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   502篇
  免费   44篇
  国内免费   85篇
化学   542篇
力学   7篇
综合类   5篇
数学   20篇
物理学   57篇
  2023年   1篇
  2019年   1篇
  2018年   2篇
  2017年   1篇
  2016年   1篇
  2015年   1篇
  2014年   30篇
  2013年   48篇
  2012年   43篇
  2011年   10篇
  2010年   1篇
  2009年   4篇
  2008年   22篇
  2007年   19篇
  2006年   15篇
  2005年   18篇
  2004年   28篇
  2003年   35篇
  2002年   85篇
  2001年   193篇
  2000年   31篇
  1999年   20篇
  1998年   10篇
  1997年   8篇
  1996年   1篇
  1995年   3篇
排序方式: 共有631条查询结果,搜索用时 15 毫秒
71.
Ni/Si2催化剂具有较好的低碳烷烃与二氧化碳重整制合成气的反应性能,添加La2O3助剂和K2O助剂可提高催化剂活性和合成气收率,从而进一步改善催化剂的低碳烷烃与CO2重整制合成气的反应性能,研制的KLaNi/Si2催化剂,用于天然气与CO2重整反应制合成气可达97%的低碳烷烃转化率和95%以上的合成气收率。  相似文献   
72.
Solid-phase methodology has been rapidly and extensively applied to the preparation of small organic molecules recently1. It might be argued that selenoxide syn-elimination provided the principal impetus for the development of organoselenium chemistry. In addition, the required selenoxides are readily available from the oxidation of the corresponding selenides, which in turn can be prepared by the reaction of selenium-stabilized carbanions with various electrophilic substrates2. However, or…  相似文献   
73.
Metal foams, now one of research foci, are a newclass of materials with low densities and novel physi-cal, mechanical, thermal, electrical and acoustic prop-erties[1—8]. Demands from high-tech make Al alloyfoam, which has much higher specific strength than ofpure Al foam, the new development focus[9—11]. Melt foaming process is one of the approaches tofabricate Al foam and Al alloy foam and their porestructure (pore diameter and porosity) has close rela-tionship with the thermal decompo…  相似文献   
74.
Structural Features of a Polysaccharide from Centella asiatica   总被引:3,自引:0,他引:3  
Centella asiatica has been used as remedy for sodation, stabilization and against lepra, anabrosis1 in the oriental countries. The low-molecular-weight constituents in Centella asiatica have been investigated1. However, no polysaccharides have been reported. 1BI was the first polysaccharide isolated from C. asiatica, which had immunostimulating activity in vitro. In present study, we report the structural features of 1BI. Experimental Extraction, isolation and purification Dried C.…  相似文献   
75.
The natural product, hainanolide 1, also under the name harringtonolide2 demonstrated antitumor and antiviral activities in preliminary test. Its structure was determined by X-ray diffraction. The total synthesis of 1 was reported recently by Mander3. A different scheme of its synthesis has been studied in our laboratory4. Here the determination of the stereochemical structure of the key intermediate 2 in the synthesis was reported. HMBC and HMQC spectra identified the skeleton and H,…  相似文献   
76.
Aiphanol was isolated from the seeds of Aiphanes aculeate Willd. (Arecaceae) collected in Peru and was reported to exhibit significant inhibitory activities against cyclooxyge- nases-1 and -2. The structure of aiphanol was elucidated by spectroscopic methods as an unprecedented stilbenolignan skeleton in which a stilbene moiety is linked to a phenylpropane unit through a dioxane bridge1. In our previous works the synthetic approach to 1,4-benzodioxane lignans were achieved2. Since aiphanol…  相似文献   
77.
Polymer-supported reagents for organic synthesis are enjoying a renewed popularity with the emergence of combinatorial chemistry in recent years1. 4-(Arylseleno)morpholines formed in situ are useful -seleno-introducing reagents for saturated aldehydes2. -Sele- noaldehydes, as a frequently used intermediates, can be converted into -haloaldehydes by halogenating reaction3. However, organic selenium reagents always have a foul smell and are quite toxic, which is often problematic in organic sy…  相似文献   
78.
The photochemistry of the vitamin D family and their precursors has been the subject of extensive studies for many years1-4. Most of the studies focus on the photoisomer- ization of 7-dehydrocholesterol and that of tachysterol to previtamin D3, which is of commercial importance in the synthesis of vitamin D34, 5. Recently the cis/trans isomerization of vitamin D analogs (Scheme 1) draws attention because of its importance in the synthesis of hydroxylated vitamin D metabolites6. However, o…  相似文献   
79.
成功地合成了石墨烯/CdTe量子点复合物,并采用透射电镜、紫外吸收光谱、荧光发射光谱、荧光衰减曲线和X射线光电子能谱对产物进行了表征。透射电镜结果显示CdTe量子点被修饰于石墨烯的表面;X射线光电子能谱结果表示石墨烯在合成过程中被还原,还表明在所合材料的表面具有羧基和羟基;荧光发射光谱和荧光衰减曲线的结果显示将CdTe量子点修饰于石墨烯表面显著提高了CdTe量子点的荧光性能。此外,基于克伦特罗和石墨烯/CdTe量子点复合物之间形成的氢键,所合成材料可用于定量分析克伦特罗。克伦特罗对石墨烯/CdTe量子点复合物具有显著的猝灭作用,荧光强度的降低(F0/F)与克伦特罗之间存在良好的线性关系,线性范围为7.22~108.30 μmol·L-1,检出限为4 μmol·L-1。  相似文献   
80.
采用密度泛函理论以及B3LYP方法和单激发组态相互作用(CIS)方法分别优化了一系列[Os(II)(CO)3(tfa)(L)](tfa为三氟乙酸; L=O^O(1), O^N(2), N^N(3), 其中O^O为六氟乙酰丙酮, O^N为羟基喹啉, N^N为3-(三氟甲基)-5-(2-吡啶基)吡唑)配合物的基态和激发态结构. 利用含时密度泛函理论(TD-DFT)结合极化连续溶剂化模型(PCM)计算了配合物在CH2Cl2溶液中的吸收和发射光谱. 研究结果表明, 优化得到的几何结构参数和相应的实验值符合得非常好, 激发态几何构型相对基态变化较小, 这与实验上观察到的较小的斯托克斯频移现象一致. 配合物1-3的最低能吸收分别在342、431和329 nm, 其磷光发射分别在521、638 和488 nm. 配合物1-3的最高占据分子轨道和最低空轨道主要表现为L配体的π和π*轨道特征, 所以它们的最低能吸收归属于π-π*电荷跃迁, 并混有少量的金属到配体的电荷跃迁(MLCT)和配体之间电荷跃迁(LLCT)微扰, 且其高能吸收也表现为配体内部(IL)和配体间(LL)的电荷跃迁. 此外, 它们的磷光发射和吸收有相似的跃迁特征.  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