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   3238篇
  免费   666篇
  国内免费   1331篇
化学   2558篇
晶体学   199篇
力学   227篇
综合类   114篇
数学   490篇
物理学   1647篇
  2024年   4篇
  2023年   33篇
  2022年   112篇
  2021年   94篇
  2020年   112篇
  2019年   123篇
  2018年   115篇
  2017年   155篇
  2016年   107篇
  2015年   175篇
  2014年   184篇
  2013年   268篇
  2012年   272篇
  2011年   283篇
  2010年   294篇
  2009年   313篇
  2008年   324篇
  2007年   338篇
  2006年   307篇
  2005年   285篇
  2004年   228篇
  2003年   182篇
  2002年   167篇
  2001年   143篇
  2000年   165篇
  1999年   97篇
  1998年   43篇
  1997年   27篇
  1996年   18篇
  1995年   31篇
  1994年   26篇
  1993年   27篇
  1992年   15篇
  1991年   13篇
  1990年   15篇
  1989年   15篇
  1988年   16篇
  1987年   15篇
  1986年   10篇
  1985年   15篇
  1984年   4篇
  1983年   15篇
  1982年   7篇
  1981年   12篇
  1980年   8篇
  1979年   4篇
  1978年   4篇
  1973年   2篇
  1965年   7篇
  1959年   2篇
排序方式: 共有5235条查询结果,搜索用时 109 毫秒
121.
The title complex Cu[C5H3N(CCH3=N-C6H5)2]2(PF6)2 has been synthesized by reaction of Schiff base C5H3N(CCH3=N-C6H5)2 and cupric sulfate in toluene solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 1041.85. The crystal structure belongs to triclinic system with space group P1 and cell parameters: a=12.6470(10)?, b=14.123(2)?, c=15.613(2)?;α=66.150(10)°,β=79.470(10)°,γ=78.290(10)°, V=2481.6(5)?3, Z=2, Dc=1.394Mg·m-3 and F(000)=1064. The final R[I >2σ(I)]:R1=0.0668, wR2=0.1927; R(all data): R1=0.1133, wR2=0.2357. The Cu(Ⅱ) was coordinated by six nitrogen, at the same time the Cu(Ⅱ) formed a distorted octahedron, besides the angles and planes of this compound were discussed . The result of kinetics of the thermal decomposition indicated that the first step of it is 2 series chemical reactions, the function of machanism is f(a)=(1-a)2, and the activation energy is 144.64E/kJ. CCDC: 180872.  相似文献   
122.
The title compound, {[n-Bu2Sn(O2CCH2CS2NC4H8)]2O}2, has been synthesized by the reaction of (tetrahydro-pyrrodithiolocarbamoylthio)acetic acid with the di-n-bubyltin oxide in 1∶1 molar ratio. The complex has been characterized by elemental analysis, IR and NMR. The crystal structure of it has been determined by X-ray single crystal diffraction. And the results showed that the crystal belongs to triclinic system with space group P1 and some crystal parameters: a=1.220 2(9) nm, b=1.315 8(10) nm, c=1.380 4(10) nm, α=111.215(9)°, β=99.357(9)°, γ=96.075(10)°, V=2.006(2) nm3, Z=1, F(000)=908, μ=1.489 mm-1, Dc=1.474 g·cm-3, R1=0.037 5, wR2=0.0839. The complex has a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn2O2 unit in which two bridged oxygen atoms both connect with an exo-cyclic tin atom which has a distorted octahedron. Each of the endo-cyclic tin atoms exhibits a distorted trigonal bipyramid coordination geometry with an additional weak coordination carboxylate oxygen. Four carboxylate ligands are divided into two types. And two of them are bidentate and connecting to each of exo-cyclic tin atoms by using both oxygen atoms, whereas the others bridge to each pair of exo-and endo-cyclic tin atoms utilizing one oxygen atom only. CCDC: 220513.  相似文献   
123.
