全文获取类型
收费全文 | 246篇 |
免费 | 24篇 |
专业分类
化学 | 181篇 |
力学 | 8篇 |
数学 | 27篇 |
物理学 | 54篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 4篇 |
2021年 | 9篇 |
2020年 | 6篇 |
2019年 | 13篇 |
2018年 | 3篇 |
2017年 | 6篇 |
2016年 | 18篇 |
2015年 | 13篇 |
2014年 | 19篇 |
2013年 | 12篇 |
2012年 | 24篇 |
2011年 | 20篇 |
2010年 | 17篇 |
2009年 | 9篇 |
2008年 | 15篇 |
2007年 | 16篇 |
2006年 | 5篇 |
2005年 | 7篇 |
2004年 | 9篇 |
2003年 | 1篇 |
2002年 | 1篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1991年 | 4篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1971年 | 3篇 |
1969年 | 1篇 |
1967年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有270条查询结果,搜索用时 187 毫秒
1.
B. Bastian T. P. Knepper P. Hoffmann H. M. Ortner 《Fresenius' Journal of Analytical Chemistry》1994,348(10):674-679
A method for the identification and quantification of aromatic sulfonic acids in industrial waste water has been developed. The preparation of the samples comprises a clean-up step and an enrichment step, utilizing i) reversed-phase extraction and ii) ion-pair solid phase extraction. The aromatic sulfonic acids are separated by ion-pair chromatography with diode-array detection. An advantage of the developed ion-pair chromatographic method is the separation of linear alkylbenzenesulfonic acids (LAS), lignosulfonic acids and aromatic sulfonic acids in one chromatographic run. Also described is an optimized clean-up procedure for collected fractions of a preparative chromatographic run to identify monosulfonic acids with GC/MS after methylation. The detection limits for aromatic sulfonic acids in industrial waste waters are at the g/l level. 相似文献
2.
Meier H Gerold J Kolshorn H Mühling B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):360-370
Four OPV series 1-4 (a-d) with a terminal dialkylamino group as electron donor were prepared by Wittig-Horner reactions. To study the influence of the push-pull effect on the long-wavelength absorption, three of the four series contained terminal acceptor groups (CN, CHO, NO(2)). The length of the chromophores strongly affects the intramolecular charge transfer (ICT)-an effect which superimposes upon the extension of the conjugation. Increasing numbers n of repeat units cause an overall bathochromic shift for the purely donor-substituted series 1 a-4 a and the series 1 b-4 b with CN as weak acceptor. The two effects annihilate each other in the series 1 c-4 c with terminal CHO groups, so that the absorption maxima are almost independent of the length of the chromophore. A hypsochromic shift is observed for the series 1 d-4 d, which contains the strong acceptor group NO(2). This anomaly disappears on protonation of the dialkylamino group because the push-pull effect disappears in the ammonium salts. The results can be explained by semiempirical quantum mechanics (AM1, INDO/S). The HOMO-LUMO transition, which is mainly responsible for the ICT, becomes less important in the electron transitions S(0)-->S(1) when the distance between donor and acceptor is increased. The commonly used VB model, which contains an electroneutral and a zwitterionic resonance structure, is contrasted with a MO model with dipole segments at both ends of the OPV chains. The latter model turned out to be more appropriate-at least for donor-acceptor-substituted OPVs with n >/= 2. 相似文献
3.
The crystal structure of [C10N2H10]2[P2Mo5O21(OH)2] · 2H2O, contains the heteropolyanion, [P2Mo5O21(OH)2]4—, together with diprotonated 4, 4′‐bipyridine. The heteropolyanion is built up from five MoO6 octahedra sharing four common edges and one common corner, capped by two PO3(OH) tetrahedra. The structure is stabilized by hydrogen bonds involving the hydrogen atoms of the 4, 4′‐bipyridine, water molecules and the oxygen atoms of the pentamolybdatobisphosphate. This is the first example that this kind of cluster could be isolated in the presence of a poly‐functional aromatic molecule ion. Crystal data: triclinic, P1¯ (No. 2), a = 9.983(2)Å, b = 11.269(2)Å, c = 17.604(4)Å, α = 73.50(3)°, β = 84.07(3)°, γ = 67.96(3)°; V = 1760.0(6)Å3; Z = 2; R1 = 0.037 and wR2 = 0.081, for 9138 reflections [I > 2σ(I)]. 相似文献
4.
Hydrothermal investigations in the system MgO/B2O3/P2O5(/H2O) yielded two new magnesium borophosphates, Mg2(H2O)[BP3O9(OH)4] and Mg(H2O)2[B2P2O8(OH)2]·H2O. The crystal structures were solved by means of single crystal X‐ray diffraction. While the acentric crystal structure of Mg2(H2O)[BP3O9(OH)4] (orthorhombic, P212121 (No. 19), a = 709.44(5) pm, b = 859.70(4) pm, c = 1635.1(1) pm, V = 997.3(3) × 106 pm3, Z = 4) contains 1D infinite chains of magnesium coordination octahedra interconnected by a borophosphate tetramer, Mg(H2O)2[B2P2O8(OH)2]·H2O (monoclinic, P21/c (No. 14), a = 776.04(5) pm, b = 1464.26(9) pm, c = 824.10(4) pm, β = 90.25(1)°, V = 936.44(9) × 106 pm3,Z = 4) represents the first layered borophosphate with 63 net topology. The structures are discussed and classified in terms of structural systematics. 相似文献
5.
Bastian Bernhardt Markus Schauermann Ephrath Solel Andr K. Eckhardt Peter R. Schreiner 《Chemical science》2022,14(1):130
The search for methods to bind CO2 and use it synthetically as a C1-building block under mild conditions is an ongoing endeavor of great urgency. The formation of heterocyclic carbene–carbon dioxide adducts occurs rapidly when the carbene is generated in solution in the presence of CO2. Here we demonstrate the reversible formation of a complex of the hitherto unreported aminomercaptocarbene (H2N––SH) with CO2 isolated in solid argon by photolysis of 2-amino-2-thioxoacetic acid. Remarkably, the complex disappears in the dark as deduced by time-dependent matrix infrared measurements, and equilibrates back to the covalently bound starting material. This kinetically excluded process below ca. 8 K is made possible through heavy-atom quantum mechanical tunneling, as also evident from density functional theory and ab initio computations at the CCSD(T)/cc-pVTZ level of theory. Our results provide insight into CO2 activation using a carbene and emphasize the role of quantum mechanical tunneling in organic processes, even involving heavy atoms.A novel heterosubstituted carbene spontaneously binds CO2 in a tunneling reaction under cryogenic conditions. 相似文献
6.
7.
8.
9.
10.