全文获取类型
收费全文 | 297篇 |
免费 | 26篇 |
专业分类
化学 | 279篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 18篇 |
物理学 | 23篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 9篇 |
2021年 | 16篇 |
2020年 | 16篇 |
2019年 | 24篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 26篇 |
2015年 | 10篇 |
2014年 | 10篇 |
2013年 | 15篇 |
2012年 | 33篇 |
2011年 | 25篇 |
2010年 | 13篇 |
2009年 | 8篇 |
2008年 | 12篇 |
2007年 | 20篇 |
2006年 | 16篇 |
2005年 | 6篇 |
2004年 | 6篇 |
2003年 | 6篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有323条查询结果,搜索用时 15 毫秒
111.
Weber L Eickhoff D Werner V Böhling L Schwedler S Chrostowska A Dargelos A Maciejczyk M Stammler HG Neumann B 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4434-4446
A series of diphenylacetylenes with one 1,3,2-benzodiazaborolyl end group (BDB) and a second end group X (X = H, OMe, NMe(2), SMe, CN and BDB) were synthesized using established 1,3,2-benzodiazaborole methodologies. The 1,3,2-benzodiazaborolyldiphenylacetylenes with X = p-H (4), p-OMe (5), p-NMe(2) (6), p-SMe (7) and p-CN (8) end groups are functionalized with cyano groups at the central ring in an ortho-position to the triple bond. Molecular structures of 2, 3, 5, 6 and 7 were determined by X-ray diffraction. These borylated systems show intense blue luminescence in cyclohexane, toluene, chloroform, dichloromethane and tetrahydrofuran, whereas green luminescence was observed in acetonitrile solutions. Thereby Stokes shifts in the range 1700-8600 cm(-1) and quantum yields of 0.60-1.00 were observed in cyclohexane solutions. The absorption maxima (308-380 nm) are well reproduced by TD-DFT computations (B3LYP/G-311G(d,p)) and arise from strong HOMO-LUMO transitions. The LUMOs in all the molecules under study are mainly located on the diphenylacetylene bridge, while with the exception of the dimethylamino derivative 6, the HOMO is largely benzodiazaborolyl in character. Thus, the S1←S0 absorption bands are assigned to π(diazaborolyl)-π*(diphenylacetylene) transitions. In contrast to this, in compound 6 the HOMO is mainly represented by the terminal dimethylaminophenyl unit. While calculated ground state dipole moments μ(g) are small (1.1-7.5 D), experimentally determined changes of the dipole moments upon excitation are large (14.8-19.7 D) and reflect a significant charge transfer upon excitation. NLO activities of the rod-structured compounds 2, 4, 6 and 8 are indicated by calculated static first-order hyperpolarizabilities β up to 76.8 × 10(-30) esu. 相似文献
112.
Arnold L Norouzi-Arasi H Wagner M Enkelmann V Müllen K 《Chemical communications (Cambridge, England)》2011,47(3):970-972
In this communication, we report the synthesis of a novel porphyrin-related macrocycle. The core modifications result in aromatic building blocks connected exclusively via aryl-aryl bonds. The concept of synthesis permits the formation of a cavity similar to that of a porphyrin combined with the ability to bind metal ions to provide neutral metal complexes. 相似文献
113.
114.
Papadopoulos P Deng X Mammen L Drotlef DM Battagliarin G Li C Müllen K Landfester K del Campo A Butt HJ Vollmer D 《Langmuir : the ACS journal of surfaces and colloids》2012,28(22):8392-8398
Describing wetting of a liquid on a rough or structured surface is a challenge because of the wide range of involved length scales. Nano- and micrometer-sized textures cause pinning of the contact line, reflected in a hysteresis of the contact angle. To investigate contact angles at different length scales, we imaged water drops on arrays of 5 μm high poly(dimethylsiloxane) micropillars. The drops were imaged by laser scanning confocal microscopy (LSCM), which allowed us to quantitatively analyze the local and large-scale drop profile simultaneously. Deviations of the shape of drops from a sphere decay at two different length scales. Close to the pillars, the amplitude of deviations decays exponentially within 1-2 μm. The drop profile approached a sphere at a length scale 1 order of magnitude larger than the pillars' height. The height and position dependence of the contact angles can be understood from the interplay of pinning of the contact line, the principal curvatures set by the topography of the substrate, and the minimization of the air-water interfaces. 相似文献
115.
116.
117.
