全文获取类型
收费全文 | 2325篇 |
免费 | 358篇 |
国内免费 | 237篇 |
专业分类
化学 | 1841篇 |
晶体学 | 15篇 |
力学 | 125篇 |
综合类 | 33篇 |
数学 | 170篇 |
物理学 | 736篇 |
出版年
2024年 | 8篇 |
2023年 | 27篇 |
2022年 | 64篇 |
2021年 | 76篇 |
2020年 | 77篇 |
2019年 | 82篇 |
2018年 | 54篇 |
2017年 | 58篇 |
2016年 | 81篇 |
2015年 | 93篇 |
2014年 | 129篇 |
2013年 | 169篇 |
2012年 | 191篇 |
2011年 | 200篇 |
2010年 | 155篇 |
2009年 | 139篇 |
2008年 | 157篇 |
2007年 | 152篇 |
2006年 | 119篇 |
2005年 | 92篇 |
2004年 | 84篇 |
2003年 | 75篇 |
2002年 | 73篇 |
2001年 | 78篇 |
2000年 | 79篇 |
1999年 | 58篇 |
1998年 | 60篇 |
1997年 | 50篇 |
1996年 | 48篇 |
1995年 | 32篇 |
1994年 | 19篇 |
1993年 | 23篇 |
1992年 | 12篇 |
1991年 | 20篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 11篇 |
1987年 | 11篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 6篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1966年 | 2篇 |
1931年 | 1篇 |
1924年 | 1篇 |
1884年 | 1篇 |
排序方式: 共有2920条查询结果,搜索用时 892 毫秒
101.
Prof. Caihong Fang Guili Zhao Zijun Zhang Qian Ding Nan Yu Zhiqing Cui Ting Bi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7351-7358
Multifunctional metal nanostructures with a hollow feature, especially for nanoframes, are highly attractive owing to their high surface-to-volume ratios. However, pre-grown metal nanocrystals are always involved during the preparation procedure, and a synthetic strategy without the use of a pre-grown template is still a challenge. In this article, a template-free strategy is reported for the preparation of novel AuPt alloy nanoframes through simply mixing HAuCl4 and H2PtCl6 under mild conditions. The alloy nanostructures show a bipyramid-frame hollow architecture with the existence of only the ten ridges and absence of their side faces. This is the first report of bipyramid-like nanoframes and a template-free method under mild conditions. This configuration merges the plasmonic features of Au and highly active catalytic sites of Pt in a single nanostructure, making it an ideal multifunctional platform for catalyzing and monitoring the catalytic reaction in real time. The superior catalytic activity is demonstrated by using the reduction of nitrobenzene to the corresponding aminobenzene as a model reaction. More importantly, the AuPt nanoframes can track the reduction process on the basis of the SERS signals of the reactants, intermediates, and products, which helps to reveal the reaction mechanism. In addition, the AuPt nanoframes show much higher electrocatalytic properties toward the methanol oxidation reaction than commercial Pt/C electrocatalysts. 相似文献
102.
Lulu Wang Jinmiao Wang Chuanbin Fan Caifeng Bi Xia Zhang Dongmei Zhang Mei Wang Yuhua Fan 《应用有机金属化学》2020,34(9):e5767
Two novel Co (II)- coordination polymers (CPs) based on 2,5-bis(4-carboxylpheny)-1,3,4-oxadiazole (bcpo), namely [Co/(bcpo)0.5(tib)(H2O)2]n (1) and [Co (bcpo)0.5(bidpe)(H2O)2]n (2) (tib = 1,3,5-tirs(1-imidazolyl)benzene, bidpe = 4,4′-bis (imidazolyl)diphenyl ether) have been synthesized under solvothermal conditions and characterized by powder X-ray diffraction (PXRD), single crystal X-ray diffraction, photochemistry as well as electrochemistry. The investigation of the photo-degradation methyl blue and methyl violet (MB, MV) properties of CPs 1–2 demonstrates that CP 1 shows great performance for the degradation of MB, and CP 2 could efficiently degrade MB/MV. Meanwhile, the possible photo-degradation mechanism has been proposed and explored. Simultaneously, electrochemistry studies show that both CPs 1 and 2 can catalyze water oxidation under an alkaline condition at the potential around 1.20 V vs. NHE with relatively low overpotential of 330–510 mV vs. NHE. 相似文献
103.
