全文获取类型
收费全文 | 9743篇 |
免费 | 552篇 |
国内免费 | 42篇 |
专业分类
化学 | 7268篇 |
晶体学 | 32篇 |
力学 | 160篇 |
数学 | 1504篇 |
物理学 | 1373篇 |
出版年
2023年 | 75篇 |
2022年 | 94篇 |
2021年 | 154篇 |
2020年 | 229篇 |
2019年 | 199篇 |
2018年 | 146篇 |
2017年 | 120篇 |
2016年 | 415篇 |
2015年 | 378篇 |
2014年 | 401篇 |
2013年 | 476篇 |
2012年 | 661篇 |
2011年 | 704篇 |
2010年 | 504篇 |
2009年 | 410篇 |
2008年 | 652篇 |
2007年 | 577篇 |
2006年 | 542篇 |
2005年 | 554篇 |
2004年 | 474篇 |
2003年 | 338篇 |
2002年 | 314篇 |
2001年 | 156篇 |
2000年 | 129篇 |
1999年 | 150篇 |
1998年 | 115篇 |
1997年 | 158篇 |
1996年 | 109篇 |
1995年 | 109篇 |
1994年 | 106篇 |
1993年 | 92篇 |
1992年 | 89篇 |
1991年 | 58篇 |
1990年 | 42篇 |
1989年 | 68篇 |
1988年 | 54篇 |
1987年 | 31篇 |
1986年 | 31篇 |
1985年 | 45篇 |
1984年 | 36篇 |
1983年 | 22篇 |
1982年 | 45篇 |
1981年 | 30篇 |
1980年 | 25篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1977年 | 18篇 |
1975年 | 22篇 |
1973年 | 16篇 |
1968年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
181.
Kammerer D Carle R Schieber A 《Rapid communications in mass spectrometry : RCM》2003,17(21):2407-2412
Anthocyanins of black carrots (Daucus carota ssp. sativus var. atrorubens Alef.) were investigated by high-performance liquid chromatography/electrospray ionization mass spectrometry. Besides the main compounds which have already been characterized in detail as cyanidin glycosides, six anthocyanins with m/z 757, 565, 595, 903, 933 and 903 were detected and unambiguously characterized as peonidin and pelargonidin glycosides, based on their fragmentation patterns. Peonidin and pelargonidin were identified after acid hydrolysis by comparison of the fragmentation patterns and retention times of the released aglycones with those of standard compounds. To the best of our knowledge this is the first report on anthocyanins in black carrots consisting of aglycones other than cyanidin. 相似文献
182.
183.
184.
Stasch A Ferbinteanu M Prust J Zheng W Cimpoesu F Roesky HW Magull J Schmidt HG Noltemeyer M 《Journal of the American Chemical Society》2002,124(19):5441-5448
The reaction of the acetylene RC triple bond CH (R = Ph, CH(2)SiMe(3)) with an excess of AlH(3).NMe(3) in boiling toluene leads to the carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph 1, CH(2)SiMe(3) 2) in good yield. Treatment of 2 with BCl(3) under varying conditions gives the chlorinated products [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] 3 and [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(2)Cl)(6)] 4, respectively. The latter clearly demonstrates that the cluster can be stepwise functionalized within the inner and outer sphere. The X-ray single-crystal structures of 1, 2, and 4 have been determined. All compounds have in common that the central core consists of a cluster having eight aluminum and six carbon atoms. The bonding properties in this cluster are described as a new manifestation of three-dimensional surface aromaticity. Each Al(4)C fragment of the cube is formed by four bonds with three electron pairs, thus leading to a strong delocalization of the electrons. A phenomenological modeling using a three-dimensional Hückel scheme with fitted parameters to reproduce the energies from ab initio calculations revealed that the orbital scheme localized at one Al(4)C fragment possesses an orbital sextet with a large HOMO-LUMO gap. This is in line with the criteria of aromaticity. The idea of aromaticity was sustained also by qualitative valence bond reasons enumerating the different resonance structures by means of graph theoretical methods. 相似文献
185.
