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971.
WANG Shou-Wu YANG Yuan LI Bao-Long ZHANG Yong 《结构化学》2007,26(7):763-766
The new cadmium(II) coordination polymer [Cd(bte)2(dca)2]n 1 (bte = 1,2-bis(1,2,4- triazol-1-yl)ethane, dca = dicyanamide) was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 8.7148(15), b = 8.6142(17), c = 15.204(3) A, β = 92.100(10)o, V = 1140.6(4) A3, Z = 2, Mr = 572.87, Dc = 1.668 g/cm3, F(000) = 572, μ = 1.004 mm-1, the final R = 0.0654 and wR = 0.1429 for 1737 observed reflections (I > 2σ(I)). The cadmium atom is coordinated equatorially by four nitrogen atoms from four bte ligands and axially by two nitrogen atoms from two dca anions to adopt a distorted octahedral geometry. Each bte molecule bridges two cadmium(II) atoms. Two strands of bte molecules are wrapped around each other, and held together by cadmium(II) atoms. 1 Forms a double chain structure containing eighteen-membered Cd2(bte)2 rings. 相似文献
972.
CHEN Man-Sheng DENG Yi-Fang ZHANG Chun-Hua KUANG Dai-Zhi② FENG Yong-Lan PENG Yun-Lin 《结构化学》2007,26(2):219-223
A new manganese coordination polymer 1, [Mn(H2O)4(L)]n(ClO4)2n·2nH2O·3nL (L = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), has been synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pn with a = 13.9176(8), b = 15.4754(9), c = 15.9670(9) , β = 99.5010(10)o, V = 3391.8(3) 3, Z = 2, C56H68Cl2MnN16O14 , Mr = 1315.10, Dc = 1.288 g/cm3, μ = 0.344 mm-1, F(000) = 1374, R = 0.0733 and wR = 0.2035. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene and four oxygen atoms from water molecules, completing an octahedral geometry. The title complex exhibits a novel supramolecular layer architecture sustained by the concurrence of coordination bonds, hydrogen bonds, and π-π stacking interactions. 相似文献
973.
E. Röder I. Pigulla und J. Troschütz 《Fresenius' Journal of Analytical Chemistry》1977,288(1-2):56-58
Zusammenfassung Die Trennung und quantitative Bestimmung von fünf biogenen aliphatischen Aminen aus wäßriger Lösung gelingt mit Hilfe der Hochdruckflüssig-Chromatographie. Dabei werden die Amine als Derivate der Chinolin-8-sulfonsäure mit einem Vierkomponenten-Verteilungssystem chromatographiert. Die Eichkurven sind im vermessenen Gewichtsbereich linear, die Erfassungsgrenze liegt bei ca. 20 ng. Norephedrin dient als interner Standard.
High-pressure liquid chromatographic determination of aliphatic biogenic amines after derivatization with quinoline-8-sulphonic acid chloride
Summary High-speed liquid chromatography is shown to be useful for the separation and quantitation of five aliphatic biogenic amines in aqueous solution. The amines are converted into derivates of quinoline-8-sulphonic acid and chromatographed with a four-component two-phase system. Calibration curves are linear within the tested range of weight. The sensivity is about 20 ng. Norephedrine is used as internal standard.
Unser Dank gilt der Deutschen Forschungsgemeinschaft für großzügige finanzielle Unterstützung dieser Arbeit sowie dem Fonds der Chemischen Industrie für die Bereitstellung von Sachbeihilfen. 相似文献
974.
E. T. Denisov 《Russian Chemical Bulletin》2004,53(8):1602-1608
The transition state of addition of free radicals and atoms to multiple bonds is considered as a result of intersecting of two parabolic potential curves. One of them characterizes the stretching vibration of the attacked multiple bond, and another curve characterizes the stretching vibration of the bond formed in the transition state. The force constant of the latter is calculated by an empirical equation that correlates the force constant with the bond dissociation energy. In the framework of this model, the thermally neutral activation energy (E
e0) and the elongation of the attacked and formed bonds (r
e) in the transition state were calculated from the experimental data (activation energy (E
e) and enthalpy of reaction (H
e)) for the addition of an H atom and methyl, alkoxyl, aminyl, triethylsilyl, and peroxyl radicals to the C=C bond and the addition of H and CH3 to the C=O and CC bonds. Analysis of the data obtained showed that E
e0 depends linearly on the |H
e| + Ee sum, i.e., Ee0/kJ mol–1 = 14.2 + 0.61 · (Ee – H
e), and the bond elongation in the transition state for addition of the most part of radicals to ethylene and acetylene vary within (0.65–0.87)·10–10 m. The factors affecting the activation energy of the radical addition reactions are discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1542–August, 2004. 相似文献
975.
