全文获取类型
收费全文 | 1435篇 |
免费 | 111篇 |
国内免费 | 184篇 |
专业分类
化学 | 1038篇 |
晶体学 | 18篇 |
力学 | 88篇 |
综合类 | 25篇 |
数学 | 270篇 |
物理学 | 291篇 |
出版年
2024年 | 1篇 |
2023年 | 27篇 |
2022年 | 30篇 |
2021年 | 55篇 |
2020年 | 55篇 |
2019年 | 64篇 |
2018年 | 67篇 |
2017年 | 50篇 |
2016年 | 68篇 |
2015年 | 69篇 |
2014年 | 84篇 |
2013年 | 106篇 |
2012年 | 128篇 |
2011年 | 134篇 |
2010年 | 80篇 |
2009年 | 105篇 |
2008年 | 81篇 |
2007年 | 69篇 |
2006年 | 72篇 |
2005年 | 56篇 |
2004年 | 38篇 |
2003年 | 35篇 |
2002年 | 20篇 |
2001年 | 18篇 |
2000年 | 28篇 |
1999年 | 25篇 |
1998年 | 33篇 |
1997年 | 25篇 |
1996年 | 21篇 |
1995年 | 17篇 |
1994年 | 14篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1983年 | 1篇 |
排序方式: 共有1730条查询结果,搜索用时 234 毫秒
61.
Concise and efficient three‐component domino [4+1+1] carbocyclization to highly substituted fluoren‐9‐one derivatives promoted by K2CO3 has been developed under microwave irradiation conditions. The direct bis‐cyanation and aryl amination residing in fluoren‐9‐one framework were achieved in a one‐pot operation. The reaction proceeds at fast rates and can be finished within 30 min, which makes workup convenient to give good to excellent chemical yields. 相似文献
62.
63.
Supercritical fluid extraction (SFE) coupled with high‐speed counter‐current chromatography (HSCCC) was successfully used for the extraction and online isolation of the unstable compounds from Rosa damascene in a single extraction and separation operation in two stages. The solvent systems of SFE/HSCCC were optimized with the help of multiexponential function model. At the first stage, the upper phase of the solvent system of n‐butanol–tert‐butyl methyl ether–acetonitrile–0.1% aqueous TFA (1.7:1.0:0.8:4.0, v/v/v/v) was used as both the SFE entrainer and the HSCCC stationary phase, and the target compounds were eluted with the corresponding lower phase to separate the hydrophobic compounds. At the second stage, the upper phase of the solvent system of n‐hexane–ethyl acetate–methanol–water (3.2:1.0:2.8:2.6, v/v/v/v) was used as both the SFE entrainer and the HSCCC stationary phase, followed by elution with the corresponding lower phase to separate the moderate hydrophobic compounds. Six compounds including formononetin, delphinidin, cyaniding, 5,6,4′‐trihydroxy‐7,8‐dimethoxy flavone, 5,3′‐dihydroxy‐7,8‐dimethoxy flavone, and 5‐hydroxy‐6,7,8,3′,4′‐pentamethoxy flavone were successfully separated in one extraction–separation operation within 300 min. The targeted compounds were identified by MS and NMR spectroscopy. This research has opened up great prospects for industrial application of SFE/HSCCC to the extraction and separation of unstable compounds. 相似文献
64.
Liping Zhao Zhenghong Guo Zhenhu Cao Tao Zhang Zhengping Fang Mao Peng 《Polymer Degradation and Stability》2013
Fullerene (C60)/high density polyethylene (HDPE) composites were studied in order to understand for their behaviors on thermal and thermo-oxidative degradation. Under different atmosphere, the influences of C60 on the thermal stability of HDPE are different. Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) demonstrate that in N2 the addition of C60 increases the onset decomposition temperature by about 10 °C with more heavy compounds (more than 34 carbon). Also the thermal stability of HDPE in air is remarkably improved with the addition of C60. When the content of C60 is 2.5 wt% the onset decomposition temperature increases by about 91 °C. The results of viscoelastic behavior and gel content reveal that C60 can trap the alkyl radicals and alkyl peroxide radicals to inhibit hydrogen abstraction to suppress the chain scission and preserve the long chain structure. However, in the absence of C60 or with low C60 concentration, hydrogen abstraction occurs, resulting in the formation of a series of alkyl radicals and alkyl peroxide radicals, which accelerates the chain scission and plays a leading role in the thermal oxidative degradation. 相似文献
65.
