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   1956篇
  免费   41篇
  国内免费   84篇
化学   1158篇
力学   32篇
综合类   5篇
数学   403篇
物理学   483篇
  2024年   7篇
  2023年   54篇
  2022年   26篇
  2021年   40篇
  2020年   24篇
  2019年   70篇
  2018年   68篇
  2017年   55篇
  2016年   35篇
  2015年   33篇
  2014年   140篇
  2013年   121篇
  2012年   101篇
  2011年   170篇
  2010年   124篇
  2009年   125篇
  2008年   132篇
  2007年   123篇
  2006年   94篇
  2005年   85篇
  2004年   101篇
  2003年   49篇
  2002年   50篇
  2001年   29篇
  2000年   25篇
  1999年   48篇
  1998年   44篇
  1997年   19篇
  1996年   18篇
  1995年   13篇
  1994年   10篇
  1993年   14篇
  1992年   4篇
  1991年   5篇
  1990年   2篇
  1989年   4篇
  1988年   2篇
  1987年   1篇
  1986年   1篇
  1985年   3篇
  1984年   3篇
  1983年   2篇
  1982年   1篇
  1981年   3篇
  1977年   1篇
  1974年   1篇
  1973年   1篇
排序方式: 共有2081条查询结果,搜索用时 15 毫秒
21.
Lignans are a group of polyphenolic phytochemicals that possess a large spectrum of chemical structures and biological activities. Here the syntheses of lignans – anwulignan, burseran, dehydroxycubebin, ruburisandrin B, and sesamin – are achieved based on a borate-mediated one-pot sequential Suzuki-Miyaura coupling of cis- and trans-fused bicyclic boranes, which were prepared by diastereoselective cyclic hydroboration of exo-cyclic diene with cyclopentyl- and thexylboranes, respectively. A one-pot sequential Suzuki-Miyaura coupling of each cyclic borate with various aryl bromides initiated by activation of the cyclic borane with the carbon nucleophile provided 2,3-dibenzylbutane derivatives with different aromatic substituents. Finally, the syntheses of naturally occurring lignans were accomplished in several steps from the products of Suzuki-Miyaura coupling.  相似文献   
22.
Marie Devert 《Tetrahedron》2010,66(35):7227-2584
The first total synthesis of (±)-17-norcamptothecin, a novel camptothecin analog possessing an α-hydroxy-γ-lactone E-ring, has been accomplished by using a short and flexible route. The stability of this new compound in aqueous medium has been evaluated through fluorescence spectroscopy.  相似文献   
23.
Iron is one of the most microbiologically and chemically important metals in natural waters. The biogeochemical cycling of iron is significantly influenced by the redox cycling of Fe(II) and Fe(III). Because of the unique chemistry of iron, it is often needed to analyze iron at nano-molar concentrations. This article describes a reverse flow injection analysis (rFIA) based method with ferrozine spectrophotometric detection to quantify total iron concentration in stream water at nanomolar concentrations. The rFIA system has a 0.65 nM detection limit and a linear dynamic range up to 1.40 μM for the total iron analysis. The detection limit was achieved using a 1.0 m long liquid waveguide capillary flow cell, 1.50 m long knotted reaction coil, 87.50 μL injection loop and a miniature fiber optics spectrophotometer. The optimized colorimetric reagent has 1.0 mM ferrozine, 0.1 M ascorbic acid, 1.0 mM citric acid and 0.10 M acetate buffer adjusted to pH 4.0. The best sample flow rate is 2.1 mL min?1 providing a sample throughput of more than 15 samples h?1. The linear dynamic range of the method can be adjusted by changing the volume of the injection loop. The rFIA manifold was assembled exclusively from commercially available components.  相似文献   
24.
This review critically evaluates the plastic accumulation challenges and their environmental (primarily) and human (secondarily) impacts. It also emphasizes on their degradation and fragmentation phenomena under marine conditions. In addition, it takes into account the leachability of the various chemical substances (additives) embedded in plastic products to improve their polymeric properties and extend their life. Regardless of their effectiveness in enhancing the polymeric function of plastic products, these additives can potentially contaminate air, soil, food, and water. Several findings have shown that, regardless of their types and sizes, plastics can be degraded and/or fragmented under marine conditions. Therefore, the estimation of fragmentation and degradation rates via a reliable developed model is required to better understand the marine environmental status. The main parameter, which is responsible for initiating the fragmentation of plastics, is sunlight/UV radiation. Yet, UV- radiation alone is not enough to fragment some plastic polymer types under marine conditions, additional factors are needed such as mechanical abrasion. It should be also mentioned that most current studies on plastic degradation and fragmentation centered on the primary stages of degradation. Thus, further studies are needed to better understand these phenomena and to identify their fate and environmental effects.  相似文献   
25.
