全文获取类型
收费全文 | 19751篇 |
免费 | 3558篇 |
国内免费 | 2531篇 |
专业分类
化学 | 14236篇 |
晶体学 | 230篇 |
力学 | 1247篇 |
综合类 | 180篇 |
数学 | 2504篇 |
物理学 | 7443篇 |
出版年
2024年 | 42篇 |
2023年 | 407篇 |
2022年 | 578篇 |
2021年 | 745篇 |
2020年 | 834篇 |
2019年 | 767篇 |
2018年 | 729篇 |
2017年 | 658篇 |
2016年 | 880篇 |
2015年 | 986篇 |
2014年 | 1114篇 |
2013年 | 1428篇 |
2012年 | 1719篇 |
2011年 | 1863篇 |
2010年 | 1313篇 |
2009年 | 1151篇 |
2008年 | 1334篇 |
2007年 | 1220篇 |
2006年 | 1071篇 |
2005年 | 902篇 |
2004年 | 693篇 |
2003年 | 622篇 |
2002年 | 661篇 |
2001年 | 529篇 |
2000年 | 375篇 |
1999年 | 413篇 |
1998年 | 347篇 |
1997年 | 258篇 |
1996年 | 289篇 |
1995年 | 286篇 |
1994年 | 237篇 |
1993年 | 195篇 |
1992年 | 167篇 |
1991年 | 175篇 |
1990年 | 180篇 |
1989年 | 130篇 |
1988年 | 104篇 |
1987年 | 88篇 |
1986年 | 65篇 |
1985年 | 76篇 |
1984年 | 35篇 |
1983年 | 39篇 |
1982年 | 28篇 |
1981年 | 23篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1974年 | 6篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Pd-catalyzed annulation of aryne and aryl ketone O-acetyloxime via C–H bond activation was realized. Through the C–H bond activation/insertion/cyclization/elimination reaction sequence, phenanthridines are successfully constructed, providing an attractive strategy to approach substituted heterocycle without preactivation of starting materials. 相似文献
992.
A convenient and regioselective one-pot synthesis of 3-chloride or 3-bromide quinoline derivatives was achieved through a Grignard addition reaction by alkynyl Grignard regent to o-trifluoroacetyl aniline and a Cu(II)-catalyzed cyclization–halogenation tandem reaction with aqueous HCl or HBr as electrophilic reagent. 相似文献
993.
Yunju Zhang Jingyu Sun Wanqiao Zhang Yizhen Tang Rongshun Wang 《Journal of computational chemistry》2014,35(22):1646-1656
The reaction of propargyl alcohol with hydroxyl radical has been studied extensively at CCSD(T)/aug‐cc‐pVTZ//MP2/cc‐pVTZ level. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. Two reaction mechanisms were revealed, namely addition/elimination and hydrogen abstraction mechanism. The reaction mechanism confirms that OH addition to C?C triple bond forms the chemically activated adducts, IM1 (·CHCOHCH2OH) and IM2 (CHOH·CCH2OH), and the hydrogen abstraction pathways (? CH2OH bonded to the carbon atom and alcohol hydrogen) may occur via low barriers. Harmonic model of Rice–Ramsperger–Kassel–Marcus theory and variational transition state theory are used to calculate the overall and individual rate constants over a wide range of temperatures and pressures. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with Ar as bath gas, IM1 (·CHCOHCH2OH) and IM2 (CHOH·CCH2OH) formed by collisional stabilization are dominant in the low temperature range. The production of CHCCHOH + H2O via hydrogen abstraction becomes dominate at higher temperature. The fraction of IM3 (CH2COHCH2·O) is very significant over the moderate temperature range. © 2014 Wiley Periodicals, Inc. 相似文献
994.
Xiao-qing Liu Fang Kong Jia-li Liao Song-dong Ding Yuan-you Yang Huang Huang Shun-zhong Luo Guo-ping Liu Xing-liang Li Ji-jun Yang Jun Tang Ning Liu 《Journal of Radioanalytical and Nuclear Chemistry》2014,302(3):1069-1076
The extraction kinetics of uranium(VI) and thorium(IV) with Tri-iso-amyl phosphate (TiAP) from nitric acid medium has been investigated using a Lewis Cell. Especially, dependences of the extraction rate on stirring speed, temperature, interfacial area were firstly measured to elucidate the extraction kinetics regimes. The experimental results demonstrated that extraction kinetic of U(VI) is governed by chemical reactions at interface with an activation energy, Ea, of 43.41 kJ/mol, while the rate of Th(IV) extraction is proved to be intermediate controlled, of which the Ea is 23.20 kJ/mol. Reaction orders with respect to the influencing parameters of the extraction rate are determined, and the rate equations of U(VI) and Th(IV) at 293 K have been proposed as $$ {\text{r}} = - {\text{dcUO}}_{ 2} \left( {{\text{NO}}_{ 3} } \right)_{ 2} /{\text{dt}} = 1. 80 \times 10^{ - 3} \left[ {{\text{UO}}_{ 2} \left( {{\text{NO}}_{ 3} } \right)_{ 2} } \right]^{ 1.0 1} \left[ {\text{TiAP}} \right]^{0. 5 5} , $$ $$ {\text{r}} = - {\text{dcTh }}\left( {{\text{NO}}_{ 3} } \right)_{ 4} /{\text{dt}} = 1. 8 8\times 10^{ - 3} \left[ {{\text{Th }}\left( {{\text{NO}}_{ 3} } \right)_{ 4} } \right]^{ 1.0 4} \left[ {\text{TiAP}} \right]^{ 1. 7 7} \left[ {{\text{HNO}}_{ 3} } \right]^{0. 3 8} , $$ respectively. 相似文献
995.
