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51.
52.
Joachim Janssen Holger Rumpf Hartwig Modrow Ralf Rablbauer Georg Frommeyer Josef Hormes 《无机化学与普通化学杂志》2003,629(10):1701-1708
The surface oxidation of FeCr alloys with 18, 28, and 43 mass‐% Cr was investigated in situ using grazing‐incidence X‐ray absorption spectroscopy (GIXAS) at the chromium and iron K‐edges. Oxidation in air was monitored in situ in the temperature range from 290 K to 680 K. The standard GIXAS data analysis is extended for the treatment of a single layer model in order to estimate the chromium concentrations of the oxide layer and of the near‐interface substrate as well as the oxide layer thickness. XANES analysis shows transitions from b.c.c. Fe to corundum type Fe2O3 and from b.c.c. Cr to corundum type Cr2O3. The initial oxide layers are 1.1‐1.4 nm thick and contain 60‐90 mass‐% chromium, while the near‐interface substrate is depleted in Cr. During heating, iron oxide growth dominates up to 560‐600 K. Then the chromium oxide layer loses its passivation effect and Cr oxidation sets in. 相似文献
53.
The title complexes, the Re(O)L(2)(Solv)(+) complexes (L = hoz, 2-(2'-hydroxyphenyl)-2-oxazoline(-) or thoz, 2-(2'-hydroxyphenyl)-2-thiazoline(-); Solv = H(2)O or CH(3)CN), are effective catalysts for the following fundamental oxo transfer reaction between closed shell molecules: XO + Y --> X + YO. Among suitable oxygen acceptors (Y's) are organic thioethers and phosphines, and among suitable oxo donors (XO's) are pyridine N-oxide (PyO), t-BuOOH, and inorganic oxyanions. One of the remarkable features of these catalysts is their high kinetic competency in effecting perchlorate reduction by pure atom transfer. Oxo transfer to rhenium(V) proceeds cleanly to afford the cationic dioxorhenium(VII) complex Re(O)(2)L(2)(+) in a two-step mechanism, rapid substrate (XO) coordination to give the precursor adduct cis-Re(V)(O)(OX)L(2)(+) followed by oxygen atom transfer (OAT) as the rate determining step. Electronic variations with PyO derivatives demonstrated that electron-withdrawing substituents accelerate the rate of Re(VII)(O)(2)L(2)(+) formation from the precursor adduct cis-Re(V)(O)(OX)L(2)(+). The activation parameters for OAT with picoline N-oxide and chlorate have been measured; the entropic barrier to oxo transfer is essentially zero. The potential energy surface for the reaction of Re(O)(hoz)(2)(OH(2))(+) with PyO was defined, and all pertinent intermediates and transition states along the reaction pathway were located by density functional theory (DFT) calculations (B3LYP/6-31G). In the second half of the catalytic cycle, Re(O)(2)L(2)(+) reacts with oxygen acceptors (Y's) in second-order reactions with associative transition states. The rate of OAT to substrates spans a remarkable range of 0.1-10(6) L mol(-)(1) s(-)(1), and the substrate reactivity order is Ph(3)P > dialkyl sulfides > alkyl aryl sulfides > Ph(2)S approximately DMSO, which demonstrates electrophilic oxo transfer. Competing deactivation and inhibitory pathways as well as their relevant kinetics are also reported. 相似文献
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55.
Matthias Westerhausen Mathias Krofta Stefan Schneiderbauer Holger Piotrowski 《无机化学与普通化学杂志》2005,631(8):1391-1396
Transmetallation of Tin(II) in [Sn(μ3‐PSitBu3)]4 by Barium – from Sn4P4 Heterocubane Structures to Heterobinuclear Cage Compounds with a Central BanSn4?nP4 Heterocubane Polyhedron (n = 1, 2 and 3) For the preparation of compounds of the type [BanSn4?n(PSitBu3)4] (n = 1 ( 2 ), 2 ( 3 ) and 3 ( 4 )) two synthetic routes are applicable: in the transmetallation reaction homometallic [Sn4(PSitBu3)4] ( 1 ) reacts with barium metal and in a deprotonation reaction (metallation) tri(tert‐butyl)silylphosphane reacts simultaneously with (thf)2Ba[N(SiMe3)2]2 and Sn[N(SiMe3)2]2. During the transmetallation reaction mixtures of the heterobimetallic cage compounds 2 to 4 are obtained, however, analytically pure compounds 2 and 3 are accessible by the metallation reaction. Compound 4 is formed as a minor product together with 3 . Due to the larger Ba‐P bond lengths compared to the Sn‐P values the substitution of tin by barium leads to strong distortions of the heterocubane moiety. With NMR‐spectroscopic experiments one could show that all the above mentioned compounds form BanSn4?nP4 heterocubane cage structures. 相似文献
56.
