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   455篇
  免费   52篇
  国内免费   64篇
化学   350篇
晶体学   4篇
力学   47篇
综合类   12篇
数学   54篇
物理学   104篇
  2024年   1篇
  2023年   4篇
  2022年   9篇
  2021年   11篇
  2020年   14篇
  2019年   8篇
  2018年   16篇
  2017年   10篇
  2016年   19篇
  2015年   19篇
  2014年   20篇
  2013年   23篇
  2012年   41篇
  2011年   33篇
  2010年   30篇
  2009年   31篇
  2008年   41篇
  2007年   43篇
  2006年   35篇
  2005年   28篇
  2004年   26篇
  2003年   20篇
  2002年   18篇
  2001年   10篇
  2000年   14篇
  1999年   7篇
  1998年   9篇
  1997年   3篇
  1996年   7篇
  1995年   8篇
  1994年   4篇
  1992年   1篇
  1991年   1篇
  1990年   5篇
  1983年   1篇
  1982年   1篇
排序方式: 共有571条查询结果,搜索用时 375 毫秒
1.
李志荣 《大学数学》2006,22(2):100-104
利用普通幂级数发生函数方法,通过对发生函数进行xD算子,得到和式∑k=0^nμ^kf(k)的计算公式,并计算该类和式+  相似文献   
2.
UV/H2O2氧化降解甲基叔丁基醚(MTBE)的试验研究   总被引:3,自引:0,他引:3       下载免费PDF全文
采用UV/H2O2技术对污染水体中的MTBE进行了氧化降解试验,考察了不同MTBE初始浓度,不同H2O2浓度,不同pH值,不同波长的紫外光对降解效果的影响,以及不同Cl^-、HCO3^-浓度的抑制作用.结果表明,在室温条件下,当紫外光波长为254nm,H2O2为15mmol/L,pH为3.0时对起始浓度为1mmol/L的MTBE具有较好的降解效果;反应60min,MTBE去除率可达97.6%.实验证明,UV/H2O2氧化技术是降解MTBE的一种有效方法.  相似文献   
3.
1-Propyl-3-methylimidazolium chloride ([C3MIm]Cl) ionic liquid and sulfamic acid (NH2SO3H), as a synergetic catalytic medium, were used for the transesterification of acetoacetate with alcohols of different structures. It shows the good ability for the chemoselective transesterificatin of β-ketoesters and maintains its catalytic activity in the reuse.  相似文献   
4.
A method was proposed for the simultaneous determination of trace cadmium and mercury by vapor generation non-dispersive atomic fluorescence spectrometry using an intermittent flow system. The effects of the parameters on the performance were studied systematically. The parameters such as acid concentration of the reaction medium, flow rate of the carrier gas and shield gas, the observation height and the atomizer temperature, etc. which affected the sensitivity, were optimized. Ascorbic acid, cobalt ion and thiourea were used as enhancement reagents or masking agents to enhance the generation efficiency of the volatile species of Cd and Hg. The mechanisms of their effects on vapor generation were investigated. In the presence of thiourea and ascorbic acid, the influences of some coexisting elements on the determination of cadmium and mercury were investigated. The detection limits (3sigma) were 0.010 microg l(-1) for Cd and 0.019 microg l(-1) for Hg, respectively. The relative standard deviations for Cd and Hg at 1.00 microg l(-1) were 2.6% and 0.97% (n = 11), respectively. The proposed method has been satisfactorily applied to the determination of trace cadmium and mercury in Chinese herbal medicine.  相似文献   
5.
A large quantity of small molecules may migrate into a network of long polymers, causing the network to swell, forming an aggregate known as a polymeric gel. This paper formulates a theory of the coupled mass transport and large deformation. The free energy of the gel results from two molecular processes: stretching the network and mixing the network with the small molecules. Both the small molecules and the long polymers are taken to be incompressible, a constraint that we enforce by using a Lagrange multiplier, which coincides with the osmosis pressure or the swelling stress. The gel can undergo large deformation of two modes. The first mode results from the fast process of local rearrangement of molecules, allowing the gel to change shape but not volume. The second mode results from the slow process of long-range migration of the small molecules, allowing the gel to change both shape and volume. We assume that the local rearrangement is instantaneous, and model the long-range migration by assuming that the small molecules diffuse inside the gel. The theory is illustrated with a layer of a gel constrained in its plane and subject to a weight in the normal direction. We also predict the scaling behavior of a gel under a conical indenter.  相似文献   
6.
研究了钍与5-(对羧基苯偶氮)-8-羟基喹啉(5-CPAHQ)的显色反应条件:在阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)存在下,pH4.4-5.4缓冲介质中,形成稳定的橙红色络合物,最大吸收波长为490nm,ε=1.10×105L·mol-1·cm-1,钍在0-9μg/25mL范围内符合比尔定律。用TBP萃淋树脂分离,该方法可用于测定矿石中的微量钍。  相似文献   
7.
索全铃  殷元骐 《分子催化》1994,8(6):462-467
负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶,李晔(内蒙古工业大学化学工程系,呼和浩特010062)殷元骐,金道森(中国科学院兰州化学物理研究所,兰州730000)关键词一氧化碳加氢,多相催化,双金属簇催化剂,钾效应。1.引言异核金属羰基簇作...  相似文献   
8.
基于稀硫酸介质中,痕量锡(Ⅳ)催化溴酸钾氧化偶氮氯膦Ⅲ(CPAⅢ)的褪色反应,建立了测定痕量锡(Ⅳ)的催化动力学光度法。方法检出限为0.25μg.L-1,线性范围为0.0~8.0μg.L-1。结合巯基葡聚糖凝胶(MDG)分离富集,用于测定环境水样、人发及岩石样品中痕量锡(Ⅳ),结果的RSD值均在9.0%以内,回收率在96.0%~103.0%之间。分析了3种岩石标准物质,所得结果与证书值相符。  相似文献   
9.
The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H3PMo6W6O40 showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and 31P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H3PMo6W6O40 are new kinds of phosphorus-containing species, which is different from {PO4[WO(O2)2]4}3−.  相似文献   
10.
A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCI-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH]+ under APCI in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0–10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of IBCIC/ICEOC and IBCIC/IFMOC are, respectively, 1.23–3.14 and 1.25–3.08 for fluorescent (FL) responses (here, I is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6–37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV<7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997. Revised: 12 December 2005 and 13 Febrauary 2006  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