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121.
Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti 相似文献
122.
Maria Gil Elena Bermejo Alfonso Castieiras Heloisa Beraldo Douglas X. West 《无机化学与普通化学杂志》2000,626(11):2353-2360
Pyridyl bis(N(4)‐substituted thiosemicarbazones), in which the substituents replacing the NH2 group on the thiosemicarbazone moieties are piperidyl, H2Plpip; hexamethyleneiminyl, H2Plhexim; diethylamino, H2Pl4DE; and dipropylamino, H2Pl4DP, have been synthesized. These bis(thiosemicarbazones) and their nickel(II) complexes have been characterized with IR, electronic, mass, and 1H and 13C NMR spectra. Crystal structures have been solved for H2Plpip and all four nickel(II) complexes. H2Plpip does not possess hydrogen bonding between the thiosemicarbazone moieties, but is in the Z isomeric form with intramolecular hydrogen bonding from both thiosemicarbazone moieties to pyridine nitrogen atoms. The nickel(II) complexes possess square‐planar N2S2 (i. e., imine nitrogen and thiolato sulfur atoms) centers and the two pyridine ring nitrogen atoms are not coordinated. 相似文献
123.
The two nickel chelates of Schiff bases, 3-hydroxy-N-{2-[(3-hydroxy-N-phenylbutyrimidoyl)-amino]-phenyl}-N′-phenylbutyramidine (M1) and bis-4-(ethyliminomethyl)naphthalene-1-ol (M2), have been synthesized and explored as ionophores for preparing PVC-based membrane sensors selective to nickel ion. The influences of membrane compositions on the potentiometric response of the electrodes have been found to substantially improve the performance characteristics. The best performance was obtained with the electrode having a membrane composition (w/w; mg) of (M1): PVC:NaTPB:CN in the ratio 5:150:5:150. The sensor shows a linear potential response for Ni2+ over a wide concentration range 1.6 × 10−7 to 1.0 × 10−2 M with Nernstian compliance (30.0 ± 0.2 mV/decade of activity) within pH range 2.5-9.5 and a fast response time of 10 s. The sensor has been found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol, and acetonitrile and could be used for a period of 4 months. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of nickel in real samples. The practical utility of the membrane electrode has also been observed in the presence of surfactants. 相似文献
124.
Zilu Chen 《Journal of solid state chemistry》2008,181(8):2078-2086
Four Cd(II) and Zn(II) complexes with the in situ-generated ligand of 3-amino-1,2,4-triazolate (AmTAZ−) were isolated from the solvothermal reactions of the corresponding Cd(II) or Zn(II) salts with 5-amino-1H-1,2,4-triazole-3-carboxylic acid (AmTAZAc). Their structures were determined by single-crystal X-ray diffraction analysis. [Zn(AmTAZ)(CH3COO)] (1) presents a two-dimensional framework constructed from Zn(II) ions and μ3-AmTAZ− ligands. A remarkable feature of [Zn4(AmTAZ)4(SO4)(OH)(C2O4)0.5]·2H2O (2) is the construction of the building units of octagonal cylinders which interact with each other by sharing one face or overlapping, resulting in the formation of a three-dimensional framework with three kinds of 1D channels. [Cd(AmTAZ)Br] (3) crystallizes in a chiral space group P212121, giving a homochiral three-dimensional framework with two types of helical channels (left- and right-handed). Different from the others, the 3-amino-1,2,4-triazole molecules in [Cd(AmTAZH)SO4] (4) behave as neutral μ2-2,4-bridges to connect the two-dimensional CdSO4 sheets into a three-dimensional framework. Of all, 2 and 3 display different fluorescent properties probably due to different metal ions, coordination environments and structural topologies. 相似文献
125.
Tandem carbonyl ylide formation-1,3-dipolar cycloaddition of α-diazo N-acetyl-tetrahydro-β-carbolin-1-one derivatives occur efficiently in the presence of a dirhodium catalyst to afford bimolecular cycloadducts in high yield. The Rh(II)-catalyzed reaction also takes place intramolecularly to give products derived from trapping of the carbonyl ylide dipole with a tethered alkene. The power of the intramolecular cascade sequence is that it rapidly assembles a pentacyclic ring system containing three new stereocenters and two adjacent quaternary centers stereospecifically in a single step and in high yield. 相似文献
126.
