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   5396篇
  免费   863篇
  国内免费   1068篇
化学   4392篇
晶体学   55篇
力学   286篇
综合类   70篇
数学   706篇
物理学   1818篇
  2024年   9篇
  2023年   81篇
  2022年   143篇
  2021年   148篇
  2020年   199篇
  2019年   182篇
  2018年   141篇
  2017年   175篇
  2016年   240篇
  2015年   266篇
  2014年   318篇
  2013年   421篇
  2012年   467篇
  2011年   448篇
  2010年   397篇
  2009年   417篇
  2008年   407篇
  2007年   383篇
  2006年   343篇
  2005年   325篇
  2004年   284篇
  2003年   308篇
  2002年   264篇
  2001年   194篇
  2000年   164篇
  1999年   112篇
  1998年   73篇
  1997年   61篇
  1996年   84篇
  1995年   39篇
  1994年   44篇
  1993年   41篇
  1992年   34篇
  1991年   34篇
  1990年   24篇
  1989年   9篇
  1988年   8篇
  1987年   13篇
  1986年   11篇
  1985年   2篇
  1984年   1篇
  1983年   5篇
  1982年   3篇
  1981年   1篇
  1977年   1篇
  1973年   1篇
  1968年   1篇
  1959年   1篇
排序方式: 共有7327条查询结果,搜索用时 15 毫秒
161.
CTMAB胶束体系中反离子缔合度的测定   总被引:2,自引:0,他引:2  
对十六烷基三甲基淡化按(CTMAB)水胶束体系,不同方法测得其反离子缔合度产值不同【‘-\且很高于由股团电化学理论所得q值0.67问.本文以离子选择性电极法测定CTMAB水胶束体系中反离子缩合度(仁0.65),并研究了外加盐和乙醇的影响·1实验部分1.工试剂和仪器十六烷基三甲基漠化技(CP)在无水乙醇中重结晶两次,纯化物经帕环法测其表面张力在CMC附近无最低声、·淡化钾(AR),水为。次蒸馏水,PXJIC型离子计,302型PB,电极(响应范围为PB,=1.6~3.3,响应时间为5分钟)222型甘汞电极·1.2实验方法在CMCV/de的稀…  相似文献   
162.
MP2/6-31+G* calculations were performed on the cation- complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B+ all the atomic cations form -type cation- complexes with ethylene. On the other hand, with cyclobutadiene Li+, N+, Na+, P+ and K+ form -type complexes, whereas H+, F+, and Cl+ form covalent -type complexes. With benzene Li+, B+, Na+, Al+, and K+ form -type complexes whereas H+, F+, and Cl+ form -type complexes. It was concluded that the driving force to form the -type complex is chemical bonding, and that for metal cations to form -type complexes is non-covalent interaction.  相似文献   
163.
Under the condition of solid-liquid phase transfer catalysis,olefins were obtained by the reaction of p-nitrobenzyldibutyltelluroniumbromide with aromatic aldehyde.Under the condition of liquid-liquid phasetransfer catalysis,however,different products were obtained due to thereactivity of different bases or aldehydes.  相似文献   
164.
Chromiumexistsindifferentoxidationstatesingroundwater,industrialwastewater,seawater,andsoilofourenvironment1,2.Chromium(III)isanessentialtraceelementforhumans,requiredforthemaintenanceofnormalglucose,cholesterol,andfattyacidmetabolism.Ontheotherhand,watersolublechromium(VI),intheformCr2O72-orCrO42-,ishighlyirritatingandtoxictohumansandanimals3.Itsacutetoxiceffectsincludeanimmediatecardiovascularshockandlatereffectsonkidney,liver,andblood-formingorgans.Therefore,itisnecessaryforriskassessme…  相似文献   
165.
