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   25451篇
  免费   4648篇
  国内免费   6953篇
化学   19647篇
晶体学   833篇
力学   1555篇
综合类   910篇
数学   3617篇
物理学   10490篇
  2024年   45篇
  2023年   242篇
  2022年   836篇
  2021年   783篇
  2020年   849篇
  2019年   923篇
  2018年   794篇
  2017年   1025篇
  2016年   967篇
  2015年   1301篇
  2014年   1545篇
  2013年   1967篇
  2012年   2075篇
  2011年   2252篇
  2010年   2099篇
  2009年   2144篇
  2008年   2388篇
  2007年   2073篇
  2006年   2026篇
  2005年   1838篇
  2004年   1377篇
  2003年   1030篇
  2002年   1091篇
  2001年   932篇
  2000年   986篇
  1999年   637篇
  1998年   376篇
  1997年   273篇
  1996年   252篇
  1995年   237篇
  1994年   194篇
  1993年   202篇
  1992年   190篇
  1991年   165篇
  1990年   115篇
  1989年   125篇
  1988年   106篇
  1987年   113篇
  1986年   76篇
  1985年   61篇
  1984年   71篇
  1983年   66篇
  1982年   41篇
  1981年   38篇
  1980年   46篇
  1979年   24篇
  1978年   11篇
  1977年   12篇
  1975年   6篇
  1959年   6篇
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
991.
周国清 《分析测试学报》2013,32(8):1016-1019
通过静电作用将带正电的Ru(bpy)23+和带负电的纳米铂制备成铂钌纳米复合物(Ru-PtNPs),并将其滴涂在Nafion分散的多壁碳纳米管(MWCNTs-Nafion)复合膜修饰的玻碳电极上,制备了一种新的基于联吡啶钌的固相电致化学发光(ECL)传感器。利用扫描电镜以及电致化学发光的方法对传感界面进行表征。实验结果表明,通过此种方式可将大量的发光试剂Ru(bpy)23+固载到电极表面,并对三丙胺(TPA)保持良好的电催化活性,Ru-PtNPs/MWCNTs-Nafion修饰电极在0.1 mol.L-1磷酸盐缓冲溶液(PBS,pH 7.4)中对TPA的响应有很好的灵敏度和稳定性,线性范围为6.67×10-7~1.00×10-3mol·L-1,检出限(S/N=3)为3.3×10-7 mol·L-1。  相似文献   
992.
建立了超高效液相色谱串联质谱测定牛奶中四环素类、青霉素类、磺胺类和泰乐菌素等11种兽药残留的检测方法。样品经乙腈超声提取后离心分离,上层清液稀释10倍后过0.2μm滤膜上机测定。在优化条件下,11种兽药在其线性范围内的相关系数均在0.998以上,定量下限(LOQ,S/N=10)为0.3~15μg/kg,在低、中、高3个水平下的加标回收率为81%~117%,相对标准偏差为0.6%~10.2%。方法用于实际牛奶样品中兽药残留量的测定,结果满意。  相似文献   
993.
别建波  周洁  徐柏玲 《合成化学》2013,21(2):147-150
以1H-吡咯[2,3-b]吡啶-2-甲酸乙酯为起始原料,经5步反应合成了新化合物3-(2-羧基乙基)-1H-吡咯[2,3-b]吡啶-2-甲酸,其结构经1H NMR和HR-MS表征。合成中间(E)-1-Ts-3-(3-乙氧基-3-氧代丙基-1-烯基)-1H-吡咯[2,3-b]吡啶-2-羧酸乙酯的最佳反应(Heck)条件为:无水DMF为溶剂,Pd(OAc)2为催化剂,dppf为配体,三乙胺为碱,收率88%。  相似文献   
994.
