全文获取类型
收费全文 | 45940篇 |
免费 | 3908篇 |
国内免费 | 6419篇 |
专业分类
化学 | 31706篇 |
晶体学 | 1407篇 |
力学 | 1057篇 |
综合类 | 273篇 |
数学 | 8686篇 |
物理学 | 13138篇 |
出版年
2024年 | 90篇 |
2023年 | 571篇 |
2022年 | 1096篇 |
2021年 | 1044篇 |
2020年 | 1359篇 |
2019年 | 1407篇 |
2018年 | 1192篇 |
2017年 | 1444篇 |
2016年 | 1489篇 |
2015年 | 1412篇 |
2014年 | 2044篇 |
2013年 | 3448篇 |
2012年 | 2282篇 |
2011年 | 3516篇 |
2010年 | 2747篇 |
2009年 | 3147篇 |
2008年 | 3320篇 |
2007年 | 3176篇 |
2006年 | 2821篇 |
2005年 | 2624篇 |
2004年 | 2280篇 |
2003年 | 1855篇 |
2002年 | 1687篇 |
2001年 | 1272篇 |
2000年 | 1226篇 |
1999年 | 1048篇 |
1998年 | 858篇 |
1997年 | 771篇 |
1996年 | 686篇 |
1995年 | 684篇 |
1994年 | 636篇 |
1993年 | 554篇 |
1992年 | 449篇 |
1991年 | 323篇 |
1990年 | 226篇 |
1989年 | 216篇 |
1988年 | 173篇 |
1987年 | 129篇 |
1986年 | 127篇 |
1985年 | 134篇 |
1984年 | 109篇 |
1983年 | 71篇 |
1982年 | 95篇 |
1981年 | 83篇 |
1980年 | 89篇 |
1979年 | 63篇 |
1978年 | 62篇 |
1977年 | 45篇 |
1976年 | 31篇 |
1973年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
2.
3.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
4.
5.
Highly dispersed palladium nanoclusters incorporated in amino‐functionalized silica spheres for the selective hydrogenation of succinic acid to γ‐butyrolactone 下载免费PDF全文
Highly dispersed palladium nanoclusters incorporated on amino‐functionalized silica sphere surfaces (Pd/SiO2‐NH2) were fabricated by a simple one‐pot synthesis utilizing 3‐(2‐aminoethylamino)propyltrimethoxysilane (AAPTS) as coordinating agent. Uniform palladium nanoclusters with an average size of 1.1 nm can be obtained during the co‐condensation of tetraethyl orthosilicate and AAPTS owing to the strong interaction between palladium species and amino groups in AAPTS. The palladium particle size can be controlled by addition of AAPTS and plays a significant role in the catalytic performance. The Pd/SiO2‐NH2 catalyst exhibits high catalytic activity for succinic acid hydrogenation with 100% conversion and 94% selectivity towards γ‐butyrolactone using 1,4‐dioxane as solvent at 240°C and 60 bar for 4 h. Moreover, the Pd/SiO2‐NH2 catalyst is robust and readily reusable without loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
6.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
7.
The effect of Re addition on the microstructure and hardening behaviour of the dual two-phase Ni3Al (L12) and Ni3V (D022) intermetallic alloy was investigated by scanning electron microscopy, transmission electron microscopy and Vickers hardness test. The two-phase eutectoid microstructure accompanying the Re-rich precipitates were observed in the channel region of the alloys in which Re substituted for Ni but not in those in which Re substituted for Al and V. The concomitant addition of Nb (or Ta) with Re more stabilized the two-phase eutectoid microstructure and consequently more induced the fine precipitates in the channel region. The annealing at temperatures below the eutectoid temperature was necessary to induce the fine precipitates in the channel region and thereby result in the precipitation hardening. The fine precipitation in the channel region and related hardening was attributed to the alloying feature so that Re is soluble in the A1 (fcc) phase at high temperatures and becomes less soluble in the two intermetallic phases decomposed from the A1 phase at low temperatures. 相似文献
8.
9.
Addition of functionalized zinc-copper reagents to the title complexes proceeds in a highly diastereoselective fashion to afford dienol complexes. The relative configurations of adducts 3d were determined by single X-ray diffraction analysis. 相似文献
10.
Rajiv Manohar G. Tripathi A.K. Srivastava A.K. Prajapati 《Journal of Physics and Chemistry of Solids》2006,67(11):2300-2304
Dielectric properties of polymer-liquid crystal mixture, having constituent polymer, poly-butyl methacrylate (PBMA) and liquid crystal, cholesteryl nonanoate, are reported as a function of frequency and temperature. The measurement has been done in a temperature range of 300-375 K and frequency range of 100 Hz-10 MHz. The dielectric permittivity and dielectric loss shows significant changes with the addition of polymer molecules in liquid crystal. The significant feature of composite formation is that the pure liquid crystal and polymer do not show dielectric relaxation in the frequency range covered, while the composite shows relaxation peak at a particular frequency. The optical transmittance of pure liquid crystal and composite has also been measured and compared. 相似文献