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991.
Kamel AM Fouda HG Brown PR Munson B 《Journal of the American Society for Mass Spectrometry》2002,13(5):543-557
Electrospray ionization (ESI) and collisionally induced dissociation (CID) mass spectra were obtained for five tetracyclines and the corresponding compounds in which the labile hydrogens were replaced by deuterium by either gas phase or liquid phase exchange. The number of labile hydrogens, x, could easily be determined from a comparison of ESI spectra obtained with N2 and with ND3 as the nebulizer gas. CID mass spectra were obtained for [M + H]+ and [M - H]- ions and the exchanged analogs, [M(Dx) + D]+ and [M(Dx) - D]- , and produced by ESI using a Sciex API-III(plus) and a Finnigan LCQ ion trap mass spectrometer. Compositions of product ions and mechanisms of decomposition were determined by comparison of the MS(N) spectra of the un-deuterated and deuterated species. Protonated tetracyclines dissociate initially by loss of H2O (D2O) and NH3 (ND3) if there is a tertiary OH at C-6. The loss of H2O (D2O) is the lower energy process. Tetracyclines without the tertiary OH at C-6 lose only NH3 (ND3) initially. MSN experiments showed easily understandable losses of HDO, HN(CH3)2, CH3 - N=CH2, and CO from fragment ions. The major fragment ions do not come from cleavage reactions of the species protonated at the most basic site. Deprotonated tetracyclines had similar CID spectra, with less fragmentation than those observed for the protonated tetracyclines. The lowest energy decomposition paths for the deprotonated tetracyclines are the competitive loss of NH3 (ND3) or HNCO (DNCO). Product ions appear to be formed by charge remote decompositions of species de-protonated at the C-10 phenol. 相似文献
992.
Michael J. Zaworotko Hassan H. Hammud Victor Ch. Kravtsov 《Journal of chemical crystallography》2007,37(3):219-231
Crystal of [Fe(Phen)3]Cl(PHB).2(PHBH).7H2O (1) is triclinic, space group P-1 with a = 12.0388(11) ?, b = 15.5286(14) ?, c = 15.7794(14) ?, α = 89.759(2)°, β = 75.818(2)°, γ = 71.900(2)° and Z = 2, (phen = phenanthroline, PHBH = p-hydroxybenzoic acid, PHB = p-hydroxybenzoate anion). The phen in adjacent Fe(phen)3
2+ cations are π–π interacted forming offset face to face (OFF) motifs. Juxtaposition of four phen ligands from two cations
encapsulate an R2
2(8) dimeric unit of H-bonded PHBH molecules within a centrosymmetric box froming a filled aryl box motif (FAB). Alternation
of OFF and FAB motifs form {OFF⋯FAB}∞ strands. The Fe(phen)3
2+ cation engages its phen ligands in π–π and/or CH–π interactions with two crystalographically different PHBH molecules and
one PHB anion. Seven water molecules and a chloride anion per iron(II) trisphenanthroline cation fill empty spaces in the
structure forming a hydrophilic cluster. Extensive intermolecular H-bond interactions occur between water molecules, chloride
anions, PHBH molecules, and PHB anions. Thermal analysis of (1) was done under N2(g). The TG, and dTG curves revealed the expected mass losses. All associated processes are endothermic as shown in the DSC curve. 相似文献
993.
Ahmad T. Kabbani Michael J. Zaworotko Heba Abourahma Rosa D. Baily Walsh Hassan H. Hammud 《Journal of chemical crystallography》2004,34(11):749-756
The title compound, [Cu2(II)(4-Cl-3-NO2–C6H3CO2)4(CH3OH)2] or [Cu2(4-chloro-3-nitrobenzoate)4(MeOH)2] has been prepared and its structure determined using X-ray crystallography. The complex crystallizes in the triclinic space group P-1 with a = 9.6887(9)Å, b = 10.6448(9)Å, c = 11.4194(10)Å, = 108.094(2), = 110.682(2), = 105.055(2), V = 952.691(15)Å3, and Z = 1. The structure consists of centrosymmetric dimers in which the Cu(II) atoms display a square pyramidal CuO5 coordination, with four carboxylate O atoms in the basal plane [CuO 1.951(2)–1.968(2)Å] and the methanol O atoms in the apical position [CuO 2.170(2)Å]. The Cu atoms are 2.614(1)Å apart and are bridged by four benzoate groups. The discrete dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol on one Cu(II) dimer and the nitro substituent on an adjacent Cu(II) dimer. The chains are interdigited and held by – stacking interactions forming 3D supramolecular array. 相似文献
994.