Zaijun Li Yinjun Fang Peipei Chen Zhongyun Wang Liping Wang Guoxiao Ren 《International journal of environmental analytical chemistry》2013,93(11):856-868
In the current paper we describe a novel sample preparation technique termed dispersive liquid-phase microextraction for the preconcentration and determination of 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol) and its degradation products in water samples that includes 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethene(2,4′-DDE), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane(4,4′-DDE) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl)ethane (2,4′-DDT) coupled with gas chromatography mass spectrometry (GC-MS), in which a new ionic liquid 1,3-diisooctylimidazolium hexafluorophosphate abbreviated as [D(i-C8)IM][PF6] was used as extraction solvent. For each one extraction, 1.00 mL of the methanol solution containing 40 µL of the ionic liquid was sprayed into 25.00 mL of water sample. In the meantime the ionic liquid was finely dispersed into the aqueous phase and analytes were rapidly migrated into the ionic liquid. After the solution was centrifuged for 2 min at 5000 rpm, the droplets of the ionic liquid are subsided in the bottom of the conical test tube (30.0 ± 0.2 µL). Moreover, the factors relevant to extraction efficiencies were investigated and optimised including the volume of the ionic liquid, disperser solvent, extraction time, sample pH and ionic strength. Under optimal conditions, the enrichment factors of the extraction were between 550 and 725 with an extraction efficiency ranging from 66% to 87% for each different analyte. Finally, 1.0 µL of the ionic liquid collected from above extraction was injected into the injector block of GC-MS instrument for analysis. The detection limit (S/N = 3), the relative standard deviations for 2.0 µg L?1 of the standard analyte (n = 5) and linearity in a calibration range were found to be 3–8 ng L?1, 1.0–2.7% and 10–3000 ng L?1, respectively. Good spiked recoveries over the range of 92.0–13.5% were obtained. The proposed method offers the advantages of simplicity of operation, rapidity, good extraction efficiency and enrichment factor; it has been successfully applied to determination of dicofol and its degradation products in environmental water samples. 相似文献
66.
67.
Dr. Baoshun Liu Dr. Xuelei Wang Dr. Liping Wen Prof. Dr. Xiujian Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10751-10759
The in situ open‐circuit voltages (Voc) and the in situ photoconductivities have been measured to study electron behavior in photocatalysis and its effect on the photocatalytic oxidation of methanol. It was observed that electron injection to the conduction band (CB) of TiO2 under light illumination during photocatalysis includes two sources: from the valence band (VB) of TiO2 and from the methanol molecule. The electron injection from methanol to TiO2 is slower than that directly from the VB, which indicates that the adsorption mode of methanol on the TiO2 surface can change between dark and illuminated states. The electron injection from methanol to the CB of TiO2 leads to the upshift of the Fermi level of electrons in TiO2, which is the thermodynamic driving force of photocatalytic oxidation. It was also found that the charge state of nano‐TiO2 is continuously changing during photocatalysis as electrons are injected from methanol to TiO2. Combined with the apparent Langmuir–Hinshelwood kinetic model, the relation between photocatalytic kinetics and electrons in the TiO2 CB was developed and verified experimentally. The photocatalytic rate constant is the variation of the Fermi level with time, based on which a new method was developed to calculate the photocatalytic kinetic rate constant by monitoring the change of Voc with time during photocatalysis. 相似文献
68.
吴丽萍 《纯粹数学与应用数学》2015,(3):245-251
研究一类"食物有限"基于比率的Holling-Tanner离散捕食者-食饵模型.利用差分方程的不等式理论及振动理论,证明在一定条件下,该系统是持久的. 相似文献
69.
Liping Li Linnan Xu Ze Li Yu Bai Huwei Liu 《Analytical and bioanalytical chemistry》2014,406(1):35-47
Sample preparation is of vital importance for proteomic analysis because of the high complexity of biological samples. The rapid development of novel nanomaterials with various compositions, morphologies, and proper surface modifications provides a category of powerful tools for the sample preparation for protein analysis. In this paper, we have summarized recent progresses for the applications of novel nanomaterials in sample preparation for the analysis of proteomes, especially for phosphoproteomes, glycoproteomes, and peptidoms. Several kinds of novel nanomaterials were also discussed for their use in other kinds of proteomics analysis. Graphical abstract
Illustration of sample preparation methods by nanomaterials for protein analysis 相似文献
70.
DNA methyltransferase (DNA MTase) can act as biomarker for many diseases and it is important to develop some new methods for sensitive detection of DNA MTase. In this work, a highly efficient electrochemiluminescence (ECL) sensor had been designed for detection of DNA MTase based on Ru(phen)32+ loaded double strand DNA (dsDNA- Ru(phen)32+) as signal tags. Ru(phen)32+ had been efficiently embed in the dsDNA produced through a simple hybridization chain reaction. First, a hairpin probe was designed, which can be specifically recognized by Dam MTase and modified with -SH at one end. It was modified on the surface of gold electrode by -SH as an immobilization probe (IP). This IP will be methylated in the present of Dam MTase and digested by DpnI following. Results in the release of capture probe (CP) which remains on the surface of gold electrode. The CP can hybridize with the single stand part of the dsDNA- Ru(phen)32+ and make the immobilization of ECL tags on the electrode surface, which results in a strong ECL signals detected. However, without the effect of Dam MTase, the hairpin structure of IP remains stable and cannot capture signal tags, and can only detecte weak ECL signals. The biosensor can detect the activity of Dam MTase in the concentration range of 0.01 U/mL to 20 U/mL with the ECL intensity and the logarithm of the concentration have a linear relationship, and the detection limit is calculated to be 7.6 mU/mL. The developed sensor has the ability to specifically detect Dam MTase, which can be differentiated from other types of DNA MTase. In addition, the designed method has good applicability to detect Dam MTase activity in serum samples and been applied to detect its inhibitor with high efficiency. 相似文献