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141.
Marita Hohmann Luise Krauth-Siegel K. Weidenhammer Wolfgang Schulze Manfred L. Ziegler 《无机化学与普通化学杂志》1981,481(10):95-106
Molecular and Crystal Structures of (CO)4W(μ-S-t-C4H9)2W(CO)4, η7-C7H7W(μ-SC6H4CH3)3W(CO)3 and η7-C7H7W(μ-S-n-C4H9)3W(CO)(μ-S-n-C4H9)2W(CO)4 The molecular structures of the two binuclear complexes (CO)4W(μ-S-t-C4H9)2W(CO)4 and η7-C7H7W(μ-SC6H4CH3)3W(CO)3 and of the tungsten cluster η7-C7H7W(μ-S-n-C4H9)3W(CO)-(μ-S-n-C4H9)2W(CO)4 respectively are described. In the nonlinear trinuclear cluster the central tungsten atom is connected to the two tungsten atoms by two and three μ-S-n-C4H9 bridges respectively and additionally by one W? W bond each. The coordination sphere of the W atoms is completed by a η7-C7H7 ring and four CO groups respectively; the central tungsten carries an additional CO group. 相似文献
142.
(Z)-2-Butenyl-dimethoxyborane adds smoothly to propanal and benzaldehyde to afford the homoallyl alcohols (R*,R*)- 1 and (R*,R*)- 2 , In contrast (E)-2-butenyl-dimethoxyborane leads to adducts having the (R*,S*)-configuration. Dimethoxy-(Z)-2-pentenylborane, dimethoxy-(Z)-(2-methyl-2-butenyl)borane and (2Z,4E)-or (2E,4Z)hexadienyl-dimethoxyborane, treated with propanal, give (R*,R*)- 3 , (R*,R*)- 4 , (E),(R*,S*)- 5 and (Z),(R*, R*)- 5 , respectively. A transition state model implying a pericyclic electron motion is in perfect agreement with the regio- and stereoselective outcome of these borane reactions. 相似文献
143.
Ring Enlargement by Lactonization of Methylated 1-(3′-Hydroxypropy1)-2-oxocyclododecane-1-carbonitriles The title compounds were prepared by Michael reaction of 2-oxocyclododecane-1-carbonitrile ( 1 ) and acrylaldehyde and its derivatives followed by NaBH4 reduction or methylation of the aldehyde group with [(CH3)2Ti(i-PrO)2] (Scheme 1). In all cases, the ring enlargement was performed with Bu4NF/THF to give different methylated derivatives of 12-cyano-15-pentadecanolide ( 13 ) in 95–99% yield. The Yields of the rearrangement products are not dependent on the positions and numbers of the CH3 groups in the side chain of 3 . The lactonization reaction is of unremarkable stereoselectivity. 相似文献
144.
Manfred Schlosser 《Angewandte Chemie (International ed. in English)》1974,13(11):701-706
Merits and drawbacks of known carbon-carbon linking procedures are outlined. Two novel methods are discussed in some detail: the copper-catalyzed alkylation of Grignard reagents and reactions with allylpotassium compounds. Both methods provide a very efficient access to saturated, unsaturated, as well as functionally substituted hydrocarbons and moreover permit an astonishing degree of regio- and stereoselective control of olefin synthesis. 相似文献
145.
During the examination of extracts from Oncinotis tenuiloba STAPF a new polyamine, N4-benzoylsperimidine ( 8 ), was isolated. For unambiguous structure elucidation, it was transformed into the diacetyl derivative 13 , and the three possible N-benzoyl-substituted isomers of spermidine 5, 8 , and 11 together with their peracetylated derivatives 12–14 , respectively, were synthesized and identified. 相似文献
146.
A bidentate ligand consisting of a 2-(diphenylphosphinoethyl)-thio moiety was attached to β-cyclodextrin at the 6-position. The corresponding norbornadiene Rh(I) complex in the form of the BF4− salt was prepared. 相似文献
147.