孙志敏  周曼溪  陈广新  李齐方 《合成化学》2013,21(2):214-216,223
以2-甲基(或乙基)蒽醌为起始原料,经氧化、酰氯化、酯化等反应合成了3个蒽醌-2-甲酸烯烃类衍生物——乙二醇-9,10-蒽醌-2-甲酸丙烯酸脂,蒽醌-2-甲酸-10-十一碳烯脂和乙二醇蒽醌-2-甲酸甲基丙烯酸脂(6~8),其结构经1H NMR表征。UV测试结果表明,6~8在三氯甲烷中的λmax均为327 nm。  相似文献   
995.
以芴(1)为原料,浓硝酸/浓硫酸为硝化剂,合成了2,7-二硝基-9,9-二辛基芴,其结构经1H NMR和IR确证。最佳反应条件为:1 20 mmol,n(1):n(HNO3)=1:18,c(H2SO4)=15.3 mol.L-1,于10℃反应7 h,收率56%。  相似文献   
996.
李媛  彭蜀晋  贾敏  吴润 《广州化学》2013,38(1):77-83
准晶体是一种介于晶体和非晶体之间的固体。按照其准周期维数的分类方法分为一维、二维、三维准晶体,具有力学性能、电学性能和磁性能。利用其优良的性能特点,可将其应用于表面改性材料和结构材料增强相中。对准晶体的基础研究主要在其原子结构测定、形成因素、成分预测、单质组元的寻找和物理性质的有效调控等方面;而应用研究主要包括其薄膜技术和微纳米化的研究等。  相似文献   
997.
The chemical castration law, which targets child molesters with recidivism, was introduced in Korea in 2011. For this, leuprolide, a gonadotropin-releasing hormone agonist, is used to decrease testosterone production and suppress libido. In order to achieve efficient law enforcement, it is necessary to monitor intentional ingestion of drugs that antagonize the effect of leuprolide. Therefore, an analytical method for the simultaneous detection of mirodenafil, sildenafil, tadalafil, udenafil, vardenafil, icariin, alprostadil, and yohimbine, which are the major impotence treatment drugs, legitimately or otherwise, in Korea, as well as their selected metabolites, in human urine was established and validated using liquid chromatography–tandem mass spectrometry (LC–MS/MS). First, different sample preparation methods, two solid-phase extractions with different cartridges and protein precipitation, were compared and protein precipitation was chosen for the entire study because it showed better matrix effects and recoveries. Thus, the drugs and metabolites in urine were extracted by protein precipitation and then filtered and analyzed by LC–MS/MS with polarity switching electrospray ionization. The validation results of selectivity, matrix effect, recovery, linearity, intra- and inter-assay precision and accuracy were satisfactory. The limits of detection ranged from 0.25 to 10 ng/mL, and the limits of quantification were 2.5 to 50 ng/mL. The drugs and metabolites in urine did not show any degradation under storage for 7 and 15 days at 4 and ?20 °C as well as after three freeze–thaw cycles. The developed method will be very useful for monitoring the illegal use of impotence treatment drugs.  相似文献   
998.
An improved online two-dimensional liquid chromatography-quadrupole time-of-flight mass spectrometry (2D LC-QToF MS) system was developed for the lipid profiling of human plasma, in which different lipid classes were separated by the first dimensional normal-phase (NP) LC and different lipid molecular species were separated by the second dimensional reversed-phase (RP) LC. This 2D LC-QToF MS system was built based on a ten-port, two-position valve as the interface, the conditions of which had been optimized and discussed in detail. As two loops were used to trap and transfer the first dimensional elute to the second dimension separately, this new interface suppressed the sample band broadening in the first dimensional column, increased the recovery and repeatability of 2D LC interface, and offered the possibility for the realization of not-stop-flow NP/RP 2D LC system. Finally, 190 endogenous lipid species out of 10 lipid classes were determined within a single run from the plasma of peritoneal patients. This method was also applied to identify the difference in lipid profile between plasma from peritoneal dialysis patients with bad volume status and peritoneal dialysis patients with good volume status. The discovery of 30 potential biomarkers would be helpful to the malnutrition, inflammation, and atherosclerosis syndrome investigation.  相似文献   
999.
1000.
A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p‐Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface‐enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface‐enhanced Raman spectroscopy bands from p‐mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions.  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