全文获取类型
收费全文 | 1481篇 |
免费 | 151篇 |
国内免费 | 171篇 |
专业分类
化学 | 1705篇 |
晶体学 | 8篇 |
力学 | 8篇 |
综合类 | 1篇 |
数学 | 38篇 |
物理学 | 43篇 |
出版年
2024年 | 1篇 |
2023年 | 30篇 |
2022年 | 23篇 |
2021年 | 40篇 |
2020年 | 62篇 |
2019年 | 63篇 |
2018年 | 64篇 |
2017年 | 53篇 |
2016年 | 71篇 |
2015年 | 42篇 |
2014年 | 97篇 |
2013年 | 137篇 |
2012年 | 125篇 |
2011年 | 91篇 |
2010年 | 88篇 |
2009年 | 95篇 |
2008年 | 88篇 |
2007年 | 102篇 |
2006年 | 84篇 |
2005年 | 94篇 |
2004年 | 75篇 |
2003年 | 44篇 |
2002年 | 57篇 |
2001年 | 23篇 |
2000年 | 17篇 |
1999年 | 19篇 |
1998年 | 13篇 |
1997年 | 13篇 |
1996年 | 19篇 |
1995年 | 10篇 |
1994年 | 14篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 3篇 |
1990年 | 8篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1803条查询结果,搜索用时 15 毫秒
1.
《Indagationes Mathematicae》2022,33(1):218-237
We define the notion of basic set data for finite groups (building on the notion of basic set, but including an order on the irreducible characters as part of the structure), and we prove that the Springer correspondence provides basic set data for Weyl groups. Then we use this to determine explicitly the modular Springer correspondence for classical types (defined over a base field of odd characteristic , and with coefficients in a field of odd characteristic ): the modular case is obtained as a restriction of the ordinary case to a basic set. In order to do so, we compare the order on bipartitions introduced by Dipper and James with the order induced by the Springer correspondence. We provide a quick proof, by sorting characters according to the dimension of the corresponding Springer fibre, an invariant which is directly computable from symbols. 相似文献
2.
Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)2] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2. 相似文献
3.
《Magnetic resonance in chemistry : MRC》2003,41(8):585-588
A novel, radical responsive MRI contrast agent based on a gadolinium chelate conjugated to a liposome through a disulfide linker was synthesized, with the aim of pursuing the in vivo mapping of radicals. The liposome was prepared by incorporating a thiol‐activated phospholipid, which was subsequently reacted with a gadolinium chelate containing a free thiol group. The long reorientational motion of the supramolecular adduct endows the paramagnetic agent with a relaxivity significantly higher than that of the free complex. The disulfide bond represents a radical‐sensitive moiety and a large decrease in contrast efficacy (T1 relaxivity) is shown upon its cleavage. A preliminary assessment of the system was made by means of in vitro gamma‐irradiation and thiol–disulfide bond exchange with dithiothreitol. Both methods showed a clear dose‐dependent decrease in T1‐relaxivity. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
4.
5.
Georg Süss-Fink Ulf Bodensieck Lisa Hoferkamp Gerd Rheinwald Helen Stoeckli-Evans 《Journal of Cluster Science》1992,3(4):469-478
The reaction of trirutheniumdodecacarbonyl with various thioureas was found to give, depending upon the substituents and the reaction conditions, a large variety of tri-, tetra-, penta-, and hexanuclear ruthenium clusters. The ligand systems observed in the products are derived from the thioureas employed; the fragmentation of the thiourea molecules involve N-H, C-S, C-H, and C-N activation processes. 相似文献
6.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
7.
Three four-step enantiospecific syntheses of different diastereomers of AES, a new biodegradable chelating agent, are described. The stereocenters in each of the isomers are accessible from l- and d-malic and aspartic acids. 相似文献
8.
Michaël Ternon 《Tetrahedron》2004,60(39):8721-8728
FRET based systems are some of the best methods available to detect and monitor proteolytic activity. To enhance fluorescent signals and hence assay sensitivity, two different systems were developed using two different dendrimeric constructs. In the first case, a triple branched dendrimer bearing three dansyl groups was used to enhance assay sensitivity and showed a significant enhancement of fluorescence following enzymatic cleavage. In another example, a tris-fluorescein probe, that undergoes self-quenching, was utilized in a combinatorial library synthesis to map the substrate specificity of proteases. 相似文献
9.
在某些金属盐存在下,醚可与酰氯反应生成酯,早期文献中对于此类反应曾有过报道,其中所用的金属盐有三氯化铁或氯化锌,其相对用量较大,酯的得率较差。其后,Alper等提出用第五族金属羰基化合物和酰氯,如Mo(CO)_4-RCOCl为试剂,进行醚的开裂;近期则有Pri-Bar等用Pd(Ⅱ)-R_3SnX- 相似文献
10.
M. Jonathan Fray Paul Allen Paul R. Bradley Clare E. Challenger Michael Closier Tim J. Evans Mark L. Lewis John P. Mathias Carly L. Nichols Yvonne M. Po-Ba Hayley Snow Mark H. Stefaniak Hannah V. Vuong 《Tetrahedron》2006,62(29):6869-6875
The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction. 相似文献