Wolfgang A. Herrmann Ricardo Serrano Adolf Schäfer Ulrich Küsthardt Manfred L. Ziegler Ernst Guggolz 《Journal of organometallic chemistry》1984,272(1):55-71
Short-wavelength photolysis of tricarbonyl(η5-pentamethylcyclopentadienyl)rhenium (1) (λ < 300 nm, quartz-glass) in tetrahydrofuran yields under partial or complete decarbonylation three novel organorhenium compounds, with the relative yields depending upon the irradiation time. Formed by exhaustive oxidative decarbonylation, the complex trioxo(η5-pentamethylcyclopentadienyl)rhenium(VII) (5) represents the first example of the new class of oxo half-sandwich complexes. The derivatives (μ-O)[(η5-C5Me5)Re(CO)2]2 (2; Me = CH3) and (η5-C5Me5)2Re2(CO)2O2 (3; Me = CH3) containing both oxo and carbonyl ligands are formed from 1 at shorter irradiation times. Both compounds are isolable intermediates along the mechanistically not yet fully established sequence 1 → → 5 as they are degraded to 5 under CO2 elimination in the presence of air and/or light. The mixed oxo carbonyl complex 2 has been characterized by means of single-crystal X-ray diffraction techniques (triclinic, space group P-Ci1; a 907.4(2), b 1040.2(3), c 1414.3(4) pm; α 79.99(2), β 88.42(2), γ 66.18(2)°; Riso = 0.068, Raniso = 0.037, Rw = 0.031). The molecular structure centres around an isosceles Re2O triangle whose metal centres exhibit a strongly distorted square-pyramidal geometry; the metal-metal distance recorded at 281.7(1) pm is in agreement with a single bond by the EAN rule. The centrically coordinated, planar five-membered ring ligands are parallel to each other (interplanar angle 2°) and occupy trans-positions with respect to the central Re2O geometry. 相似文献
148.
Wide rim tetraurea calix[4]arenes monofunctionalized at the narrow rim by COOH or NH2 have been synthesized in five steps from t-butylcalix[4]arene tripropylether. Their covalent linkage via the narrow rim to a central calix[4]arene fixed in the 1,3-alternate conformation led to pentacalix[4]arenes 9 bearing four tetraurea derivatives in the cone conformation in a flexible tetrahedral arrangement. Their self-assembly via the formation of hydrogen bonded dimeric capsules has been studied under different conditions. A fourfold heterodimerisation of tetrakis-tetraurea derivatives of type 9 with tetratosylurea 10 has been confirmed by 1H NMR-spectroscopy and dynamic light scattering. 相似文献
149.
The Oxidation of 3-(1-Nitro-2-oxocycloalkyl)propanal Oxidation of the title compound 1 with KMnO4 under neutral conditions led to the corresponding acid 2 , 5-(2,3,4,5-tetrahydro-2-nitro-5-oxo-2-furyl)pentanoic acid ( 4 ), and 4-oxononadioic acid ( 6 ). On the basis of experimental results the mechanism of the formation of 4 is discussed (Scheme 1). Oxidation of 1 with KMnO4 under basic conditions gave 6 which was transformed to (E)-4,5-dihydro-5(2′-oxocyclopentyliden)furan-2(3H)-one ( 12 ) with benzene/TsOH (Scheme 3). In contrast to this result the corresponding 4-oxoheptandioic acid ( 22 ) yields 1,6-dioxaspiro[4,4]nonan-2,7-dione ( 23 ) only (Scheme 4). 相似文献
150.
Müller U Rätzsch M Schwanninger M Steiner M Zöbl H 《Journal of photochemistry and photobiology. B, Biology》2003,69(2):97-105
The yellowing and IR-changes of spruce wood as a result of UV-irradiation were studied using two different types of xenon lamps (lambda>300 nm; I(o)=50 mW cm(-2) and lambda>280 nm; I(o)=17.5 mW cm(-2)). Changes in the IR spectra as well as the yellowing of the irradiated wood surfaces show the influence of UV light on the wood modules. The UV-irradiation (72 h; lambda>300 nm; I(o)=50 mW cm(-2)) decreased the lignin content on the surface by up to 20% of the original values. The colour difference of yellowing (deltaE) exhibited a systematic trend to higher values with increasing irradiation time. Our results show that the photoyellowing (UV-Vis detection) correlates very well with lignin degradation (IR detection). This result is in agreement with the quinone formation as the chromophoric reaction product of lignin decay. The degradation, yellowing, and oxidation kinetics differed only little using different light sources. The absorbed light intensity, which depends on wavelength, the intensity distribution of the light source and the absorption spectrum of lignin, influenced the degradation rate. Under the current experimental conditions, the absorption spectrum of lignin was the most important factor. Therefore, irradiation with lambda>280 nm is useful for rapidly monitoring the UV-degradation of wood 相似文献