Qingpei Xiang Dongfeng Tian Fanhua Hao Chengsheng Chu Ge Ding Jun Zeng Fei Luo 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(3):1439-1445
In recent years, the cerium-doped lanthanum bromide, LaBr3 (Ce = 5 %) detector is increasingly playing an important role in radiation measurements because of its higher energy resolution (~3 % at 662 keV), faster luminescence decay time (~35 ns) and higher detection efficiency compared to 7.65 cm × 7.65 cm NaI(Tl) detector. Intrinsic spectra between 1,800 and 3,000 keV derived from internal radioactivity within LaBr3(Ce) scintillators have been investigated in some literatures, and these results are confirmed by the experiments in this work. In this paper, a new method for LaBr3(Ce) detector energy calibration from 100 to 2,000 keV is proposed using the intrinsic spectra (self-calibration) instead of the standard gamma sources. Proof-of-concept experiment results show that self-calibration can guarantee energy accuracy of better than 0.815 % and can be applied outside the laboratory. The stability and applicability of this method are also investigated systematically. 相似文献
996.
997.
998.
Simultaneous determination of ten organophosphate pesticide residues in fruits by gas chromatography coupled with magnetic separation
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
In this study, γ‐Fe2O3/chitosan magnetic microspheres were synthesized and evaluated by X‐ray diffraction, SEM, thermogravimetric analysis, and static and kinetic adsorption experiments. Results showed that the magnetic microspheres exhibited good adsorption ability, and offered fast kinetics for the adsorption of trichlorfon, methamidophos, malathion, methyl parathion, dimethoate, omethoate, phosphamidon, phorate, isocarbophos, and chlorpyrifos. Based on magnetic separation, a simple method of magnetic SPE coupled to GC for the simultaneous determination of ten trace organophosphate pesticide residues was developed. Under the optimal conditions, the enrichment factor for ten organophosphorus pesticides was 10.1–364.7 and linear range was 0.001–10.0 mg/L. The LOD (S/N = 3) of the method for the ten pesticides was 0.31–3.59 μg/kg. The RSD for three replicate extractions of spiked samples was between 2.5 and 6.3%. The pear and apple samples spiked with ten organophosphate pesticides at 20 and 200 μg/kg levels were extracted and determined by this method with good recoveries ranging from 79.9 to 98.7%. Moreover, the method has been successfully applied for the determination of the ten organophosphate pesticide residues in peach samples. 相似文献
999.
1000.
Synthesis,Persistent Luminescence,and Thermoluminescence Properties of Yellow Sr3SiO5:Eu2+,RE3+ (RE=Ce,Nd, Dy,Ho, Er,Tm, Yb) and Orange‐Red Sr3−xBaxSiO5:Eu2+, Dy3+ Phosphor
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Ye Li Baohong Li Chenchen Ni Shuxia Yuan Jing Wang Prof. Qiang Tang Prof. Qiang Su 《化学:亚洲杂志》2014,9(2):494-499
Sunlight‐excitable orange or red persistent oxide phosphors with excellent performance are still in great need. Herein, an intense orange‐red Sr3?xBaxSiO5:Eu2+,Dy3+ persistent luminescence phosphor was successfully developed by a two‐step design strategy. The XRD patterns, photoluminescence excitation and emission spectra, and the thermoluminescence spectra were investigated in detail. By adding non‐equivalent trivalent rare earth co‐dopants to introduce foreign trapping centers, the persistent luminescence performance of Eu2+ in Sr3SiO5 was significantly modified. The yellow persistent emission intensity of Eu2+ was greatly enhanced by a factor of 4.5 in Sr3SiO5:Eu2+,Nd3+ compared with the previously reported Sr3SiO5:Eu2+, Dy3+. Furthermore, Sr ions were replaced with equivalent Ba to give Sr3?xBaxSiO5:Eu2+,Dy3+ phosphor, which shows yellow‐to‐orange‐red tunable persistent emissions from λ=570 to 591 nm as x is increased from 0 to 0.6. Additionally, the persistent emission intensity of Eu2+ is significantly improved by a factor of 2.7 in Sr3?xBaxSiO5:Eu2+,Dy3+ (x=0.2) compared with Sr3SiO5:Eu2+,Dy3+. A possible mechanism for enhanced and tunable persistent luminescence behavior of Eu2+ in Sr3?xBaxSiO5:Eu2+,RE3+ (RE=rare earth) is also proposed and discussed. 相似文献