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991.
Reactions among Cu(ClO4)2 · 6H2O, Cu(acac)2/VO(acac)2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu2L(acac)(H2O)2]ClO4 (1), [Cu4L2(acac)2(py)2](ClO4)2 (2) and (VO2)2L2Cu2(acac)2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO4− anion, and an extended 1D structure in complex 2 constructed by weak ππ stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1. 相似文献
992.
E. O. Chukhajian A. A. Khachatryan A. R. Gevorkyan G. A. Panosyan 《Chemistry of Heterocyclic Compounds》2007,43(6):701-707
The intramolecular cyclization of dialkyl(2-butynyl-4-hydroxy)[3-(p-chlorophenyl)propargyl]ammonium chlorides, catalyzed by
aqueous KOH, was realized. It was shown that the obtained products — 2,2-dialkyl-6-chloro-4-hydroxymethylbenzo[f]isoindolinium
chlorides — readily undergo recyclization under the action of a twofold molar amount of KOH in aqueous solution with heating
with the formation of 4-dialkylaminomethyl-8-chloro-1,3-dihydronaphtho[1,2-c]furans.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 834–840, June, 2007. 相似文献
993.
合成了一个新配合物[Mn(napn)(CH3OH)2]ClO4 (C26H26 Cl N2O8Mn,Mr = 584.88,H2napn = 双a-萘酚醛缩乙二胺),并测定了其晶体结构。晶体属于三斜晶系,空间群P ,a = 7.813(1),b = 13.025(2),c = 14.089(2) ? = 64.89(3), = 83.98(3), = 78.11(3)海琕 = 1270.16 ?,Z = 2, Dc = 1.529 g/cm3, F(000) = 604, R = 0.0837, wR = 0.1636。锰(Ⅲ)离子的配位构型为拉长的八面体。Schiff碱配体napn2-中的N2O2在赤道平面与锰(Ⅲ)形成四配位,2个CH3OH中的O原子分别在赤道平面两侧轴向位置与锰(Ⅲ)配位。由于Jahn-Teller效应,轴向上的MnO平均键长为2.52 拧A硗猓О写嬖诜肿幽诤头肿蛹淝饧? 相似文献
994.
Sang-Soo PacGunzi Saito 《Journal of solid state chemistry》2002,168(2):486-496
The complex formation of hexamethylenetetratellurafulvalene (HMTTeF) with 28 kinds of organic electron acceptors yielded 31 charge transfer (CT) complexes. The infrared and ultra-violet-visible-near-infrared spectra of the complexes were examined to study the ionicity of their ground states in solid. A plot of CT transition energies and the difference of redox potentials; ΔE(DA) of donor (D) and acceptor (A) molecules indicated that four complexes have a neutral ground state. Four other complexes exhibit characteristic features of a fully ionic ground state based on the vibrational spectra. Notably, the HCBD, F4TCNQ and DDQ complexes indicate both a relatively low first CT band and high conductivity in a solid in spite of the fully ionic character being very plausible. Twenty-three complexes having a partially ionic ground state have a CT band below 4×10 cm−1 and are highly conductive. The preparation of good single crystals of the HMTTeF complexes for structural analysis was only successful with Et2TCNQ and BTDA-TCNQ, which have the structure of DA alternately stacking. These two complexes indicate high conductivities in spite of their disadvantageous packing manner. The intermolecular interactions are found to be strongly enhanced by both the bulky molecular orbital of HMTTeF and the decreased on-site Coulomb repulsion in the HMTTeF complexes. These two factors in particular seem to prevent both the fully ionic and the DA alternating HMTTeF complexes from becoming insulators, even though the redox parameters and the crystal structures predict them to be insulating. 相似文献
995.
Shota Niibayashi 《Journal of organometallic chemistry》2005,690(2):276-285
A series of titanocene(III) alkoxides L2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me2C6H3(1c), 2,6-tBu2-4-Me-C6H2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO)3]2 [M = Mo, W], [CpRu(CO)2]2, and Co2(CO)8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO)3]2 [M = Mo, W] to form heterobimetallic complexes L2Ti(OR)(μ-OC)(CO)2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co2(CO)8 resulted in formation of Ti-Co1 heterobimetallic complexes, from 2a, 2e, or 2f, or Ti-Co3 tetrametallic complexes, Cp2Ti(OtBu)(μ-OC)Co3(CO)9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides. 相似文献
996.