Oxidation of a series of phenols with cerium(IV) ammonium nitrate (CAN) in acetonitrile under mild conditions yields the mixture of corresponding nitrophenols. In the cases of methylphenols and hydroxy ‐carboxylic acids, the steric effect may reduce the nitration reaction. Compounds 3a and 4b showed selective activities to Hep 3B and Hep G2 cancer cell lines, respectively. Compound 2c showed selective activities to Hep G2 and MDA‐MB‐231 cancer cell lines. Furthermore, compound 10b showed selective activities to Hep G2, Hep 3B, MCF‐7 and MDA‐MB‐231 cancer cell lines.  相似文献   
166.
The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero‐point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6‐311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6‐311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007  相似文献   
167.
水蒸气处理对P-ZSM-5催化性能的影响   总被引:2,自引:0,他引:2       下载免费PDF全文
在不同温度下,用水蒸气对P-ZSM-5催化剂进行了处理,利用XRD、NH3-TPD、比表面和孔径物理吸附仪等手段对催化剂进行了表征,研究了水蒸气处理对P-ZSM-5催化1-丁烯裂解反应性能的影响.实验结果表明:P-ZSM-5催化剂具有良好的水热稳定性;合适的水蒸气处理,有利于催化剂孔容和孔径的增加;水蒸气处理降低了P-ZSM-5催化剂的酸量和酸强度,明显提高了丁烯裂解生成丙烯的选择性、收率和催化剂的抗积炭性能.最佳的水蒸气处理温度为580℃,P-ZSM-5催化剂催化1-丁烯裂解反应的丙烯选择性为39.4%,收率为34.2%.  相似文献   
168.
Synthesis and characterization of the ligand, [2-tetradecyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid, H5L] and its Gd(Ⅲ) chelate are described. Protonation constants for H5L (lgKiH = 10.80, 8.40, 4.30, 2.80, 2.15) and the stability constant for GdL2- (lgKGdL2-= 22.75) were determined by potentiometric titration and are similar with the related values of DTPA and Gd-DTPA respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after introduction of a linear chain tetradecyl group at the terminal acetic acid residue of DTPA.  相似文献   
169.
A double metal‐cyanide catalyst based on Zn3[Co(CN)6]2 was prepared. This catalyst is very effective for the ring‐opening polymerization of propylene oxide. Polyether polyols of moderate molecular weight having low unsaturation (<0.015 meq/g) can be prepared under mild conditions. The molecular weight of polymer is entirely controlled by a reacted monomer‐to‐initiator ratio. The polymers prepared with stepwise addition of monomer exhibit a narrower molecular weight distribution as compared with those prepared with one‐step addition of monomer. Various compounds containing active hydrogen, except basic compounds and low‐carbon carboxylic acid, may be used as initiators. The reaction rate increases with increasing catalyst amount and decreases with rising initiator concentration. Polymerization involves a rapid exchange reaction between the active species and the dormant species. It was also proven that, to a certain extent, the chain termination of this catalytic system is reversible or temporary. 13C NMR analysis showed that the polymer has a random distribution of the configurational sequences and head‐to‐tail regiosequence. It is assumed that the polymerization proceeds via a cationic coordination mechanism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1142–1150, 2002  相似文献   
170.
建立了同时测定化妆品中苯扎溴铵、2-溴-2-硝基-1,3-丙二醇、5-溴-5-硝基-1,3-二■烷、甲基二溴戊二腈、溴氯芬5种含溴防腐剂的高效液相色谱-电感耦合等离子体质谱法(HPLC-ICP-MS)。样品经含0.1%甲酸的甲醇溶液超声提取后,采用Agilent Eclipse-C_(18)(150 mm×4.6 mm,5μm)色谱柱分离,以0.1%甲酸-甲醇为流动相进行梯度洗脱,ICP-MS测定组分中的~(79)Br,以保留时间定性,外标法定量。5种含溴防腐剂均在0.5~100 mg/L范围内线性关系良好(r0.999),检出限为1.5~3.0μg/g,不同基质化妆品中的回收率为91.2%~108%,相对标准偏差(n=6)为1.3%~4.2%。该方法快速、准确、灵敏、专属性强,适用于化妆品中5种含溴防腐剂的定性定量分析。  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