AES depth profiles on ceramic powders (untreated/hydrolyzed/oxidized/ (Al, Y)2O3 coated Si3N4, [BaO, SiO2] coated Al2O3) are feasible on thin, homogeneous layers or m sized agglomerations prepared on an Au foil. By means of the depth profiles one can qualitatively characterize the coating around the particles. Factor analysis of the depth profiles on the differently treated Si3N4 powders suggests the existence of an Si2N2O phase on the oxidized sample.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday 相似文献
57.
To get informations on both the structure and dynamics of hydrogen chelates 1 of heteroaromatic systems, a great variety of quinazoline-2-acetonitrile chelates were synthesized (see 2–4 ). Similarly to the situation of the corresponding H-chelates in the pyrimidine-2-acetonitrile series, the investigation of these new derivatives 2–4 by NMR spectroscopic methods (DNMR, COSY, NOESY, ROESY, EXSY, HMQC, HMBC) confirms the presence of an equilibrium of the two possible H-chelate structures (two ‘rotamers’ I and II , i.e., (E)/(Z) isomers; see Scheme). The corresponding equilibria I ? II were determined by complete 1H-NMR signal assignment at low temperatures (after freezing the rotational processes). In addition, the tautomer equilibria A ? B (relative energies of the two minima of the nonsymmetrical double-well potential) for both ‘rotamers’ are ascertained by H,H and C,H couplings. The results are an important basis for the interpretation of both the UV/VIS absorptions and the dependence of fluorescence and fluorescence quantum yields on temperature. 相似文献
58.
59.
New Complexes of the Lanthanoides with Bidentate Ligands. The Crystal Structures of [(C17H17N2)GdBr2(thf)2] and [(C17H17N2)3Ln] (L = Sm, Gd) Reaction of [(AIP)Li] with GdBr3 leads to a new mononuclear complex [(AIP)GdBr2(thf)2] 1 . In contrast to this with SmI2 the compound [(AIP)3Sm] 2 is build up. Such complexes are also formed with Gd(OR*)3 (R* = OtBu2C6H3) and [(AIP)Li] in a 1:3 ratio, [(AIP)3Gd] 3 . The structures of 1–3 were characterized by X-ray single crystal structure analysis ( 1 : space group Pna21 (No. 33), Z = 4, a = 1 972.7(9) pm, b = 984.7(5) pm, c = 1 425.0(8) pm, α = β = γ = 90°; 2 · 2 THF: space group C2/c (No. 15), Z = 8, a = 3 644.4(9) pm, b = 1 437.5(5) pm, c = 2 334.4(7) pm, β = 1 21.07(6)°; 3 : space group P2(1)/c (No. 14), Z = 4, a = 1 872.9(1) pm, b = 1 064.6(1) pm, c = 2 282.4(2) pm, β = 103.75(8)°). 相似文献
60.
Keil O LeRiche T Deppe H Volmer DA 《Rapid communications in mass spectrometry : RCM》2002,16(8):814-820
This paper focuses on the technical aspects of chemical screening from 384-well plate nano-scale single-bead combinatorial libraries. The analytical technique utilized is a combination of capillary liquid chromatography with ultraviolet detection and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The HPLC/MALDI-MS hyphenation is achieved by means of a micro-fraction collector with a peak detection system that automatically collects the peaks onto the MALDI targets for subsequent characterization. Several experimental parameters such as type of 384-well plate, well-plate sealing foils, and a column-switching procedure were investigated using a small test library of nine components. Additionally, the influence of different MALDI matrices, different MALDI targets and sample-spotting techniques on the MALDI detection sensitivity as well as the ruggedness and sample throughput capacity of this technique were studied. Optimum results for the analytes investigated were obtained with 2,5-dihydroxybenzoic acid using on-line mixing of HPLC effluent and matrix solution. To demonstrate the potential of this capillary HPLC/MALDI-TOFMS method, its application to several single-bead libraries was investigated. The instrumental method allowed for the rapid identification and purity assessment of combinatorial libraries with detection limits down to the higher femtomole level using both UV detection and MALDI mass spectrometry. 相似文献