首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   567篇
  免费   23篇
  国内免费   4篇
化学   383篇
晶体学   1篇
力学   10篇
数学   97篇
物理学   103篇
  2024年   3篇
  2023年   10篇
  2022年   20篇
  2021年   21篇
  2020年   28篇
  2019年   19篇
  2018年   25篇
  2017年   18篇
  2016年   29篇
  2015年   19篇
  2014年   32篇
  2013年   41篇
  2012年   27篇
  2011年   39篇
  2010年   24篇
  2009年   15篇
  2008年   27篇
  2007年   22篇
  2006年   23篇
  2005年   23篇
  2004年   16篇
  2003年   15篇
  2002年   7篇
  2001年   2篇
  2000年   6篇
  1999年   7篇
  1997年   3篇
  1996年   4篇
  1995年   5篇
  1994年   3篇
  1993年   3篇
  1991年   3篇
  1990年   2篇
  1988年   6篇
  1987年   4篇
  1986年   4篇
  1985年   5篇
  1984年   2篇
  1978年   2篇
  1977年   2篇
  1976年   3篇
  1975年   2篇
  1973年   2篇
  1971年   3篇
  1969年   1篇
  1968年   3篇
  1967年   1篇
  1966年   1篇
  1964年   2篇
  1963年   2篇
排序方式: 共有594条查询结果,搜索用时 359 毫秒
131.
Crystalline thin films of π-conjugated molecules are relevant as the active layers in organic electronic devices. Therefore, materials with enhanced control over the supramolecular arrangement, crystallinity, and thin-film morphology are desirable. Herein, it is reported that hydrogen-bonded substituents serve as additional structure-directing elements that positively affect crystallization, thin-film morphology, and device performance of p-type organic semiconductors. It is observed that a quaterthiophene diacetamide exhibits a denser packing than that of other quaterthiophenes in the single-crystal structure and, as a result, displays enhanced intermolecular electronic interactions. This feature was preserved in crystalline thin films that exhibited a layer-by-layer morphology, with large domain sizes and high internal order. As a result, organic field-effect transistors of these polycrystalline thin films showed mobilities in the range of the best mobility values reported for single-crystalline quaterthiophenes. The use of hydrogen-bonded groups may, thus, provide an avenue for organic semiconducting materials with improved morphology and performance.  相似文献   
132.
We present herein a new nanocatalyst, namely binary CuPt alloy nanoparticles (NPs) supported on reduced graphene oxide (CuPt‐rGO), as a highly active heterogeneous catalyst for the transfer hydrogenation (TH) protocol that is demonstrated to be applicable over the reduction of various unsaturated organic compounds (olefins, aldehydes/ketones and nitroarenes) in aqueous solutions at room temperature. CuPt alloy NPs were synthesized by the co‐reduction of metal (II) acetylacetonates by borane‐tert‐butylamine (BTB) complex in hot oleylamine (OAm) solution and then assembled on reduced graphene oxide (rGO) via ultrasonic‐assisted liquid phase self‐assembly method. The structure of yielded CuPt NPs and CuPt‐rGO nanocatalyst were characterized by TEM, XRD and ICP‐MS. The activity of Cu7Pt3‐rGO nanocatalysts were then tested for the THs that were conducted in a commercially available high‐pressure tube using water as sole solvent and ammonia borane as a hydrogen donor at room temperature. The presented catalytic TH protocol was successfully applied over nitroarenes, olefines and aldehydes/ketones, and all the tested compounds were converted to corresponding reduction products with the yields reaching up to 99% under ambient conditions. Moreover, the Cu7Pt3‐rGO nanocatalyst was also reusable in the TH by providing 99% yield after five consecutive runs in TH of nitrobenzene as an example.  相似文献   
133.
Two Bis-β-diketonate zinc (II) complexes were synthesized using 1-(thiophen-2-yl)butane-1,3-dione and 1-(thiophen-2-yl)-3-(thiophen-3-yl)propane-1,3-dione as ligands. By electropolymerization of their thiophenyl groups, the metallopolymers deposited on FTO electrodes were obtained. The main objective was to study the reactivity of these compounds as ROP catalysts for PLA synthesis, using directly the zinc complexes (homogeneous catalysis) and also the modified electrodes with metallopolymers (heterogeneous catalysis). The homogeneous catalysis studies allowed the optimization of the polymerization conditions, such as reaction time, catalyst concentration, and the use of benzyl alcohol as cocatalyst, as well as their influence on the conversion rate, average molecular weight and polydispersity of PLA, using rac-LA and L-LA as monomers. Also, the effect on tacticity and thermal properties were discussed. Finally, the ROP studies using immersed modified electrodes in the polymerization medium were carried out under optimized experimental conditions. These tests were positive for one of the studied compounds, reaching conversions of up to 67%. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 557–567  相似文献   
134.
