全文获取类型
收费全文 | 3297篇 |
免费 | 78篇 |
国内免费 | 22篇 |
专业分类
化学 | 2061篇 |
晶体学 | 11篇 |
力学 | 145篇 |
数学 | 495篇 |
物理学 | 685篇 |
出版年
2024年 | 4篇 |
2023年 | 35篇 |
2022年 | 78篇 |
2021年 | 114篇 |
2020年 | 100篇 |
2019年 | 80篇 |
2018年 | 58篇 |
2017年 | 45篇 |
2016年 | 129篇 |
2015年 | 91篇 |
2014年 | 134篇 |
2013年 | 168篇 |
2012年 | 222篇 |
2011年 | 252篇 |
2010年 | 142篇 |
2009年 | 123篇 |
2008年 | 199篇 |
2007年 | 193篇 |
2006年 | 207篇 |
2005年 | 191篇 |
2004年 | 146篇 |
2003年 | 127篇 |
2002年 | 126篇 |
2001年 | 49篇 |
2000年 | 23篇 |
1999年 | 29篇 |
1998年 | 32篇 |
1997年 | 38篇 |
1996年 | 36篇 |
1995年 | 21篇 |
1994年 | 22篇 |
1993年 | 17篇 |
1992年 | 7篇 |
1991年 | 15篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 9篇 |
排序方式: 共有3397条查询结果,搜索用时 15 毫秒
121.
Bellussi G Millini R Montanari E Carati A Rizzo C Parker WO Cruciani G de Angelis A Bonoldi L Zanardi S 《Chemical communications (Cambridge, England)》2012,48(59):7356-7358
ECS-14, a crystalline microporous hybrid organic-inorganic aluminosilicate, has been synthesized by using 1,4-bis-(triethoxysilyl)-benzene (BTEB) as a source of silica. Its structure contains a system of linear channels with 12-membered ring openings, running along the [001] direction, resembling the pore architecture of the AFI framework type. 相似文献
122.
N-(β-Hydroxy)amides can be cyclised by reaction with diisopropylcarbodiimide (DIC) to give the corresponding 2-oxazolines in high yields. The reaction requires only very mild Lewis-acid catalysis (5 mol % Cu(OTf)2) and can be accomplished with simple heating, or in very short reaction times under microwave irradiation. 相似文献
123.
The salts [S(NMe2)3][MF6] (M = Nb, 2a; M = Ta, 2b) and [S(NMe2)3][M2F11] (M = Nb, 2c; M = Ta, 2d) have been prepared by reacting MF5 (M = Nb, 1a; M = Ta, 1b) with [S(NMe2)3][SiMe3F2] (TASF reagent) in the appropriate molar ratio. The solid state structure of 2b has been ascertained by X-ray diffraction. The 1:1 molar ratio reactions of 1a with a variety of organic compounds (L) give the neutral adducts NbF5L [L = Me2CO, 3a; L = MeCHO, 3b; L = Ph2CO, 3c; L = tetrahydrofuran (thf), 3d; L = MeOH, 3e; L = EtOH, 3f; L = HOCH2CH2OMe, 3g; L = Ph3PO, 3h; L = NCMe, 3i] in good yields. The complexes MF5L [M = Nb, L = HCONMe2, 3j; M = Nb, L = (NMe2)2CO, 3k; M = Ta, L = (NMe2)2CO, 3l; M = Nb, L = OC(Me)CHCMe2, 3m] have been detected in solution in admixture with other unidentified products, upon 2:1 molar reaction of 1 with the appropriate reagent L. The ionic complexes [NbF4(tht)2][NbF6], 4a, and [NbF4(tht)2][Nb2F11], 4b, have been obtained by combination of tetrahydrothiophene (tht) and 1a, in 1:1 and 2:3 molar ratios, respectively. The treatment of 1 with a two-fold excess of L leads to the species [MF4L4][MF6] [M = Nb, L = HCONMe2, 5a; M = Ta, L = HCONMe2, 5b; M = Nb, L = thf, 5c; M = Ta, L = thf, 5d; M = Nb, L = OEt2, 5e]. The new complexes have been fully characterised by NMR spectroscopy. Moreover, the revised 19F NMR features of the known compounds MF5L [M = Ta, L = Me2CO, 3n; M = Ta, L = Ph2CO, 3o; M = Ta, L = MePhCO, 3p; M = Ta, L = thf, 3q; M = Nb, L = CH3CO2H, 3r; M = Nb, L = CH2ClCO2H, 3s; M = Ta, L = CH2ClCO2H, 3t], TaF4(acac), TaF4(Me-acac) and [TaF(Me-acac)3][TaF6] (Me-acac = methylacetylacetonato anion) are reported. 相似文献
124.
Egle M. Beccalli Prof. Elena Borsini Stefano Brenna Dr. Simona Galli Dr. Micol Rigamonti Gianluigi Broggini Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1670-1678
The isolation of σ‐alkylpalladium Heck intermediates, possible when β‐hydride elimination is inhibited, is a rather rare event. Performing intramolecular Heck reactions on N‐allyl‐2‐halobenzylamines in the presence of [Pd(PPh3)4], we isolated and characterized a series of stable bridged palladacycles containing an iodine or bromine atom on the palladium atom. Indolyl substrates were also tested for isolation of the corresponding complexes. X‐ray crystallographic analysis of one of the indolyl derivatives revealed the presence of a five‐membered palladacycle with the metal center bearing a PPh3 ligand and an iodine atom in a cis position with respect to the nitrogen atom. The stability of the σ‐alkylpalladium complexes is probably a consequence of the strong constraint resulting from the bridged junction that hampers the cisoid conformation essential for β‐hydride elimination. Subsequently, the thus obtained bridged five‐membered palladacycles were proven to be effective precatalysts in Heck reactions as well as in cross‐coupling processes such as Suzuki and Stille reactions. 相似文献
125.