Green chemistry is also called environment harmless or environment friendly chemistry.Green chemistry requires to use new synthetic methods, engineering technologies and processes to eliminate or reduce by-products, wastes or products that harmful to human health, community safety,and ecology environment. Green chemistry pursues to control the usage of the harmful and toxic materials, reduce waste emission, avoid necessity to treat the wastes; Green Chemistry advocates wastes management from the beginning, improving the efficiency of atoms, optimizing the use of resources and energy, lowering the cost of production. Green Chemistry technologies are the ultimate path to the clean chemical production in the future.Insight Co. takes "hospital of enterprises" and "bank of technologies" as our characteristics in business, and deems the development and spread of green chemistry as our mission. We developed an unique business model which combines education, research and production. In the past 8 years,we had applied and obtained more than 30 patents and received more than ten national and provincial awards in technology progress.We had made great progress in the manufacturing of organophosphorus pesticides, especially the production of omethoate, methamidophos, paraquat and glycyrrhizinic phosphor, etc., which made a stable foundation for INSIGHT's development. We had also achieved great success in the high efficiency low toxic pesticides, such as imidacloprid, etofenprox, metalaxyl and in the new synthetic methods in various amino acids as well as in the pharmaceutical intermediates. The new method of preparation indigo using N-phenylglycinonitrile is an advanced process in the world in terms of the clean production technology for Ferro cyanide and HCN's transformation rate improvement. We solved the pollution problem of the old route. The newly developed substituted product for indigo using a clean production technology which greatly reduced the material consumption and environmental pollution. Insight has facilities producing nearly 20 photo-initiators and developed the new technique for light-curing lubricity, water-born resin, the technique for water-bon coating and their associated applications. The successfully developed technology of new high performance emulsion will promote the technology advancement in the coating industry and the wide spread of new coating in China.Insight has developed a series of new technologies, including a novel reactor technology - using a newly designed patented blade, has been characterized as high efficiency & energy saving reactor.The novel technology research and development are widely applied in INSIGHT's ten-year practice.We studied and confirmed the non-thermal catalyzing effect of microwaves, proposed a "weak microwave" theory, and a chemical reaction rate equation. We proposed that in the existence of microwave magnesium ions and phosphate, amino acid can be activated to form peptide which maybe the path of the origin of life.A 3000mt/a pilot plant in Chongqing using carbon monoxide and hydrogen to produce dimethyl ether in a single step has been built via collaboration with the Dept. of Chemical Engineering at Tsinghua University. The large scale, low cost production of dimethyl ether may possible through comprehensive technology improvement. This technology will take full advantage of current ammonia production facilities, and try to solve the global fuel shortage problem.  相似文献   
124.
介孔分子筛的制备与苯加氢反应的催化性能   总被引:1,自引:0,他引:1  
1992年美国Mobil公司的研究人员首次报道合成出具有规则孔结构的M41S系列介孔分子筛材料.由于介孔材料独特的性质,引起了人们极大的兴趣,在其合成与性能等方面进行了大量的研究,合成出了多种系列不同性能的介孔分子筛,并研究了介孔分子筛作为催化剂或催化剂载体在各类催化反应中的催化性能.  相似文献   
125.
桥联双核配合物[(DPC)2Co2(H2O)5]·2H2O的合成与晶体结构   总被引:9,自引:0,他引:9  
The new complex formulated [(DPC)2Co2(H2O)5]·2H2O (HDPC- is pyridine-2,6-dicarboxylate) has been synthesized and the crystal structure was determined by X-ray diffraction. The crystal structure of the complex belongs to monoclinic system with space group P21/c, a=0.83850(10) nm, b=2.7386(4) nm, c=0.9610(2) nm, β=98.280 (10) °, V=2.1838(6) nm3, Z=4, Dc=1.746 g·cm-3, μ=1.597 mm-1. In the crystal the two Co2+ are in distorted octahedrons. The part of [Co(DPC)2] possess an approximate D2d symmetry, while the part of [OCo(2)(OH2)5] has an approximate C2 symmetry.  相似文献   
126.