Two novel potentiometric sensors that are highly selective to Hg2+ ions are described. These are based on the use of 5,5'-dithio-bis(2-nitrobenzoic acid) (DTNB) and tricyclazole (TCZ) as neutral carriers in plasticized poly(vinyl chloride) membranes. Fast Nernstian responses are obtained for Hg2+ ions over the concentration ranges 7.0 x 10(-6) - 1.0 x 10(-2) and 7.7 x 10(-6) - 1.0 x 10(-2) mol l(-1) at pH 1.8 - 3.3 with lower detection limits of 5.0 x 10(-6) and 5.6 x 10(-6) mol l(-1) (approximately 1 microh ml(-1)) and calibration slopes of 30.0 and 29.7 mV decade(-1) with DTNB- and TCZ-based membrane sensors, respectively. Validation of the assay method reveals good performance characteristics, including long life span, good selectivity for Hg2+ ions over a wide variety of other metal ions, long term response stability, and high reproducibility. Applications for direct determination of mercury in hazardous wastes including dental amalgam, mercury bulbs, and fluorescent lamps give results with good correlation with data obtained using cold vapor atomic absorption spectrometry. 相似文献
995.
Hassan A. Ewais 《国际化学动力学杂志》2008,40(3):103-113
The mechanism of oxidation of ternary complexes, [CoII(nta)(S)(H2O)2]3? and [CoII(nta)(M)(H2O)]3? (nta = nitrilotriacetate acid, S = succinate dianion, and M = malonate dianion), by periodate in aqueous medium has been studied spectrophotometrically over the (20.0–40.0) ± 0.1°C range. The reaction is first order with respect to both [IO4?] and the complex, and the rate decreases over the [H+] range (2.69–56.20) × 10?6 mol dm?3 in both cases. The experimental rate law is consistent with a mechanism in which both the hydroxy complexes [CoII(nta)(S)(H2O)(OH)]4? and [CoII(nta)(M)(OH)]4? are significantly more reactive than their conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of the [CoII(nta)(S)(H2O)2]3?, k1 (3.60 × 10?3 s?1), is greater than the value of k6 (1.54 × 10?3 s?1) for the oxidation of [CoII(nta)(M)(H2O)]3? at 30.0 ± 0.1°C and I = 0.20 mol dm?3. The thermodynamic activation parameters have been calculated. It is assumed that electron transfer takes place via an inner‐sphere mechanism. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 103–113, 2008 相似文献
996.
997.
This paper presents a novel approach for the analysis of a fourth-order parabolic equation dealing with vibration of beams by using the decomposition method. In this regard, a general approach based on the generalized Fourier series expansion is applied. The obtained analytic solution is simplified in terms of a given set of orthogonal basis functions. The result is compared with the classical modal analysis technique which is widely used in the field of structural dynamics. It is shown that the result of the decomposition method leads to an exact closed-form solution which is equivalent to the result obtained by the modal analysis method. Some examples are given to demonstrate the validity of the present study. 相似文献
998.
Chaos control of a spinning disk model via delayed feedback method is presented. The feedback gain is obtained and adapted according to a minimum entropy (ME) algorithm. In this method, stabilizing an unstable fixed point of the system Poincare map is achieved by minimizing the entropy of point distribution on the Poincare section. Simulation results show the feasibility of the proposed method in applying the delayed feedback technique for chaos control of spinning disks. 相似文献
999.
1000.