全文获取类型
收费全文 | 4061篇 |
免费 | 118篇 |
国内免费 | 19篇 |
专业分类
化学 | 2641篇 |
晶体学 | 19篇 |
力学 | 126篇 |
数学 | 733篇 |
物理学 | 679篇 |
出版年
2023年 | 30篇 |
2022年 | 66篇 |
2021年 | 80篇 |
2020年 | 78篇 |
2019年 | 82篇 |
2018年 | 68篇 |
2017年 | 47篇 |
2016年 | 107篇 |
2015年 | 97篇 |
2014年 | 107篇 |
2013年 | 167篇 |
2012年 | 209篇 |
2011年 | 302篇 |
2010年 | 170篇 |
2009年 | 171篇 |
2008年 | 219篇 |
2007年 | 217篇 |
2006年 | 214篇 |
2005年 | 165篇 |
2004年 | 146篇 |
2003年 | 125篇 |
2002年 | 132篇 |
2001年 | 51篇 |
2000年 | 42篇 |
1999年 | 39篇 |
1998年 | 27篇 |
1997年 | 38篇 |
1996年 | 62篇 |
1995年 | 35篇 |
1994年 | 47篇 |
1993年 | 35篇 |
1992年 | 34篇 |
1991年 | 29篇 |
1990年 | 29篇 |
1989年 | 22篇 |
1988年 | 28篇 |
1987年 | 21篇 |
1986年 | 27篇 |
1985年 | 52篇 |
1984年 | 54篇 |
1983年 | 40篇 |
1982年 | 33篇 |
1981年 | 39篇 |
1980年 | 44篇 |
1979年 | 49篇 |
1978年 | 23篇 |
1977年 | 17篇 |
1976年 | 20篇 |
1974年 | 19篇 |
1970年 | 15篇 |
排序方式: 共有4198条查询结果,搜索用时 15 毫秒
101.
Eva Schneiderman Bruno Perly Elwood Brooks Apryll M. Stalcup 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(1-2):43-50
The characterization of binary and ternary complexes of benzoate, lauryl hexaoxyethylene (C12E6) and -CD is presented. The complexation equilibrium was characterized by UV-Vis spectrophotometry, titration microcalorimetry, capillary electrophoresis, and 2D ROESY 1H-NMR. Results suggested that -CD forms one complex with C12E6in the stoichiometric ratio of -CD : C12E61.5 : 1, with a stability constant 1.3 × 105 M-1.5. The 2-D ROESY 1H-NMR spectrum indicated that C12E6is included inside the -CD cavity. The primary binding site of C12E6 is on the lauryl subunit of this molecule. Analogous to a previously reported study of -CD, the combination of -CD and C12E6precipitated from the solution. Addition of benzoate seemed to dissolve the precipitate and nearly doubled the apparent stability constant of the complex. Results from the various techniques supported formation of ternary complexes between -CD, C12E6, and benzoate. 相似文献
102.
Balandina A Kalinin A Mamedov V Figadère B Latypov S 《Magnetic resonance in chemistry : MRC》2005,43(10):816-828
(1)H, (13)C and (15)N NMR chemical shifts for a variety of novel quinoxalines were determined by different 2D methods and were calculated using the GIAO DFT approach. Comparison with experimental data shows good correlations in the case of (1)H, (13)C and (15)N chemical shifts. Different combinations of basis sets were tested. In non-polar solvents quinoxalines exist as dimers owing to strong hydrogen bonding. Calculations for dimers improve the correlation between experiment and theory. Additive empirical methods for estimating chemical shifts have drawbacks and have to be used with a great care for this type of compound. 相似文献
103.
Photochemistry of ε,ζ-Methano-α,γ-dienones and 7,8-Methano-1,3,5-trienes Irradiation of the δ-cyclopropyl-dienone (E)- 6 (λ ≥ 347 nm) gives (Z)- 6, 10 (1,5-sigmatropic H-shift), (E/Z)- 9 (electrocyclic process involving C(ε), C(ζ)-cleavage) and 11 (ring opening). The corresponding 6-cyclopropyl-triene (E)- 7 gives on singlet excitation (δ > 280 nm) 14 (1,5-sigmatropic H-shift) and, to a smaller extent, the bicyclo [3.2.0] heptenyl-dienes (E/Z)- 13 . However, on triplet excitation (λ ≥ 347 nm, benzophenone) (E)- 7 gives (E/Z)- 13 as the main products. On both 1π,π*- and 3π,π*-excitation, (Z)- 7 and 15 are formed in small amounts. 相似文献
104.
Vincenza Bruno Anna Castaldo Roberto Centore Augusto Sirigu Felice Sarcinelli Mauro Casalboni Roberto Pizzoferrato 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1468-1475
The synthesis of the new chromophores 2‐{4‐[4‐(N,N‐dihydroxyethylamino)‐phenylazo]‐phenyl}‐6‐nitrobenzoxazole ( 1 ) and 4‐[4‐(N,N‐dihydroxyethylamino)phenylazo]‐benzoic acid ( 2 ) is described. Three homopolymers obtained by the polycondensation of 1 with propyloxy‐terephthalic acid and 1 and 2 with 2,4‐tolylenediisocianate as well as two copolymers obtained by polycondensation of appropriate mixtures of chromophores 1 and 2 with 2,4‐tolylene‐diisocianate were prepared and characterized. All as‐prepared polymers but one (homopolyurethane of 1 ) were amorphous and exhibited good optical clarity, good thermal stability above the glass transition, and solubility in organic solvents. The second‐order nonlinear optical behavior of the amorphous polymers was investigated on spin‐coated corona‐poled films through second harmonic generation (SHG) experiments at 1064 nm. At this wavelength, resonance‐enhanced values of the SHG coefficient d33 were found in the range between 6 and 34 pm/V where higher values were observed for polymers with a higher molar content of 1 . © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1468–1475, 2002 相似文献
105.