Jens Hartig Andreas Schnepf L. Jos de Jongh David Bono Hansgeorg Schnöckel Prof. Dr. 《无机化学与普通化学杂志》2007,633(1):63-76
Towards the Understanding of the Unexpected Properties of the Metalloid Cluster Compound [Ga84(N(SiMe3)2)20][Li6Br2(THF)20]·2Toluol In several short communications we have recently reported on the electrical and superconducting properties of the crystalline title compound 1 which contains anionic Ga84R20‐moieties. Here we present a collection of these results, complemented and interpreted by using DFT‐calculations on model clusters (Ga84(NH2)20?). These calculations allow a) a first insight into the dynamics of the Ga84‐moieties (e.g. a rotation of the central Ga2‐dumbbell) and thus an explanation of the temperature‐dependent Ga‐NMR‐spectra described recently, and b) estimations on the lattice energy of 1 and its resulting unexpected energetic stabilization compared to metallic gallium. A possible contribution of the cations in the electrical conduction mechanism of 1 can also be made feasible with model calculations. The basis for all the results presented is to be found in the “perfect” arrangement of nanoscopic Ga84‐clusters in the crystal. This theoretically predicted condition for superconductivity in a “chain” of identical metal cluster molecules is a requirement which can hardly be realized by means of physical fabrication methods. Therefore, on the one hand the results presented here make for some disillusionment in the field of nanoscience, but on the other hand, especially in the field of synthetic chemistry, they present rewarding challenges for fundamental work in the future. 相似文献
186.
Zhu L Ostash B Rix U Nur-E-Alam M Mayers A Luzhetskyy A Mendez C Salas JA Bechthold A Fedorenko V Rohr J 《The Journal of organic chemistry》2005,70(2):631-638
The angucycline antibiotic family of the landomycins displays potent antitumor activity. To elucidate early post polyketide synthase (PKS) tailoring steps of the landomycin E biosynthetic pathway in Streptomyces globisporus 1912, the mutant S. globisporus M12 was prepared through gene replacement experiment of lndM2. It encodes an enzyme with putative oxygenase and reductase domains, according to sequencing of the gene and its counterpart lanM2 from S. cyanogenus S136 landomycin A biosynthetic gene cluster. The isolation of the novel shunt products 11-hydroxytetrangomycin and 4-hydroxytetrangomycin along with the well-known angucyclines tetrangomycin and tetrangulol from the culture of S. globisporus M12 provides evidence for the involvement of lndM2 in the early biosynthetic pathway of the landomycins, in particular in the formation of the alicyclic 6-hydroxy function of the landomycin aglycon. We therefore propose LndM2 to be responsible for both hydroxylation of the 6-position and its subsequent reduction. These reactions are necessary before the glycosylation reactions can occur. The results are in agreement with the originally published structure of landomycin but do not support the recently suggested revised structure. 相似文献
187.
An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties. 相似文献
188.
Wang W Buchholz A Ivanova II Weitkamp J Hunger M 《Chemical communications (Cambridge, England)》2003,(20):2600-2601
A general method for the synthesis of quaternary ammonium cations in acidic zeolites by a direct reaction of tertiary amines and alcohols is described. 相似文献
189.
As supported PtxNi1–x catalysts are used for hydrogenation reactions, it seemed necessary to assess the surface composition of the reduced samples. To approach the usual reduction conditions we applied in situ reduction in a reaction chamber (1 mbar H2 up to 500 °C) placed in ultra high vacuum recipient (UHV: 10–9 to 2.10–10mbar). All ion scattering spectroscopy measurements were performed in UHV. Charging of the samples was avoided by electron bombardment (5 eV). The variation of the surface composition was determined after subsequent sputtering, thermal treatment at 500 °C and during oxygen adsorption. A comparison with previous results of surface compositions of binary alloys (polycrystalline foils [1, 2] and single crystals PtxNi1–x [3]) is given.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
190.
Andreas Stockhammer Klaus-Hermann Dahmen Tobias Gerfin Luigi M. Venanzi Volker Gramlich Walter Fetter 《Helvetica chimica acta》1991,74(5):989-992
The cluster compounds [Pt3(μ-CO)3(PR3)3] act as Lewis bases towards the metal halides of Group XI, MX, Group XII, MX2, and Group XIII, MX3, to form cluster compounds of the composition [{MXn}{Pt3(μ-CO)3(PR3)3}]. The X-ray crystal structure, NMR and IR data are given for the compound [{ZnI}{Pt3(μ-CO)3(PPh(i-Pr)2)3}]. 相似文献