A. Moghimi Sh. Sheshmani A. Shokrollahi H. Aghabozorg M. Shamsipur G. Kickelbick M. Carla Aragoni V. Lippolis 《无机化学与普通化学杂志》2004,630(4):617-624
A novel 1:2 proton transfer self‐associated compound LH2 , (GH+)2(pydc2—), was synthesized from the reaction of dipicolinic acid, pydcH2, (2, 6‐pyridinedicarboxylic acid), and guanidine hydrochloride, (GH+)(Cl—). The characterization was performed using IR, 1H and 13C NMR spectroscopy and single‐crystal X‐ray diffraction. LH2 · H2O crystallizes in the space group C2/c of the monoclinic system and contains eight molecules per unit cell. The unit cell dimensions are: a = 26.480(5)Å, b = 8.055(2)Å, c = 14.068(3)Å. The first coordination complex (GH)2[Cd(pydc)2] · 2H2O, was prepared using LH2 and cadmium(II) iodide, and characterized by 1H and 13C NMR spectroscopy and X‐ray crystallography. The crystal system is triclinic with space group P1¯ with one molecule per unit cell. The unit cell dimensions are: a = 8.5125(7)Å, b = 11.0731(8)Å, c = 13.2404(10)Å. The cadmium(II) atom is six‐coordinated with a distorted octahedral geometry. The two pydc2— units are almost perpendicular to each other. The protonation constants of the building blocks of the pydc‐guanidine adduct, the equilibrium constants for the reaction of pydc2— with guanidine and the stoichiometry and stability of the Cd2+ complex with LH2 in aqueous solution were accomplished by potentiometric pH titration. The solution studies strongly support a self‐association between pydc2— and GH+ with a stoichiometry for the CdII complex similar to that observed for the isolated crystalline complex. In fact, the [Cd(pydc)2]2— complex was found as the most abundant species in solution (> 90 %) at a pH >5. 相似文献
997.
Summary Sedimentation field-flow fractionation was shown to permit the precise evaluation of surface concentrations of human IgG, adsorbed to polystyrene latex spheres of different sizes. Unlike conventional techniques for measuring protein uptake by colloidal substrates, this method allowed a direct evaluation of mass adsorbed per unit area, without the need for potentially destructive labelling reactions. Thus, a four hour adsorption of IgG from a 3–10 fold excess of protein in solution yielded surface concentrations which were 1.4±0.1 mg/m2 on a 272 nm latex and 1.9±0.1 mg/m2 on a latex with a diameter of 142 nm. The lower value coincided with the estimated monolayer surface coverage. The IgG-PS 272 nm adsorption complex was shown to take up negligible amounts of HSA from a 10 mg/mL solution, while its specific uptake of a polyclonal rabbit anti-human IgG was 2.6 molecules per molecule of adsorbed antigen. The same ratio was found for the smaller particles. The surface concentration of adsorbed second antibody, often crucial in immunodiagnostic quantifications, was therefore found to be significantly enhanced by the increased substrate curvature presented by the smaller particles.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday. 相似文献
998.
To explore the properties of cyclodextrins (CDs) as an optical sensing phase, the behavior of immobilized CD in interaction with analytes was studied in this work. CDs having different cavity sizes were immobilized onto the surface of infrared (IR) internal reflection-sensing element (IRE) to kinetically monitor the behavior of CD in interaction with analytes. Several aromatic compounds having various molecular sizes and functional groups were used to characterize the interaction mechanism. A two-layer modification method was proposed in this work, which utilized a thin hydrophobic film (polyvinyl benzyl chloride) to stick on the IRE and to covalently bond to the CDs through an ethylene diamine linker. The synthesized CD phases exhibited high stability in aqueous solution. To analyze the behavior during the formation of complexes between the guest molecules and the CD phases, we modeled the interaction behavior and treated the kinetic data with the theoretical equations developed in this work. The results indicate that the behavior of the interaction between guest molecules and CDs was explained by considering the formation of two types of complexes: adsorbed complexes and inclusion complexes. The formation of the inclusion complexes was relatively fast, the time required to reach equilibrium could be shorter than a few minutes. The adsorbed complexes were also observed, but their rate of formation was relatively slow; equilibrium could be reached at times greater than 60 min. Based on the signals observed under equilibrium conditions, the concentration of inclusion complexes was approximately three times than that of the adsorbed complexes. 相似文献
999.
1INTRODUCTIONRecently,considerableattentionhasbeenpaidtotheinvestigationofcoordinationchemistryofmanganeseindifferentoxidationstatesnotonlybecauseofthediscoveryoftightlyboundmanganeseatomsinvariousbiomolecules[libutalsobecauseoftheirinterestingstructural,magneticandspectroscopicfeatures.Wehavepreparedseveralcomplexesofmanganese(n)withdifferentligands.Thestructuresandfeaturesofthesecompoundsarestudiedsystematically.Inthispaperwedescribethestructureofthecomplexwiththeligandsofphenanthroline… 相似文献
1000.