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   3045篇
  免费   240篇
  国内免费   472篇
化学   3545篇
晶体学   14篇
力学   4篇
综合类   20篇
物理学   174篇
  2024年   7篇
  2023年   23篇
  2022年   91篇
  2021年   87篇
  2020年   144篇
  2019年   120篇
  2018年   99篇
  2017年   116篇
  2016年   110篇
  2015年   132篇
  2014年   146篇
  2013年   295篇
  2012年   186篇
  2011年   150篇
  2010年   140篇
  2009年   152篇
  2008年   158篇
  2007年   144篇
  2006年   148篇
  2005年   150篇
  2004年   148篇
  2003年   137篇
  2002年   79篇
  2001年   72篇
  2000年   72篇
  1999年   79篇
  1998年   83篇
  1997年   48篇
  1996年   69篇
  1995年   51篇
  1994年   55篇
  1993年   56篇
  1992年   49篇
  1991年   28篇
  1990年   19篇
  1989年   15篇
  1988年   14篇
  1987年   9篇
  1986年   15篇
  1985年   10篇
  1984年   15篇
  1983年   7篇
  1982年   9篇
  1981年   6篇
  1980年   5篇
  1979年   5篇
  1978年   1篇
  1977年   1篇
  1973年   1篇
  1972年   1篇
排序方式: 共有3757条查询结果,搜索用时 15 毫秒
231.
To detect, identify, and quantify the polycyclic aromatic hydrocarbons (PAHs) released into the environment, the PAHs need to be isolated from the soil matrix. In this work, a modified quick, easy, cheap, efficient, rugged and safe (QuEChERS) method with ionic liquid was combined with liquid chromatography to identify 16 selected PAHs in soil. Ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim]PF6) was applied as an extractant component to enhance the process. The [Hmim]PF6 content in acetonitrile (ACN) was optimized. The [Hmim]PF6 modified QuEChERS method has the advantages defined by its name and a similar recovery to other extraction methods reported in the literature. Adding [Hmim]PF6 may eliminate the co-extract proportion and achieve a more effective extraction. Compared with ACN alone, the matrix effect (ME) of ACN containing 5% [Hmim]PF6 was reduced by approximately 35%. Additionally, the ME of using ACN containing [Hmim]PF6 without a clean-up procedure was similar to that of using ACN followed by a clean-up procedure. The recoveries of the QuEChERS method implemented with [Hmim]PF6 ranged from 75.19% to 100.98%. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.86 to 4.51 µg/kg and from 2.87 to 15.13 µg/kg, respectively.  相似文献   
232.
Three biscoumarin dyes bridged by polycyclic aromatic bridges (anthracen, pyrene and dibenzo[g,p]chrysene) were prepared as the emissive materials for the application of organic light-emitting devices. The relationship between their structures, photophysical properties, electrochemical properties and performances of organic light-emitting devices are described. The multilayered doped devices with a configuration of ITO/NPB (20 nm)/TBADN: biscoumarin compound (x wt%, 30 nm)/TPBi (30 nm)/Liq (2 nm)/Al (100 nm) have been successfully fabricated by vacuum-deposition method. All the devices showed green emission with high electroluminescent efficiencies. Especially, the device based on the compound containing pyrene as a bridge group at 7% doping concentration showed the best performance with a maximum brightness of 10552 cd/m2, maximum luminous efficiency of 5.39 cd/A and maximum external quantum efficiency (EQE) of 2.35%.  相似文献   
233.
The present study aims to introduce three known and three new stable polycyclic aromatic compounds synthesized. With MALDI-Mass, 1H and 13C NMR spectroscopy, all new compounds were characterized. In the DMF solution were carried out the electrochemical and photophysical properties of the polyaromatic compounds. The compounds are highly fluorescent showing green-red emission when excited at one single wavelength. For the compound 3, it was shown that the highest Stokes Shift (191 nm) appeared which may be due to the excited state energy transfer. The compounds also indicated the blue-orange region of the electromagnetic spectrum strong emission bands. Additionally, compounds 1, 3, 4, and 5 were investigated for their in vitro cytotoxic activities against PC-3 prostate cancer cells, L-929 non-cancerous cells, and MDA-MB-231 breast cancer for 24 h, 48 h and 72 h. The results obtained from the experiment demonstrated that compounds had different cytotoxic activity against cell lines. Compound 3 was indicated to be inactive against L-929 cells and MDA-MB-231 cancer cells, whereas compounds 1, 4 and 5 indicated a dose and time-dependent cytotoxic activity against PC-3, MDA-MB-231, and L-929 cell lines. It was found that the most sensitive cells to compound 5 were MDA-MB-231 human breast cancer cells. Additionally, it became clear that compounds 1 and 3 had significant selectivity for human PC-3 prostate cancer cells, and compounds 1, 4 and 5 had considerable selectivity for human MDA-MB-231 breast cancer cells. Also, the quantum chemical examinations of six organic compounds were conducted at the B3LYP/6-31G level in the gas phase and water. According to calculated results, compound 5 was found to be the best candidate for NLO applications.  相似文献   
234.