S. A. Mitchenko T. V. Krasnyakova I. V. Zhikharev 《Theoretical and Experimental Chemistry》2008,44(5):316-319
We report the catalysis of the hydrochlorination of acetylene on the surface of dry K2PdCl4 subjected to prior mechanical activation in an atmosphere of acetylene or propylene. The stereochemistry of the reaction
corresponds to trans addition of the halogen and hydrogen atoms to the C-C triple bond. The hydrogen halide is the source
of the halogen atom in the reaction product. The mechanical activation of K2PdCl4, in contrast to the case of K2PtCl4, is also capable of activating the C-C double bond: propylene is hydrochlorinated under similar conditions to isopropyl chloride.
Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 5, pp. 306–309, September–October, 2008. 相似文献
127.
A new method of preparing 2,2′‐bipyridines with short reaction times by using microwave assistance and heterogeneous catalysts has been developed. With a Negishi‐like protocol, it was found that Ni/Al2O3–SiO2 afforded 2,2′‐bipyridine products in up to 86 % yield in 1 h. Palladium supported on alumina also provided yields of 2,2′‐bipyridines comparable to those seen for homogeneous PEPPSITM (1,3‐diisopropylimidazol‐2‐ylidene)(3‐chloropyridyl)palladium(II)dichloride) and tetrakis(triphenylphosphanyl)palladium complexes. 相似文献
128.
This article describes the highly sensitive and selective determination of epinephrine (EP) using self‐assembled monomolecular film (SAMF) of 1,8,15,22‐tetraamino‐phthalocyanatonickel(II) (4α‐NiIITAPc) on Au electrode. The 4α‐NiIITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α‐NiIITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α‐NiIITAPc SAMF modified electrode was found to be 1.94×10?2 cm s?1 which was much higher than that at the bare Au electrode. Further, it was found that 4α‐NiIITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α‐NiIITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection. 相似文献
129.
A new category of dinucleating macrocyclic Schiff base ligands with ring sizes from 34- to 52-membered have been synthesised employing metal template procedures involving the reaction of o-phenylenediamine with a series of α,ω-bis(3′-hydroxy-4′-formylphenyloxy)alkanes in the presence of calcium(II), barium(II) or manganese(II). The latter cations act as ‘transient’ templates for formation of the corresponding metal-free Schiff base macrocyclic ligands, H4Ln (where n signifies the number of carbons in each linking bis-alkoxy chain); the macrocycles corresponding to n = 4, 6 and 8 were isolated and characterised while, for n = 1, in which single methylene groups acts as the bridges between salicyl moieties, the cyclic product was used directly for preparation of its dinuclear complex, [Zn2L1], without prior isolation. Evidence for the templating role of barium in the preparation of H4L6 and H4L8 was obtained by isolation of the corresponding species of type H4Ln·2Ba(ClO4)2 (n = 6 or 8) as ‘intermediates’ before generation of the respective metal-free macrocycles. Reaction of zinc(II) acetate with the free macrocycles in methanol yielded complexes of type [Zn2Ln] in all cases. A related non-cyclic ligand, H2L0 and its corresponding mononuclear complex, [ZnL0]·H2O, were also synthesised and its spectral properties compared with those of the macrocyclic derivatives. The elemental analyses, 1H NMR, IR, UV–Vis and MS spectra of the respective zinc complexes in each case were in accord with the formation of the expected 2:2 condensation product. The results of DFT calculations to probe aspects of the electronic and structural natures of both H2L1 and H4L4 are briefly presented. 相似文献
130.
The interaction of diethyl (pyridyn-2-ylmethyl)phosphonate (2-pmpe) with Cu(NO3)2 · 6H2O leads to a partial hydrolysis of the starting ligand and formation of the compound of the formula Cu2(2-mpmpe)2(H2O)2(NO3)2, where 2-mpmpe = monoethyl (pyridyn-2-ylmethyl)phosphonate. The crystal and molecular structure of a copper(II) compound was determined by single X-ray diffraction method. Its structure consists of five-coordinated in distorted square planar geometry (CuNO4 chromophore) copper(II) ions doubly bridged by OPO from phosphonate. The Cu?Cu distance is 4.69 Å. The crystal packing is determined by the interdinuclear hydrogen bond system, which leads to a three-dimensional (3D) H-bonds network. The compound was characterized by infrared, ligand field, EPR spectroscopy, and magnetic studies. The magnetic properties of the title compound investigated over the 1.8–300 K, revealed the occurrence of a weak ferromagnetic coupling through phosphonate bridge (J = 1.86 cm−1) and interdimer superexchange coupling through H-bond network (zJ′ = −0.17 cm−1). Spectroscopic and magnetic properties are presented in the light of crystal structure. 相似文献