Bruno Therrien Ludovic Vieille-Petit Petr Štěpni?ka Georg Süss-Fink 《Journal of organometallic chemistry》2004,689(15):2456-2463
A series of arene-ruthenium complexes of the general formula [RuCl2{η6-C6H5(CH2)2R}L] with R=OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc=ferrocenyl) and L=PPh3, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 · nH2O to afford [RuCl2{η6-C6H5(CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{η6-C6H5(CH2)3OH}L] to give [RuCl2{η6-C6H5(CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{η6-C6H5(CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{η6-C6H5(CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system. 相似文献
106.
Castagnola M Rossetti DV Inzitari R Vitali A Lupi A Zuppi C Cabras T Fadda MB Petruzzelli R Giardina B Messana I 《Electrophoresis》2003,24(5):801-807
Measurements by capillary electrophoresis (CE) of bacitracin A(1) effective mobility at different pH values permitted to estimate the five acidic dissociation constants and the Stokes radii at different protonation stages of the macrocyclic dodecapeptide. The pK(a) values were 3.6 and 4.4 for the two carboxylic groups of the lateral chains of D-Asp-11 and D-Glu-4, respectively, 6.4 for the aza-atom of the imidazole ring of His-10, 7.6 for the amino group of N-terminal Ile-1 and 9.7 for the delta-amino group of D-Orn-7, very close to the values obtained by other researchers by titration experiments. In agreement with a rigid macrocyclic structure the Stokes radii of different protonated forms ranged only between 14.3 and 14.8 A. Best fitting procedures performed on experimental mobility measured at two different pH values (5.50 and 6.72) in the presence of increasing Zn(+2) concentration allowed confirming the model that assumes the binding of Zn(+2) to P(0) peptide form with a 1.5 x 10(3) M(-1) intrinsic association constant. Following to Zn(+2) binding, the pK(a) of the amino group of N-terminal Ile-1 is shifted from 7.6 to 5.9 and the Stokes radius is reduced of about 3 A. The mean charge of the bacitracin A(1)-Zn(+2) complex resulted +1.67 and +1.12 at pH 5.50 and 6.72, respectively. These results suggest that the amino group of N-terminal Ile-1 is not essential for Zn(+2) binding. 相似文献
107.
A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH3OH]+ and [M + H]+ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]+) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H]– ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach. 相似文献
108.
On singlet excitation (λ = 254 nm, THF, pentane or hexane), the diastereoisomeric methano-epoxydienes (E)- 6 and (E)- 7 undergo interconversion and yield the products 8 – 11 . The main process is the cleavage of the oxirane ring to the vinyl carbene intermediate e which undergoes addition to the adjacent double bond furnishing the cyclopropene 8 . The alternative carbene intermediate f is evidenced by the formation of the cyclobutene 10 . For the fragmentation leading to 11 , the carbene f as well as the dipolar species h are considered as possible intermediates. On triplet sensitization (acetone, λ > 280 nm), (E)- 7 shows behavior typical of epoxydienes, undergoing fission of the C? O bond of the oxirane ring and isomerization to the compounds 13 , 14 and (E/Z)- 15 . 相似文献
109.
Employing tin and lead solution calorimetry, the formation enthalpies of those phases having platinum and palladium as major component have been determined in the PdGa, PdIn, PdTl, PtGa und PtIn systems. These enthalpies are highly exothermic and suggest strong atomic interaction betweens palladium and platinum on the one hand and the third subgroup elements on the other. The experimental values have been compared with those obtained from the Miedema model. The thermodynamic data are discussed and related to the crystal structures found with these alloys. 相似文献
110.
P. Bruno M. Caselli M. L. Curri P. Favia R. Lamendola A. Mangone A. Traini C. Laganara 《Fresenius' Journal of Analytical Chemistry》1994,350(3):168-177
Medieval ceramic sherds have been studied by inductively coupled plasma (ICP) emission spectroscopy and X-ray photoelectron spectroscopy (XPS) in order to acquire knowledge about technological achievements in pottery production in Apulia during the Middle Ages. The XPS results allow to characterize the surface glazes, which are transparent owing to the presence of PbO or opaque-white in case of Sn addition. The study of coloured glossy surfaces, after an optimized chemical etching, has also shed light on the pigment nature of the painted decorations, whose red colour is to be attributed to the presence of Pb3O4 and not of Fe oxides. Quantitative determinations were performed by ICP measurements on samples of differently coloured glazes, clayey slips and ceramic bulks. Pb and Cu, present in one green glaze, were also determined by differential pulsed anodic stripping voltammetry (DPASV). The analytical results were treated by different statistical techniques of multivariate analysis. 相似文献