全文获取类型
收费全文 | 2017篇 |
免费 | 117篇 |
国内免费 | 18篇 |
专业分类
化学 | 1560篇 |
晶体学 | 6篇 |
力学 | 21篇 |
数学 | 348篇 |
物理学 | 217篇 |
出版年
2024年 | 3篇 |
2023年 | 20篇 |
2022年 | 16篇 |
2021年 | 34篇 |
2020年 | 57篇 |
2019年 | 69篇 |
2018年 | 34篇 |
2017年 | 27篇 |
2016年 | 70篇 |
2015年 | 55篇 |
2014年 | 69篇 |
2013年 | 97篇 |
2012年 | 130篇 |
2011年 | 138篇 |
2010年 | 66篇 |
2009年 | 77篇 |
2008年 | 139篇 |
2007年 | 143篇 |
2006年 | 132篇 |
2005年 | 131篇 |
2004年 | 107篇 |
2003年 | 88篇 |
2002年 | 92篇 |
2001年 | 37篇 |
2000年 | 28篇 |
1999年 | 31篇 |
1998年 | 19篇 |
1997年 | 30篇 |
1996年 | 27篇 |
1995年 | 24篇 |
1994年 | 25篇 |
1993年 | 23篇 |
1992年 | 7篇 |
1991年 | 20篇 |
1990年 | 7篇 |
1989年 | 11篇 |
1988年 | 8篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 7篇 |
1982年 | 3篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1974年 | 5篇 |
1973年 | 1篇 |
1951年 | 1篇 |
排序方式: 共有2152条查询结果,搜索用时 0 毫秒
81.
Carsten Bolm Konrad Weickhardt Margareta Zehnder Dorothea Glasmacher 《Helvetica chimica acta》1991,74(4):717-726
The synthesis of the complexes 3 of various metals ligated to chiral 4,5-dihydro-2-(2′-oxidophenyl-?O)oxazoles-?N is described (Scheme). Three of them, i.e. 3a , 3e , and 3f containing CuII, ZnII and NiII, respectively, were analyzed by X-ray diffraction studies. A series of CuII complexes ( 6a – d ) with differently substituted dihydrooxazoles have been synthesized. 相似文献
82.
Wolfgang Zarges Jonathan Hall Jean-Marie Lehn Carsten Bolm 《Helvetica chimica acta》1991,74(8):1843-1852
The chiral tris, and pentakis(bipyridine) ligand strands 3a and 4 were synthesised, each in optically pure form with (S,S)-configuration. Ligand 3a yielded substituted double-helical metal complexes, derived from the parent trihelicate structure 2 , with CuI and AgI ions. The spectral data, in particular the 1H-NMR spectra and the large positive Cotton effect, indicate that helicate formation occurs with very high induction of helicity. Together with consideration of the steric effects in the two possible helical diastereoisomers (P)- 1 and (M)- 1 that may be formed, the data favour the preferential generation of the right-handed double helicate (P)- 1 from the tris(bipyridine) strand 3a of(S,S)-configuration. 相似文献
83.
Dr. Konrad Viehrig Dr. Frank Surup Dr. Carsten Volz Dr. Jennifer Herrmann Dr. Antoine Abou Fayad Sebastian Adam Dr. Jesko Köhnke Prof. Dr. Dirk Trauner Prof. Dr. Rolf Müller 《Angewandte Chemie (International ed. in English)》2017,56(26):7407-7410
Secondary metabolome mining efforts in the myxobacterial multiproducer of natural products, Chondromyces crocatus Cm c5, resulted in the isolation and structure elucidation of crocagins, which are novel polycyclic peptides containing a tetrahydropyrrolo[2,3-b]indole core. The gene cluster was identified through an approach combining genome analysis, targeted gene inactivation in the producer, and in vitro experiments. Based on our findings, we developed a biosynthetic scheme for crocagin biosynthesis. These natural products are formed from the three C-terminal amino acids of a precursor peptide and thus belong to a novel class of ribosomally synthesized and post-translationally modified peptides (RiPPs). We demonstrate that crocagin A binds to the carbon storage regulator protein CsrA, thereby inhibiting the ability of CsrA to bind to its cognate RNA target. 相似文献
84.