García-Ramos JC Toledano-Magaña Y Talavera-Contreras LG Flores-Álamo M Ramírez-Delgado V Morales-León E Ortiz-Frade L Gutiérrez AG Vázquez-Aguirre A Mejía C Carrero JC Laclette JP Moreno-Esparza R Ruiz-Azuara L 《Dalton transactions (Cambridge, England : 2003)》2012,41(34):10164-10174
A new synthetic pathway was reported to obtain N6 donor ligand 2,9-bis-(2',5'-diazahexanyl)-1,10-phenanthroline (L1) and its coordination compounds of essential divalent metal ions Mn, Fe, Co, Ni, Cu and Zn. Complete characterization of all compounds was done with the conventional techniques. Crystal structures of [NiL1](PF(6))(2) and [ZnL1](PF(6))(2)·H(2)O were also reported. Electrochemical studies have shown an active participation of the aromatic moiety of the ligand in redox reactions. The in vitro tests of the cytotoxic activity against human tumour cell lines HeLa (cervix) and CHP-212 (neuroblastoma) showed that all coordination compounds that involve redox active metal ions exhibit noteworthy antiproliferative activity, superior in all cases to cisplatin. [CuL1](2+) showed the lower IC(50) value in the HeLa cell line with 1.84 μM, meanwhile, [CoL1](2+) showed the lower value in neuroblastoma CHP-212 with IC(50) = 45.28 μM. None of these compounds were active against the SK-N-SH neuroblastoma cell line. In Entamoeba histolytica cultures, remarkable nanomolar IC(50) values were found for [NiL1](2+) and [MnL1](2+) with 60 nM and 80 nM respectively, improving the antiproliferative activity more than 1000 times compared with the first choice drug for clinical treatments of human amoebiasis, metronidazole. On the other hand, a free ligand does not show antiproliferative activity either on human tumor cell lines or on Entamoeba histolytica trophozoites, highlighting the role played by metal ions to produce cytotoxicity in tumor cells and protozoa systems. 相似文献
118.
L Weber H Kuhtz L Böhling A Brockhinke A Chrostowska A Dargelos A Mazière HG Stammler B Neumann 《Dalton transactions (Cambridge, England : 2003)》2012,41(34):10440-10452
A series of 1,4-phenylenes X-C(6)H(4)-BDB with a 1,3,2-benzodiazaborolyl (BDB) and a phosphorus based end group [X = PPh(2) (2), P(O)Ph(2) (3), P(S)Ph(2) (4), P(Se)Ph(2) (5), P(AuCl)Ph(2) (6) and P(Me)Ph(2) (7)] as well as 2-(2')thienyl-1,3,2-benzodiazaboroles with a second end group X [X = PPh(2) (8), P(S)Ph(2) (9), P(Se)Ph(2) (10) and P(Me)Ph(2) (11)] in the 5' position were synthesised using established methodologies. Molecular structures of 2-9 and 11 were determined by X-ray diffraction. Compounds 3, 4, 6, 7, 9 and 11 show intense blue luminescence in cyclohexane, toluene, chloroform, dichloromethane and tetrahydrofuran with pronounced solvatochromism. Thereby Stokes shifts in the range of 8950-10?440 cm(-1) and quantum yields up to 0.70 were observed in dichloromethane solutions. In contrast to this, for the selenides 5 and 10 quantum yields are small (<0.1). The absorption maxima (298-340 nm) are well reproduced by TD-DFT computations (B3LYB/G-311G(d,p)) and arise from strong HOMO-LUMO transitions. With the exception of 5 and 10 the HOMOs of the molecules under study are mainly located on the benzodiazaborole group. In 5 and 10 the HOMOs are on the selenium atoms. The LUMOs of all new neutral molecules are mainly represented by the phenylene or thiophene bridge. In the phosphonium cations the LUMOs have additional contributions from the phosphonium unit. 相似文献
119.
120.
MJ Balunas MF Grosso FA Villa N Engene KL McPhail K Tidgewell LM Pineda L Gerwick C Spadafora DE Kyle WH Gerwick 《Organic letters》2012,14(15):3878-3881
Four unsaturated polyketide lactone derivatives, coibacins A-D, were isolated from a Panamanian marine cyanobacterium, cf. Oscillatoria sp. The two different types of termini observed in these co-occurring metabolites, either a methyl cyclopropyl ring as seen in curacin A or a methyl vinyl chloride similar to that observed in the jamaicamides, suggest an intriguing flexibility in the "beta branch" forming biosynthetic process. The coibacins possess selective antileishmanial activity as well as potent anti-inflammatory activity. 相似文献