reduction in resolution for MEEKC whereas they caused a poor resolution for the MEKC system. Although separations with baseline resolution were achieved by the optimized MEEKC and MEKC methods, the separation selectivity resulting from the proposed MEEKC method was completely different from that of MEKC. 相似文献
36.
This study was based upon the responses of 116 Taiwanese primary school children aged nine-ten years to a questionnaire concerning their emotional and motivational responses to mathematical problems. A cluster analysis revealed four distinct patterns of response, which were differentially related to attainment. These patterns of emotional response were subsequently investigated further with a smaller sample of children using a repertory grid technique and an associated interview. The four patterns were found to have differential characteristics and development processes in terms of emotional variables and preferred problem types. Emotion is an indispensable part of cognitive activities, such as mathematical problem-solving. Burton (1994) indicates that children as mathematicians often strive for progression and newness to enhance capacity, but also experience anxiety when confronted with the need to integrate new ideas with existing patterns of understanding. Mason, Burton and Stacey (1996) point out key moments in the problem-solving process, in which distinct emotional issues are likely to be raised, such as relief, excitement and confidence. 相似文献
37.
38.
Y. Y. Shu J. E. Dowdall C. Chiu R. C. Lao 《International journal of environmental analytical chemistry》2013,93(2-4):185-194
Abstract Polychlorinated biphenyls (PCBs) are toxic, perssstent, global environmental contaminants which were formulated as complex mixtures of congeners. Many methods have been developed in the past to analyze PCB in transformer oil samples for regulatory purposes. The most important consideration in the cleanup procedure is the ability to remove the oil from the sample matrix, since trace amount of oil will interfere with the subsequent GC-MS analysis. Electron capture detection (ECD) has been the most common method for gas chromatographic analysis of PCBs because of its high sensitivity toward halogenated compounds. ECD can also respond to some non-PCB compound resulting in biased concentrations of PCB. In this work, a two-stage cleanup method, using DMSO liquid/liquid extraction and HPLC column chromatography. has been applied to two types of transformer oil. Five internal standards have been selected to show their performance in the presence of different oil matrices. The comparison of the PCB quantification at different conditions for GC-MS and GC-ECD will be demonstrated. 相似文献
39.
We have recently established preparative procedures for titanium(III) reduction of sulfoxides to sulfides1 and nitroarenes to amines.2 In continuation of this program which is aimed at exploring the synthetic potential of titanium(III) ion, we have found that α-haloketones undergo facile dehalogenation upon treatment with titanium trichloride. 相似文献
40.
Exploring Regioselective Bond Cleavage and Cross‐Coupling Reactions using a Low‐Valent Nickel Complex 下载免费PDF全文
Addison N. Desnoyer Florian W. Friese Weiling Chiu Marcus W. Drover Dr. Brian O. Patrick Prof. Dr. Jennifer A. Love 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):4070-4077
Recently, esters have received much attention as transmetalation partners for cross‐coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ‐η2:η2‐C6H6)] (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η2‐carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl?S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross‐coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η2‐carbonyl complex, phenyl esters were found to predominantly undergo Caryl?O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2‐naphthyl acetate was also found to undergo clean Caryl?O bond cleavage, and although stoichiometric cross‐coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive. 相似文献