104.
Mixed matrix materials, containing poly(dimethylsiloxane), phosphine oxide-based polyimide, and zeolite Y were prepared by means of blending hybridisation. The thermal stability of the materials and the hydrophobic properties were enhanced. The decrease in the glass transition temperature of the materials with the increase in poly(dimethylsiloxane) content supported the polymer-chain flexibility. The pristine polyimide and the zeolite-filled polyimide exhibited the highest transparency. Fourier transform infrared (FTIR) spectroscopy confirmed that the increase in the amount of the lowest molecular mass poly(dimethylsiloxane) ingredient indicated strong alkyl and Si-O-Si stretching modes, whilst the alkyl and Si-O-Si stretching intensity decreased in the presence of the highest amount of and the highest molecular mass poly(dimethylsiloxane). The hydrophobic poly(dimethylsiloxane) moiety created an inverse relationship between the porosity of the materials (surface roughness) and the hydrophilicity. The nanocrystallite domain, identified by X-ray diffraction analysis (XRD) and possessing an exotherm crystallisation peak, occurred in the lowest amount of poly(dimethylsiloxane) with the highest molecular mass-based hybrid material. The nanocrystallite enhanced the storage modulus as determined by the dynamic mechanical analyser (DMA). The nanocrystalline formation resulted in a slight increase in the alkyl stretching and the Si-O-Si stretching of the lowest amount of and the highest molecular mass poly(dimethylsiloxane)-containing material over those of the lowest molecular mass poly(dimethylsiloxane) in the same amounts of material involved. 相似文献
105.
Goto J. Oshima M. Sugawara M. Yamaguchi Y. Bi C. Bamba S. Morimoto T. 《Journal of Radioanalytical and Nuclear Chemistry》2017,314(3):1707-1714
Charged particle activation analysis (CPAA) is a rapid method with high accuracy which can analyze multi-elements simultaneously. Since multiple γ-ray detection method is expected to improve the detection efficiency and the signal-to-noise ratio, we study what design of the γ-ray detector array is the most suitable for CPAA. We take up four design candidates and investigated the responses by the radiation simulation code Geant 4. From the results, we have deduced the best design with 5 germanium detectors in close geometry. By inspecting the sensitivity in CPAA, the method is proved to be useful and applicable to 116 nuclides.
相似文献106.
107.
Low-phosporous nickel-coated carbon microcoils: Controlling microstructure through an electroless plating process 总被引:1,自引:0,他引:1
Carbon microcoils (CMCs) have been coated with a nickel-phosphorus (Ni-P) film using an electroless plating process, with sodium hypophosphite as a reducing agent in an alkaline bath. CMC composites have potential applications as microwave absorption materials. The morphology, elemental composition and phases in the coating layer of the CMCs and Ni-coated CMCs were investigated by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD), respectively. The effects of process parameters such as pH, temperature and coating time of the plating bath on the phosphorus content and deposition rate of the electroless Ni-P coating were studied. The results revealed that a continuous, uniform and low-phosphorous nickel coating was deposited on the surface of the CMCs for 20 min at pH 9.0, plating bath temperature 70 °C. The as-deposited coatings with approximately 4.5 wt.% phosphorus were found to consist of a mix of nano- and microcrystalline phases. The mean particle size of Ni-P nanoparticles on the outer surface of the CMCs was around 11.9 nm. The deposition rate was found to moderately increase with increasing pH, whereas, the phosphorous content of the deposit exhibited a significant decrease. Moreover, the material of the coating underwent a phase transition between an amorphous and a crystalline structure. The thickness of the deposit and the deposition rate may be controlled through careful variation of the coating time and plating bath temperature. 相似文献
108.