构建了快速测定血清中甲胎蛋白(AFP)含量的电流型免疫传感器,该免疫传感器是用壳聚糖固定电子媒介体亚甲基蓝和辣根过氧化物酶(HRP)标记的甲胎蛋白抗体于一次性丝网印刷碳电极(SPCE)表面制备而成。当该免疫传感器在含AFP样品的溶液中于30℃培育40 min后,抗原抗体的免疫结合会导致HRP标记对过氧化氢电催化氧化的效率降低。在优化的测定条件下,催化效率的降低与AFP浓度在5.0~110.0μg.L-1范围内呈线性关系,免疫分析的检出限为1.4μg.L-1(3σ)。对免疫传感器的精密度作了试验,同一支传感器测试结果的相对标准偏差为6.6%;当取3支用同一方法制备的传感器进行测试时,相对标准偏差为9.3%。放置7d后,传感器对AFP的响应值相当于初试值的88%,在pH 7.0的缓冲溶液中的还原电流为原值的96%。  相似文献   
127.
应用等温流动微量热法测定了298.15 K时互为旋光异构体的D-甘露醇与D-山梨醇在不同浓度的氯化钠水溶液中的稀释焓, 利用 McMillan-Mayer 理论计算了D-甘露醇与D-山梨醇在不同浓度的氯化钠水溶液中的焓对相互作用系数. 结果表明, D-甘露醇和D-山梨醇在氯化钠水溶液中的焓对相互作用系数h2均为正值, h2的值随着氯化钠浓度的增加皆逐渐增大, 但D-山梨醇的焓对相互作用系数h2增大的速率[dh2 /dm(NaCl)]比 D-甘露醇的要大. 根据两多元醇分子构象结构的差异, 溶质-溶质相互作用和溶质-溶剂相互作用对结果进行了解释.  相似文献   
128.
殷开梁 《化学教育》2019,40(4):40-42
受私董会U型7步研讨法的启发,提出了可用于研究型教与学的一种新方法:U型7步探究法。"U型"即探究问题有一个先下沉寻找本质再使问题清晰的过程,躬问、探究等7步为具体操作流程,由教练引导,案主为主,全员受益。还以一次成功的运作实例对方法进行了详细说明。  相似文献   
129.
含氮杂环及其衍生物的氮氧化方法研究进展   总被引:1,自引:0,他引:1  
李再峰  罗富英 《有机化学》2002,22(4):233-238
含氮杂环及其衍生物中的N-氧化反应是合成许多精细化工产品,如日用化学 品、医药、农药的重要反应,但该反应选择性较高,只要求在杂环氮上进行氧化而 不影响分子其它部位,从氮杂环及其衍生物应用不同氧化剂选择性氧化综述了该类 化合物的N-氧化反应。  相似文献   
130.
Cr掺杂对K2La2Ti3O10光催化活性的影响   总被引:1,自引:0,他引:1  
通过溶胶-凝胶法制备了层状钙钛矿结构的K2La2Ti3O10及Cr掺杂的K2La2Ti3O10,采用X-射线衍射(XRD)、紫外可见漫反射光谱(DRS)、X射线光电子能谱(XPS)等对K2La2Ti3O10及Cr掺杂K2La2Ti3O10进行了表征。以I-为电子给体、分别在紫外和可见光辐射下研究了K2La2Ti3O10及Cr掺杂K2La2Ti3O10光催化分解水的产氢活性。采用第一性原理,计算了Cr掺杂对K2La2Ti3O10半导体能带结构和态密度的影响,从电子结构的变化揭示了掺杂引起光催化活性差异的原因。结果表明,Cr的掺入能够改善和提高K2La2Ti3O10的光解水的产氢活性;Cr改善和提高K2La2Ti3O10的光解水的产氢活性存在一个最佳的掺杂浓度;当Cr与Ti的物质量的比为0.02∶1时,紫外光催化分解水产氢速率为1 500 μmol·L-1·h-1,可见光催化分解水产氢速率为83.6 μmol·L-1·h-1,分别为K2La2Ti3O10掺杂改性前产氢速率的26和5倍。  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