全文获取类型
收费全文 | 2747篇 |
免费 | 186篇 |
国内免费 | 444篇 |
专业分类
化学 | 3068篇 |
晶体学 | 20篇 |
力学 | 3篇 |
综合类 | 20篇 |
数学 | 63篇 |
物理学 | 203篇 |
出版年
2024年 | 11篇 |
2023年 | 120篇 |
2022年 | 44篇 |
2021年 | 70篇 |
2020年 | 118篇 |
2019年 | 111篇 |
2018年 | 104篇 |
2017年 | 79篇 |
2016年 | 97篇 |
2015年 | 87篇 |
2014年 | 119篇 |
2013年 | 247篇 |
2012年 | 124篇 |
2011年 | 157篇 |
2010年 | 123篇 |
2009年 | 161篇 |
2008年 | 168篇 |
2007年 | 185篇 |
2006年 | 170篇 |
2005年 | 153篇 |
2004年 | 153篇 |
2003年 | 87篇 |
2002年 | 77篇 |
2001年 | 53篇 |
2000年 | 53篇 |
1999年 | 60篇 |
1998年 | 81篇 |
1997年 | 46篇 |
1996年 | 54篇 |
1995年 | 41篇 |
1994年 | 36篇 |
1993年 | 36篇 |
1992年 | 22篇 |
1991年 | 29篇 |
1990年 | 20篇 |
1989年 | 14篇 |
1988年 | 8篇 |
1987年 | 14篇 |
1986年 | 7篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1970年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有3377条查询结果,搜索用时 31 毫秒
1.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
2.
Edward G. Sheetz Zhao Zhang Alyssa Marogil Minwei Che Dr. Maren Pink Dr. Veronica Carta Prof. Dr. Krishnan Raghavachari Prof. Dr. Amar H. Flood 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201584
The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF3−). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF3−, by cyanostar macrocycles that are size-complementary to the inorganic BF4− progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K+ salts of R−BF3− anions. 相似文献
3.
Hydrodynamic cavitation experiments in microfluidic systems have been performed with an aqueous solution of luminol as the working fluid. In order to identify where and how much reactive radical species are formed by the violent bubble collapse, the resulting chemiluminescent oxidation reaction of luminol was scrutinized downstream of a constriction in the microchannel. An original method was developed in order to map the intensity of chemiluminescence emitted from the micro-flow, allowing us to localize the region where radicals are produced. Time averaged void fraction measurements performed by laser induced fluorescence experiments were also used to determine the cavitation cloud position. The combination void fraction and chemiluminescence two-dimensional mapping demonstrated that the maximum chemiluminescent intensity area was found just downstream of the cavitation clouds. Furthermore, the radical yield can be obtained with our single photon counting technique. The maximum radical production rates of 1.2*107 OH/s and radical production per processed liquid volume of 2.15*1010 HO/l were observed. The proposed technique allows for two-dimensional characterisation of radical production in the microfluidic flow and could be a quick, non-intrusive way to optimise hydrodynamic cavitation reactor design and operating parameters, leading to enhancements in wastewater treatments and other process intensifications. 相似文献
4.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes 下载免费PDF全文
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
5.
关于绝对半素环和绝对半素根 总被引:3,自引:0,他引:3
张宪君 《纯粹数学与应用数学》1993,9(2):57-60
本文了绝对半素环的概念,研究了绝对半素与与半素环及素环之间的关系,讨论了由全体绝对半素环类决定的上根--绝对半半素根及其性质。 相似文献
6.
烷基硫酸盐表面张力的量子化学研究 总被引:1,自引:0,他引:1
用AMl量子化学计算法优化了十三烷基硫酸根阴离子和——CH3在不同取代位的十二烷基硫酸根阴离子的几何构型,得到最优构型时最高占据分子轨道能级EHOMO、最低空轨道能级ELUMO、电子能量Eele和偶极矩μ等数据.将这些电子结构数据分别与表面张力相拟合,得到很好的相关性。文中讨论了——CH3在不同位置取代对表面张力的影响。 相似文献
7.
Ernesto Quesada 《Tetrahedron letters》2004,45(25):4877-4881
The first syntheses of newly isolated members of the Preussomerin family, Preussomerins K and L, are reported. Key steps include the functionalisation of a 2-arylacetal anion, one-pot Friedel-Crafts cyclisation-deprotection and reductive opening of epoxides. 相似文献
8.
Grishin D. F. Semyonycheva L. L. Telegina E. V. Smirnov A. S. Nevodchikov V. I. 《Russian Chemical Bulletin》2003,52(2):505-507
Organometallic compounds Cp2TiCl2, (EtC5H4)2NbCl2, and (PriC5H4)2WCl2 were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed. 相似文献
9.
Using radical chemistry novel highly condensed heterocycles have been synthesized. The mechanism for their formation is discussed. 相似文献
10.
Zhu Linsheng 《东北数学》1998,(1)
in this paper, the classification and realization of complete Lie algebras withcommutative nilpotent radicals are given. From this, some results on the radicals of thesecomplete Lie algebras are obtained. 相似文献