The mixed‐valent oxotantalate Eu1.83Ta15O32 was prepared from a compressed mixture of Ta2O5 and the metals in a sealed Ta ampoule at 1400 °C. The crystal structure was determined by means of single crystal X‐ray diffraction: space group R3¯, a = 777.2(6) pm and c = 3523.5(3) pm, Z = 3, 984 symmetrically independent reflections, 83 variables, RF = 0.027 for I > 2σ (I). The structure is isotypic to Ba2Nb15O32. The salient feature is a [Ta(+8/3)6O12iO6a] cluster consisting of an octahedral Ta6 core bonded to 12 edge‐bridging inner and six outer oxygen atoms. The clusters are arranged to slabs which are sandwiched by layers of [Ta(+5)3O13] triple octahedra. Additional Ta(+5) and Eu(+2) atoms provide the cohesion of these structural units. Twelve‐fold coordinated Eu(+2) atoms are situated on a triply degenerate position 33 pm displaced from the threefold axis of symmetry. A depletion of the Eu(+2) site from 6 to 5.5 atoms per unit cell reduces the number of electrons available for Ta‐Ta bonding from 15 to 14.67 electrons per cluster. Between 125 and 320 K Eu1.83Ta15O32 is semi‐conducting with a band gap of 0.23 eV. The course of the magnetization is consistently described with the Brillouin function in terms of a Mmol/(NAμB) versus B/T plot in the temperature range 5 K — 320 K and at magnetic flux densities 0.1 T — 5 T. At moderate flux densities (< 1 T) the magnetic moment agrees fairly well with the expected value of 7.94 μB for free Eu (2+) ions with 4f7 configuration in 8S7/2 ground state. Below 5 K, anisotropic magnetization measurements at flux densities B < 1 T point to an onset of an antiferromagnetic ordering of Eu spins within the layers and an incipient ferromagnetic ordering perpendicular to the layers. 相似文献
976.
Marit Rolandsgard 《Tetrahedron》2005,61(16):4129-4140
Preparation of α-oxo derivatives of spiro[4.4]nonane, spiro[4.5]decane and spiro[5.5]undecane derivatives is described. An efficient method for spiroannulation by Rh(I)-catalysed intramolecular hydroacylation provides α,α′-difunctionalised spiro[4.5]decanes. The α,α′-dioxo groups have been converted into vinyl triflates for arylation by Pd-catalysed cross-coupling reactions under Stille, Negishi or Suzuki conditions depending on relative reactivities. Stereoselective saturation of the conjugated aryl olefinic bonds by catalytic hydrogenation over Pd-carbon provides methodology for stereoselective preparation of α-aryl- and α,α′-cis,cis-diaryl spiranes, the latter with a sandwich like structure. Single crystal X-ray analyses have been used in the structural assignments. 相似文献
977.
Jing Liu Ji-jun Wang Ting Li Yong Zhou De-yan Shen Yun Huang Shou-ke Yan State Key Laboratory of Polymer Physics Chemistry Institute of Chemistry The Chinese Academy of Sciences Beijing China Physics Department Peking University Beijing China 《高分子科学》2007,(2):207-215
Aggregation process of isotactic poly(methyl methacrylate) (i-PMMA) has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95$±0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements. 相似文献
978.
A series of novel bidentate pyrazolone based Schiff base ligands were synthesized by interaction of 4-benzoyl-3-methyl-1-(4′-methylphenyl)-2-pyrazolin-5-one with various aromatic amines like aniline, o-,m-,p-chloroaniline and o-,m-,p-toluidine in a ethanolic medium. All of these ligands have been characterized on the basis of elemental analysis, IR and 1H NMR data. The molecular geometries of five of these ligands have been determined by single crystal X-ray study. Crystallographic study reveals that these ligands exist in the amine-one tautomeric form in the solid state. NMR study also suggests the existence of the amine-one form in solution at room temperature. Ab initio calculations for representative ligand HL1 has been carried out to know the coordination site of the ligand. Novel vanadium Schiff base complexes of these ligands with general formula [OV(L1–7)2(H2O)] have been prepared by interaction of aqueous solution of vanadyl sulfate pentahydrate with DMF solution of the appropriate ligands. The resulting complexes have been characterized on the basis of elemental analysis, vanadium determination, molar conductance and magnetic measurements, thermo gravimetric analysis, infrared and electronic spectral studies. Suitable distorted octahedral structures have been proposed for these complexes. 相似文献
979.
980.