Martin Hoefling Francesco Iori Dr. Stefano Corni Dr. Kay‐Eberhard Gottschalk Dr. 《Chemphyschem》2010,11(8):1763-1767
The interactions of amino acids with inorganic surfaces are of interest for biologists and biotechnologists alike. However, the structural determinants of peptide–surface interactions have remained elusive, but are important for a structural understanding of the interactions of biomolecules with gold surfaces. Molecular dynamics simulations are a tool to analyze structures of amino acids on surfaces. However, such an approach is challenging due to lacking parameterization for many surfaces and the polarizability of metal surfaces. Herein, we report DFT calculations of amino acid fragments in vacuo and molecular dynamics simulations of the interaction of all amino acids with a gold(111) surface in explicit solvent, using the recently introduced polarizable gold force field GolP. We describe preferred orientations of the amino acids on the metal surface. We find that all amino acids preferably interact with the gold surface at least partially with their backbone, underlining an unfolding propensity of gold surfaces. 相似文献
126.
Vincenzo Sibillo Stefano Guido Francesco Greco Pier Luca Maffettone 《Macromolecular Symposia》2005,228(1):31-40
In this article, we discuss the dynamics of a single drop immersed in an immiscible liquid, under an imposed shear flow. The two situations of a viscoelastic matrix with a Newtonian drop and of a viscoelastic drop in a Newtonian matrix are considered, both systems being characterized by a viscosity ratio equal to one, and by the same elasticity parameter. Experimental data are taken with a rheo-optical computer-assisted shearing device, allowing for drop observation from the vorticity direction of the shear flow. Data favourably compare with predictions of the recently proposed Maffettone-Greco model, where the drop is described as a deforming ellipsoid. 相似文献
127.
Size‐Controlled Formation of Noble‐Metal Nanoparticles in Aqueous Solution with a Thiol‐Free Tripeptide 下载免费PDF全文
Stefano Corra Dr. Urszula Lewandowska Dr. Edmondo M. Benetti Prof. Dr. Helma Wennemers 《Angewandte Chemie (International ed. in English)》2016,55(30):8542-8545
A combinatorial screening revealed the peptide H‐His‐d ‐Leu‐d ‐Asp‐NH2 ( 1 ) as an additive for the generation of monodisperse, water‐soluble palladium nanoparticles with average diameters of 3 nm and stabilities of over 9 months. The tripeptide proved to be also applicable for the size‐controlled formation of other noble‐metal nanoparticles (Pt and Au). Studies with close analogues of peptide 1 revealed a specific role of each of the three amino acids for the formation and stabilization of the nanoparticles. These data combined with microscopic and spectroscopic analyses provided insight into the structure of the self‐assembled peptidic monolayer around the metal core. The results open interesting prospects for the development of functionalized metal nanoparticles. 相似文献
128.
Dr. Eva‐Maria Rummel Prof. Dr. Piero Mastrorilli Dr. Stefano Todisco Prof. Mario Latronico Dr. Gábor Balázs Dr. Alexander V. Virovets Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(42):13301-13305
By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}3], [Al{OC(CF3)3}4]), two phosphaalkynes could be coordinated side‐on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] ( 1 ) and [Ag(η2‐P≡CtBu)2][Al{OC(CF3)3}4] ( 2 ). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square‐planar coordination mode of the phosphaalkynes at Ag+ was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH3)2CO)Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] ( 3 ) and [(C7H8)2Ag(η2‐P≡CtBu)][FAl{OC12F15}3] ( 4 ). All of the compounds were comprehensively characterized in solution and in the solid state. 相似文献
129.
Krystyna Kurdziel Andrzej Okruszek Tadeusz G?owiak Stefano Materazzi 《Journal of organometallic chemistry》2006,691(5):869-878
Two coordination compounds of palladium(II) with N-allylimidazole (l) of the general formula [PdL4]Cl2 · 3H2O (1) and trans-[PdL2Cl2] (2) have been synthesized. The crystal and molecular structure of complexes 1 and 2 was established by single-crystal X-ray diffraction analysis. The X-ray structural data were supplemented by solid-state 13C NMR measurements (CP MAS and PASS 2D). The 1D and 2D NMR studies in solution reveal that complex 1 is unstable at room temperature and undergoes reversible decomposition to 2. The method for how to preserve a complex with four allyl-imidazole ligands in solution is shown. 相似文献
130.
Zhou Q Henderson WA Appetecchi GB Montanino M Passerini S 《The journal of physical chemistry. B》2008,112(43):13577-13580
Two ionic liquids based upon N-alkyl-N-methylpyrrolidinium cations (PY(1R)(+)) (R=3 for propyl or 4 for butyl) and the bis(fluorosulfonyl)imide (FSI(-)), N(SO2F)2(-), anion have been extensively characterized. The ionic conductivity and viscosity of these materials are found to be among the highest and lowest, respectively, reported for aprotic ionic liquids. Both ionic liquids crystallize readily on cooling and undergo several solid-solid phase transitions on heating prior to melting. PY13FSI and PY14FSI are found to melt at -9 and -18 degrees C, respectively. The thermal stability of PY13FSI and PY14FSI is notably lower than for the analogous salts with the bis(trifluoromethanesulfonyl)imide (TFSI(-)), N(SO2CF3)2(-), anion. Both ionic liquids have a relatively wide electrochemical stability window of approximately 5 V. 相似文献