Silica-supported mono-metal (such as Ni, Cu) complexes and mixed metal (such as Cu/Zn, Cu/Cr) complexes of chitosan have been prepared. It is found that these non-noble metal complexes could be used as efficient catalysts for the hydrogenation of aromatic nitro compounds. The effects of type of metal, reaction temperature and pressure, solvent, nitrogen/metal molar ratio in the complex catalysts on the yields from nitrobenzene to aniline have been examined. It was also found that catalysts are active for the catalytic hydrogenation of other aromatic nitro compounds such as 2-nitroanisole, 2-nitroaniline, 2-nitrotoluene and 1-chloro-4-nitrobenzene.  相似文献   
235.
Marinating is one of the most common methods of pre-processing meat. Appropriate selection of marinade ingredients can influence the physicochemical properties of the meat and can reduce the level of polycyclic aromatic hydrocarbons (PAHs) in the final product. The effects of the inclusion of natural plant extracts such as bay leaf (BL), black pepper (BP), turmeric (TU), jalapeno pepper (JP) and tamarind paste (TA) in marinades on the physicochemical properties of grilled pork neck were studied. The addition of spice extracts to marinades increased the proportion of colour components L* and b*. The use of TU, TA, JP, MX and C marinades lowered the hardness and pH of the meat. The highest phenolic compound levels were observed in the case of the mixture of all extracts (MX) and JP marinades, and the highest total antioxidant capacity was exhibited by the BL and MX marinades. The highest PAH content was recorded in the CON marinade (Σ12PAH 98.48 ± 0.81 µg/kg) and the lowest in the JP marinade (4.76 ± 0.08 µg/kg), which had the strongest, statistically significant reducing effect (95% reduction) on PAH levels. Analysis of correlation coefficients showed a relationship between the total antioxidant capacity of the marinades and the PAH content in grilled pork.  相似文献   
236.
汤又文  郎丽 《合成化学》2006,14(2):160-161
以手性芳胺为母体,丙烯酰氯为酰化试剂,合成了新型手性功能单体(1)。用1合成了一系列手性分子印迹聚合物。1的结构经1H NMR,IR,MS及元素分析确证。  相似文献   
237.
杨波  余刚  张祖麟 《化学进展》2006,18(1):87-92
本文介绍了电化学方法用于氯代芳烃污染物去除的原理、反应历程及影响因素,分析了进一步实用化应考虑的主要问题,展望了该方向今后的发展趋势。  相似文献   
238.
 应用红外光谱技术研究了在乙酸锌催化作用下1,5-萘二胺与碳酸二甲酯甲氧基羰基化反应机理. 结果表明,二水合乙酸锌只有失去两个结晶水变成无水乙酸锌后才能产生催化活性. 无水乙酸锌与1,5-萘二胺形成一个新的配位络合物,该配位络合物是一个适宜的亲核试剂,能与碳酸二甲酯进行亲核反应,生成1,5-萘二胺的甲氧基羰基化产物. 在无水乙酸锌与1,5-萘二胺形成配位络合物的过程中,无水乙酸锌的结构从双齿型转变成单齿型.  相似文献   
239.
Diphenylmethane and substituted diphenylmethane are important compounds forsynthesis chemistry as well as industrial chemistry. These compounds are easilysynthesized by the benzylation of aromatic compounds with benzyl chloride or benzylalcohol catalyzed by homogeneous acid catalysts, such as AlCl3, FeCl3, H2SO4, HF andBF3. However, these catalytic systems are highly corrosive, and usually proceed withlow selectivity. In addition, they are less satisfactory from the environmen…  相似文献   
240.
在超声波下以吲哚、芳香醛、丙二酸亚异丙酯为原料一锅法合成了β-吲哚衍生物——5-[(3-吲哚基).芳甲基]-2,2-二甲基-1,3-二氧六环4,6-二酮,其结构经IR和1H NMR确认。  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