摘 要:采用微波消解-石墨炉原子吸收光谱法分析测定食用菌中总砷。取可食部分的食用菌粉碎均匀,采用微波消解对样品进行消解,将消解液于140℃赶酸至0.5mL ,用超纯水转移定容至25mL。以0.1%的硝酸钯为基体改进剂,塞曼扣背景,用石墨炉原子吸收光谱法测定总砷。方法检出限为0.4μg/L,线性范围为0~30 μg/L,线性相关系数(r)大于0.998,采用精密度考察方法重现性,不同浓度水平的RSD%均小于6.6%;三个浓度水平的加标回收率为80.6% ~ 103.9%,有证标准物质测定结果符合要求。实验结果表明,方法操作简便、灵敏、准确,适合食用菌中总砷的测定。对砷形态复杂的野生食用菌,微波消解后可直接采用石墨炉原子吸收光谱法测定总砷。  相似文献   
26.
In this study, the efficacy of inorganic additives in the removal of total ammonia nitrogen (TAN) and sulfide in the aqueous phase of slaughterhouse waste undergoing anaerobic digestion in the batch reactor was investigated. A mixture of natural inorganic additives processed from the anthill and red rock soil samples collected from Arusha, Tanzania were used as adsorbents in different ratios. These materials were chosen in regard to their abundance in the local environment, surface properties, and elemental composition. Before analysis, the materials were pulverized and calcined at 700 and 900 °C for 2 h in a furnace and then sieved to 250 μm fine particle size. XRD analysis revealed that the anthill soil sample is endowed with major mineral phases of quartz and hematite while red rock soil contains albite, pyroxene, and quartz as predominant phases. The anthill and red rock soil samples calcined at 900 °C displayed higher BET surface areas of 815.35 and 852.35 m2/g, respectively. The mixture of anthill soil and red rock soil in a ratio of 3:1 had a higher TAN removal efficiency of 92% at a contact time of 30 min compared to other ratios. On the other hand, a ratio of 1:2 showed a higher sulfide removal efficiency of 79% at a contact time of 60 min. Adsorption isotherm studies revealed that the Jovanovich model fitted better to the experimental data than the Langmuir and Freundlich models. The results demonstrated further that inorganic additives have a synergistic effect on stimulating methanogenesis as well as eliminating ammonia and sulfide during anaerobic digestion of slaughterhouse waste. Our findings demonstrate that anthill and red rock soils can be exploited as affordable, ecofriendly, and efficient adsorbents for mitigation of TAN and sulfide from the liquid phase and sustenance of methanogenesis.  相似文献   
27.
以2-(3,4-环己基类二氧-5-异丙基)苯基乙醇(2)和3-异丙氧基-5,5-二甲基-1,3-环己烯酮(4)为原料,利用羰基α-位的烷基化反应和分子内的Friedel-Carfts反应为关键步骤,经9步反应,合成了多氧芳香型三环二萜类天然产物Salvinolone。  相似文献   
28.
The heat production of Wistar rat polymorphonuclear leukocytes (PMN) was measured by an LKB 2277 Thermal Activity Monitor. When PMN were activited with phorbol-12-myristate13-acetate (PMA), the respiratory burst was recorded by greatly incr eased heat production. Experiment was also carred out in the present of the inhibitor, Total Flavonoids of Lycium Barbarum L. (TFL). The respiratory burst heat production peak was disappeared, but the heat production curve was higher than that of PMA because TFL increased the metabolic activities of PMN.  相似文献   
29.
Collective syntheses of five spiro[4.5]decane framework bearing sesquiterpenoids, namely, α & β-vetispirenes, β-vetivone, agarospirol and hinesol as well as formal synthesis of axenol and gleenol from a readily available precursor cyclohexanone-β-ketoester via the intermediacy of a versatile intermediate (2,10-dimethylspiro[4.5]dec-1-en-6-one) have been accomplished in a concise manner.  相似文献   
30.
Cladosporin, a secondary metabolite isolated from fungal sources like Cladosporium cladosporioides and Aspergillus flavus was found to exhibit selective nano-molar activity against malarial parasite Plasmodium falciparum by inhibiting parasitic protein biosynthesis. In addition, this natural product has a broad range of bioactivities including, antiparasitic, antifungal, antibacterial as well as plant growth inhibition. However, it has limited availability from the natural sources for further development. Herein, we report a modified and improved synthetic route which led us to produce this potent natural product in a gram scale. Conversion of the undesired diastereomer to desired one via Mitsunobu inversion of secondary alcohol and carbon monoxide insertion reaction towards the construction of isocoumarin unit are the key features of the present synthesis.  相似文献   
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