The present work describes the persistence, dissipation behaviour, half-life, risk assessment and novel gas chromatography method for the residue estimation of cypermethrin in green pea by spraying cypermethrin 10EC at 50 g a.i. ha−1 at fruiting stage followed by another application at a 10 day interval. The sample extraction and cleanup was followed bya modified quick, easy, cheap, effective, rugged, and safe method, and the residues of cypermethrin were determined using a validated gas chromatography method. The initial deposits were found to be 1.21 mg kg−1 following the application of insecticide at 50 g a.i. ha−1. Cypermethrin residues declined to below the detection limit of 0.05 mg kg−1 after 15 days at the recommended dosage. The half-life of cypermethrin was 2.66 days at 50 g a.i. ha−1. For risk assessment studies, the waiting period of 15 days is recommended as safe for consumption for the insecticide. The GC-ECD method was validated according to the SANTE guidelines by various analytical parameters including linearity, accuracy, detection and quantification limits. The developed method is simple, selective and repeatable, and can be used for the standardization of pesticides on fruits and vegetables.  相似文献   
135.
A previously reported rearrangement of pyrimidine-5-carboxylic acids esters to 5-acylpyrimidones does not, in fact, occur in any of the examples studied by us.  相似文献   
136.
由野生及突变株云芝IBL-04制得细胞外锰过氧化物酶(MnPs),并经过硫酸铵沉淀、透析、离子交换和凝胶渗透层析法等步骤提纯.纯化的酶在十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)上于43 kDa区域呈现单一谱带,它适宜的pH值和温度分别为5.0和40°C.突变株MnPs表现出比野生株MnPs更宽的活性pH值范围和更高的热稳定性.从所选突变株所得纯化的MnPs表现出与野生株MnP几乎相同的电泳性质、稳态动力学、金属离子和EDCs降解效率.该生物酶与Mn2+一起催化的反应速率最快,但最高的亲和性对应于ABTS、甲氧基羟苯基乙二醇、4-氨基苯酚和活性染料. Mn2+和Cu2+可显著提高MnPs的活性,但Zn2+, Fe2+, EDTA和半胱氨酸则会不同程度地抑制其活性, Hg2+是最强的活性抑制剂.所有来源的MnPs均可有效催化EDCs、壬基苯酚和二氯苯氧氯酚降解,处理3 h可除去80%以上,在MnPs-介质体系中可进一步提高到90%.综上,云芝MnPs生物酶具有较高的pH适用性和热稳定性、独特的Michaelis-Menten动力学参数和高的EDCs去除效率等特点,因而有望工业化应用.  相似文献   
137.
138.
The effect of Ni substitution on the microstructure, dielectric, impedance, magnetic and power loss properties has been investigated on a series of Li0.35-0.5xCd0.3NixFe2.35-0.5xO4 (0.00≤x≤0.08) ferrite prepared by citrate precursor method. Dielectric and impedance measurements have been determined in the frequency range 100 Hz-10 MHz. An enhancement in permittivity was observed with Ni concentration and exhibits the maximum value of ∼7×103 for x=0.02 sample. The impedance spectroscopy technique has been used to study the effect of grain and grain boundary on the electrical properties of all the samples. Power loss measurements have been carried out in the frequency range 50 kHz-5 MHz at induction condition of B=10 mT. Power loss has been found to be quite low, less than 100 kW/m3 up to 500 kHz, with the substitution of Ni in Li0.35-0.5xCd0.3NixFe2.35-0.5xO4 ferrite, which is useful for technological aspects.  相似文献   
139.
Advanced nanotechnology is an enormously growing area due to its massive scope of applications for diverse domains of applied science and engineering. Numerous types of synthetic procedures are utilized for the creation of nanoparticles (NPs) due to their myriad application scenarios. However, known conventional physical and chemical strategies have a number of shortcomings. Consequently, the designs of facile, clean, safer, non-noxious, reliable, inexpensive and eco-friendly processes for manufacturing of NPs are being explored actively to circumvent these barriers. The phytogenic fabrication of NPs is much safer, one-pot, facile, and a sustainable methodology. Hence, divergent biological means like the use of plants, biopolymers, fungi, fibres, bacteria, enzymes, etc., are pursued the procurable biogenic fabrication of metallic NPs. In this review paper, current findings on the bio-inspired fabrication of silver chloride nanoparticles (AgCl-NPs) are deliberated, which have with their useful appliances in assorted sectors. The experimental protocols, advanced characterization techniques along with diverse applications of biogenically synthesized AgCl-NPs have been highlighted.  相似文献   
140.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号