85.
Chukwuemeka Okolie Yasmeen F. Belhseine Yimeng Lyu Dr. Matthew M. Yung Dr. Mark H. Engelhard Dr. Libor Kovarik Dr. Eli Stavitski Dr. Carsten Sievers 《Angewandte Chemie (International ed. in English)》2017,56(44):13876-13881
The conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value‐added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria–zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady‐state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox‐active CZ support, which also stabilizes the small NiO clusters. 相似文献
86.
Xiaolin Xing Dr. Rongji Liu Kecheng Cao Prof. Ute Kaiser Prof. Carsten Streb 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11098-11104
The rapid development of renewable-energy technologies such as water splitting, rechargeable metal–air batteries, and fuel cells requires highly efficient electrocatalysts capable of the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER). Herein, we report a facile sonication-driven synthesis to deposit the molecular manganese vanadium oxide precursor [Mn4V4O17(OAc)3]3− on multiwalled carbon nanotubes (MWCNTs). Thermal conversion of this composite at 900 °C gives nanostructured manganese vanadium oxides/carbides, which are stably linked to the MWCNTs. The resulting composites show excellent electrochemical reactivity for ORR and OER, and significant reactivity enhancements compared with the precursors and a Pt/C reference are reported. Notably, even under harsh acidic conditions, long-term OER activity at low overpotential is reported. In addition, we report exceptional activity of the composites for the industrially important Cl2 evolution from an aqueous HCl electrolyte. The new composite material shows how molecular deposition routes leading to highly active and stable multifunctional electrocatalysts can be developed. The facile design could in principle be extended to multiple catalyst classes by tuning of the molecular metal oxide precursor employed. 相似文献
87.
Ion Neda Carsten Melnicky Alexander Vollbrecht Axel Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(6):1047-1059
The reaction of methylisatoic acid anhydride 1 with benzylamines led to the N-benzyl-N′-methylanthranilamide derivatives 2 – 4 . Their reaction with phosphorus trichloride furnished the 2-chloro-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 5 – 7 which, upon reaction with bis-(2-chloroethyl)ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 8 – 10 and 12 . With 2-chloroethylammonium chloride/triethyl-amine the P? NHCH2CH2Cl-substituted compound 11 was obtained from the PIIICl-species 6 . The reaction of 8 – 10 and 12 with hexafluoroacetone (HFA) took an unusual course: apart from the oxidative addition of HFA and formation of the perfluoropinacolyl ring system, one of the two CH2CH2Cl groups was found to alkylate the CH3N atom with formation of a five-membered (diazaphospholane) ring in the tricyclic phosphoranes 13 – 16 . The reaction of 11 with HFA also produced a spirophosphorane 17 which involved a λ5-oxazaphosphetidine ring system. In the reaction of 8, 10 and 12 with tetrachloro-o-benzoquinone, an oxidative addition reaction with concomitant N-alkylation and formation of the tricyclic phosphoranes 18 – 20 was found to take place. Single crystal X-ray structure determinations are described for the phosphoranes 13, 14 and 16 , and for the precursor compound 9 . The following features are common to the isostructural compounds 13 and 16 and the diethyl ether hemisolvate of 14 : the (λ5)-spiro phosphorus atom lies out of the plane of the other atoms of the rings to which it is common, and the dioxaphospholane rings display a twist conformation. In the λ3P-compound 9 the phosphorus atom also lies out of the plane of the other ring atoms. 相似文献
88.
89.
90.
Hao Yu Dr. Zhen Li Prof. Dr. Carsten Bolm 《Angewandte Chemie (International ed. in English)》2018,57(1):324-327
Free NH‐sulfoximines were directly prepared from sulfoxides through iron catalysis by applying a readily available, shelf‐stable hydroxylamine triflic acid salt. No additional oxidant is needed, and the substrate scope is broad, including a range of heterocyclic compounds. 相似文献