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   4415篇
  免费   572篇
  国内免费   434篇
化学   3266篇
晶体学   33篇
力学   311篇
综合类   26篇
数学   285篇
物理学   1500篇
  2024年   3篇
  2023年   41篇
  2022年   73篇
  2021年   141篇
  2020年   171篇
  2019年   162篇
  2018年   114篇
  2017年   156篇
  2016年   205篇
  2015年   184篇
  2014年   264篇
  2013年   398篇
  2012年   214篇
  2011年   287篇
  2010年   233篇
  2009年   256篇
  2008年   243篇
  2007年   246篇
  2006年   246篇
  2005年   250篇
  2004年   192篇
  2003年   158篇
  2002年   155篇
  2001年   116篇
  2000年   120篇
  1999年   111篇
  1998年   84篇
  1997年   102篇
  1996年   87篇
  1995年   69篇
  1994年   75篇
  1993年   49篇
  1992年   25篇
  1991年   32篇
  1990年   17篇
  1989年   17篇
  1988年   16篇
  1987年   23篇
  1986年   14篇
  1985年   9篇
  1984年   11篇
  1983年   7篇
  1982年   12篇
  1981年   11篇
  1979年   5篇
  1978年   4篇
  1977年   4篇
  1976年   2篇
  1975年   2篇
  1974年   2篇
排序方式: 共有5421条查询结果,搜索用时 234 毫秒
111.
Y. Shen  M. L. Lee 《Chromatographia》1996,43(7-8):373-379
Summary Polyethylene oxide (PEO)-based polymers with hydroxy, methoxy, and aminopropoxy terminal groups were coated on diol functionalized and hexamethyldisilazane end-capped silica particles. Proton-donor and proton-acceptor test solutes, including carboxylic acids, hydroxy-containing compounds, arylamines, and alkylamines were used to evaluate the chromatographic performances of these polymer coated particles under SFC conditions with neat CO2 as mobile phase. It was found that the particles coated with hydroxy-terminated PEO were suitable for the separation of proton-donor compounds such as hydroxy-containing compounds and carboxylic acids, and the particles coated with aminopropoxy-terminated PEO could be used for the separation of amines. That is, the proton-accepting stationary phase is suitable for the separation of proton accepting solutes, including strong basic alkylamines (pKb4), using neat CO2 as mobile phase, while the protondonating stationary phase is suitable for the separation of proton-donating compounds such as carboxylic acids (pKa4). Hydrogen bond basicity was found to be a critical factor for the chromatography of basic amines. Low volatility acidic and basic drugs were chromatographed using the new stationary phases. The stability of the PEO coated particles was determined by measuring the loss of organic carbon under SFC conditions. It was found that approximately 18 % of the coating (average molecular weight of 15,000) was washed out of the particles by supercritical CO2 after 7 h at 350 atm and 50°C  相似文献   
112.
尼龙-1010的聚集态结构   总被引:1,自引:0,他引:1  
用WAXD、DSC、方差-范围函数.密度测量等方法,研究了经不同热处理的尼龙-1010的聚集态结构.发现退火处理更有利于尼龙-1010结晶的生成和稳定,且尼龙-1010的结晶,有一个最佳的热处理温度.在该温度附近,尼龙-1010的结晶度和微晶尺寸里最大值.  相似文献   
113.
The catalytic combustion of particulate material was studied on cobalt catalysts promoted with potassium using different supports for its preparation. Silica, aluminium oxides and hydroxides, zirconium oxide and hydroxide were used as supports. The catalytic activity for combustion depends on the type of support used, the higher activity corresponding to the supported catalyst on zirconium oxide. TPR studies indicate that the interaction metal/support allows to explain the higher activity of the CoK/SiO2 catalyst with respect to the CoK/Al2O3 but the high activity found in CoK/ZrO2is not explained by this interaction. In all cases the Co and K improved the performance of the catalysts.  相似文献   
114.
具有优良NLO性质的芪唑盐(记为S)已被用于制备LB薄膜,但其成膜性不好,稳定性差;S和花生酸镉(记为A)的混合系虽可改善成膜性,但在此混合膜系中,S相的稳定性仍然不佳。应用SAXS和微机模型拟合(MCMI)研究了上述两类LB薄膜的凝聚态结构,结果指出:在LB薄膜的二维类晶系结构中,S分子中呈哑铃形的芪唑基倾向于作倾斜状的密堆砌,S分子中的丙条脂肪链则倾向于采取全反式燕尾式构象,而且脂肪链只占S分子长的2/3,这就导致了S分子在二维类晶系结构中凝聚力的下降,以及造成LB薄膜层状超分子结构的破坏和崩塌。  相似文献   
115.