109.
Chunxiao Lv Qing Li Yaowen Zhang Zhenyu Sui Bosai He Huarong Xu Yidi Yin Xiaohui Chen Kaishun Bi 《Journal of mass spectrometry : JMS》2013,48(8):904-913
A fast, sensitive and reliable ultra fast liquid chromatography‐tandem mass spectrometry (UFLC‐MS/MS) method has been developed and validated for simultaneous quantitation of polygalaxanthone III (POL), ginsenoside Rb1 (GRb1), ginsenoside Rd (GRd), ginsenoside Re (GRe), ginsenoside Rg1 (GRg1) and tumulosic acid (TUM) in rat plasma after oral administration of Kai‐Xin‐San, which plays an important role for the treatment of Alzheimer's disease (AD). The plasma samples were extracted by liquid–liquid extraction using ethyl acetate–isopropanol (1:1, v/v) with salidrdoside as internal standard (IS). Good chromatographic separation was achieved using gradient elution with the mobile phase consisting of methanol and 0.01% acetic acid in water. The tandem mass spectrometric detection was performed in multiple reaction monitoring mode on 4000Q UFLC‐MS/MS system with turbo ion spray source in a negative and positive switching ionization mode. The lower limits of quantification were 0.2–1.5 ng/ml for all the analytes. Both intra‐day and inter‐day precision and accuracy of analytes were well within acceptance criteria (±15%). The mean absolute extraction recoveries of analytes and IS from rat plasma were all more than 60.0%. The validated method has been successfully applied to comparing pharmacokinetic profiles of analytes in normal and AD rat plasma. The results indicated that no significant differences in pharmacokinetic parameters of GRe, GRg1 and TUM were observed between the two groups, while the absorption of POL and GRd in AD group were significantly higher than those in normal group; moreover, the GRb1 absorbed more rapidly in model group. The different characters of pharmacokinetics might be caused by pharmacological effects of the analytes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
110.
Binbin Wei Qing Li Ronghua Fan Dan Su Xiuli Ou Kelin Chen Xiaohui Chen Ying Jia Kaishun Bi 《Journal of mass spectrometry : JMS》2013,48(4):448-458
Schisandra chinensis (Turcz.) Baill., a traditional Chinese medicine, has been clinically used for the treatment of insomnia for centuries. The insomnia mechanism and the possible active ingredients of S. chinensis remain largely unknown. The objective of this study was to develop a method to detect its components which could pass through the blood brain barrier (BBB) by determining the brain microdialysate and brain tissue homogenate samples and then obtain the pharmacokinetic profile in brain for comprehensive understanding of its hypnotic clinical efficacy. Therefore, an efficient, sensitive and selective ultra fast liquid chromatography/tandem mass spectrometry method for the simultaneous determination of six sedative and hypnotic lignans (schisandrin, schisandrol B, schisantherin A, deoxyshisandrin, γ‐schisandrin and gomisin N) of Schisandra chinensis (Turcz.) Baill. in rat brain tissue homogenate and brain microdialysates has been developed and validated. The analysis was performed on a Shim‐pack XR‐ODS column (75 mm × 3.0 mm, 2.2 µm) using gradient elution with the mobile phase consisting of acetonitrile and 0.1% formic acid water. The method was validated in brain homogenate and microdialysate samples, which all showed good linearity over a wide concentration range (r2 > 0.99), and the obtained lower limit of quantification was 0.1 ng · ml?1 for the analytes in brain microdialysate samples. The intra‐ and inter‐day assay variability was less than 15% for all analytes. The study proved the six lignans, as sedative and hypnotic ingredients, could pass through the BBB with brain targeting, distributed mainly in the hypothalamus and possessed complete pharmacokinetics process in brain. The results also indicated that significant difference in pharmacokinetic parameters of the analytes was observed between two groups, while absorptions of these analytes in insomniac group were significantly better than those in normal group. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献