 Recently, we reported that multi-hollow polymer particles can be prepared from carboxylated polymer particles by the stepwise alkali/acid method. In this article, an attempt was made to prepare similar particles from acid-swellable polymer particles by the stepwise treatment with acid and alkali, which was named the stepwise acid/alkali method. The acid-swellable particles were produced by emulsion terpolymerization of styrene, butyl acrylate, and dimethyl 2-amino ethyl methacrylate. The effects of initial pH value, temperature, and time in the acid and alkali treatment processes on the multi-hollow structure were examined. Received: 18 December 1996 Accepted: 11 March 1997  相似文献   
116.
A new reactor and a novel in-situ sampling technique were developed for the study of the synthesis of CeO2 powders produced from dissolved cerium nitrate salts. The conical reactor minimized particle recirculation and provided a highly symmetrical and undisturbed plasma flow suitable for the analysis of the phenomena affecting the formation of CeO2 powders. Both a calorimetric study of the reactor and a thermodynamic analysis of CeO2 formation were conducted. The sampling probe is described and near-isokinetic sampling was achieved. The sampled particles were collected using a miniature wet collection system, i.e. a mist atomizer and a custom-made spray chamber. A numerical simulation of the velocity and temperature fields of the plasma gas in the reactor was done using Fluent. A comprehensive droplet-to-particle formation mechanism presented elsewhere is revisited and expanded based on calorimetry, thermodynamics of CeO2 formation, numerical simulations and collected particles. No traces of other oxidation states other than CeO2 were found.  相似文献   
117.
The interactions between copolymers of sodium styrene sulfonate (SSS) and N-isopropylacrylamide (NIPAM), anionic polyelectrolytes, and dodecyltrimethylammonium chloride (DTAC), a cationic surfactant, were studied in aqueous solutions of various ionic strengths. The copolymers were found to be thermoresponsive, showing a lower critical solution temperature (LCST). The influence of the polymer composition, the surfactant concentration, and the ionic strength on the LCST was studied. The surfactant was found to interact strongly with the polymer, forming mixed polymer-surfactant micelles. The critical aggregation concentration (cac) of the polymer-surfactant system was found from fluorescence spectroscopy using pyrene as a fluorescent probe. A strong dependence of the anionic polyelectrolyte-cationic surfactant interactions on the structure of the ionic comonomer was observed.  相似文献   
118.
Conjugated polymers and oligomers can serve as highly responsive fluorescent reporters for biosensor applications. However, their optical properties in aqueous media are highly dependent upon environmental conditions. The structure of the paracyclophane framework provides a platform for designing optical reporters that show little sensitivity to surfactants, and thus is well-suited for fluorescent assays. The permanent intramolecular delocalization through the paracyclophane core dominates intermolecular perturbations in spontaneously formed aggregates.  相似文献   
119.
程晓红  傅长金   《中国化学》2007,25(11):1762-1765
本文从商品化的间溴苯甲醚和对甲氧基苯甲醛出发,通过傅-克酰基化反应、串联的羟醛缩合及1,4-迈克尔加成反应,得到三芳基取代的1,5-二酮,然后用查尔酮(Chalcone)作氧化剂,二酮与BF3.Et2O 反应形成吡喃鎓盐,再与苯基乙酸钠盐缩合得到芳香二溴代衍生物,产物的DMA溶液在DBU和钯催化剂的作用下,160°C 加热12 h进行脱卤化氢环化反应, 生成四甲氧基取代的二苯并并四苯(DBN)类衍生物。并报道了产物的晶体结构和在溶液中的聚集效应。  相似文献   
120.
We studied a population of paraplegic patients in order to give prominence to a possible relationship between the topography of their spinal lesion and the occurrence of special articular diseases (P.O.A.). According to the motor and sensory state of their spinal cord, we first tried to obtain a classification of these lesions (the usual one schematically separates ‘flaccid’ and ‘rigid’ paraplegics). We mainly put the emphasis on this clustering step of the study:
    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