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1.
An efficient and sensitive analytical method based on molecularly imprinted solid‐phase extraction (MISPE) and reverse‐phase ultrasound‐assisted dispersive liquid–liquid microextraction (USA‐DLLME) coupled with LC–MS/MS detection was developed and validated for the analysis of urinary 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a tobacco‐specific nitrosamine metabolite. The extraction performances of NNAL on three different solid‐phase extraction (SPE) sorbents including the hydrophilic‐lipophilic balanced sorbent HLB, the mixed mode cationic MCX sorbent and the molecularly imprinted polymers (MIP) sorbent were evaluated. Experimental results showed that the analyte was well retained with the highest extraction recovery and the optimum purification effect on MIP. Under the optimized conditions of MIP and USA‐DLLME, an enrichment factor of 23 was obtained. Good linearity relationship was obtained in the range of 5‐1200 pg/mL with a correlation coefficient of 0.9953. The limit of detection (LOD) was 0.35 pg/mL. The recoveries at three spiked levels ranged between 88.5% and 93.7%. Intra‐ and inter‐day relative standard deviations varied from 3.6% to 7.4% and from 5.4% to 9.7%, respectively. The developed method combing the advantages of MISPE and DLLME significantly improves the purification and enrichment of the analyte and can be used as an effective approach for the determination of ultra‐trace NNAL in complex biological matrices.  相似文献   
2.
A chiral coordination compound {(Δ)[Fe(II)(phen)3][(Δ)Fe(III)(C2O4)3](NH4)(H2O)3(DMF)}n (phen = 1,10‐phenanthroline), (DMF = N,N'‐Dimethylformamide), has been synthesized, and the structure has been revealed by infrared spectroscopy and X‐ray single‐crystal diffraction. The framework consists of two chiral subunits. One subunit (Δ)[(Fe(III)(C2O4)3]3? which as host anion forms a chiral porous three‐dimensional supermolecular network with lattice water, lattice DMF and lattice ammonium cation through hydrogen bonds. And then the other is Δ[Fe(II)(phen)3]2+ which as guest cation fills in the chiral cavity located in the previously mentioned host porous network.  相似文献   
3.
Quantum chemistry methods are applied to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of Iridium (III) complexes [Ir(C∧N)2(L)2]+ (L = 4‐pyCO2Et; C∧N = 2‐phenylpyridine, 1 ; 2‐(4‐tolyl)pyridine, 2 ; 2‐(4,6‐difluorophenyl)pyridimato, 3 ; benzoquinoline, 4 ), which may be used as emitters on organic light emitting diodes (OLEDs). Calculations of ionization potentials and electron affinities are used to evaluate the injection abilities of holes and electrons into these complexes. The reorganization energy (λ) calculations show that the four complexes are suitable as emitters in OLEDs. The absorptions and emissions can be tuned by adding substituent to the ppy ligand or extending the π‐conjugation effect of the C∧N ligand, and quantum yields of 1 – 4 are investigated. In addition, no solvent effect is observed in the absorption and emission spectra. © 2012 Wiley Periodicals, Inc.  相似文献   
4.
In this study, the initial oxidation behaviour of laser‐treated Al/NiCrAlY bond‐coat is investigated. Two approaches, (i) Al film sputtering on the surface of bond‐coat and (ii) laser treatment, have been taken to enhance the oxidation resistance of NiCrAlY bond‐coat. Experimental results showed that after laser treatment, the Al/NiCrAlY bond‐coat exhibited a columnar dendritic microstructure without cracks and voids. A dense and continuous α‐Al2O3/Cr2O3 multilayer was found to form on the bond‐coat surface. Results on the cyclic oxidation at 1200 °C (for time ≤ 204 h) revealed that the laser‐treated Al/NiCrAlY bond‐coat exhibited better oxidation resistance compared to as‐sprayed NiCrAlY, Al/NiCrAlY and laser‐remelted NiCrAlY bond‐coat. The formation of θ‐Al2O3, NiO, Cr2O3 and NiCr2O4 spinel oxides was observed to be suppressed due to the preformed α‐Al2O3 scale during initial oxidation on the surface of laser pre‐oxidized Al/NiCrAlY bond‐coat. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
5.
Quinoline bridged imidazolium precursors 5,8‐bis(NR‐imidazolylidenylmethylene)quinoline PF6 salts [H2L](PF6)2 [R = Me ( 1a ), R = naphthylmethyl ( 1b )] were prepared by quaternization of N‐methylimidazole and N‐naphthylmethylimidazole with 5,8‐bis(bromomethyl)quinoline, respectively. Reaction of the imidazolium ligands 1a and 1b with Hg(OAc)2 and Ag2O in acetonitrile gave the macrocyclic transition metal carbene complexes [Hg2L2](PF6)4 ( 2a and 2b ) and [Ag2L2](PF6)2 ( 3a and 3b ), respectively. All the N‐heterocyclic carbene complexes were characterized in detail by NMR, ESI‐MS, and elemental analysis. Structures of complexes 2a and 3a were determined by X‐ray diffraction studies. Structural studies revealed that the coordination arrangement of the central mercury atom in complex 2a displays a tricoordinate mode and the molecular conformation results in a“closed” form with the bridging quinoline functionality in the macrocycle, whereas the silver complex 3a does not show an coordiantion between the bridging quinoline and the AgI ion, which results in an “open” conformation of the macrocycle. The HgII and AgI NHC complexes showed similar UV absorption and luminescence in acetonitrile solutions.  相似文献   
6.
Two metal‐organic frameworks, [Zn(dmtrz)(btrc)1/3]n ( 1 ) and [Zn2(dmtrz)2(btec)(H2O)2]n ( 2 ) (dmtrz = 3, 5‐dimethyl‐1‐H‐1, 2,4‐triazole, btrc = 1, 3,5‐benzenetricarboxylate, btec = 1, 2,4, 5‐benzenetetracarboxylate), were synthesized by hydrothermal reaction. The crystal structure analysis reveals that compound 1 is a dense 3D framework with Schläfli symbols of {43}2{46 · 66 · 83}3, which is a loh1 structure. Compound 2 is a 2D network. In addition, the photoluminescence of two compounds were studied in solid state at room temperature, together with their thermal analysis.  相似文献   
7.
The cage‐like complex, Ag4L4(NO3)4 ( 1 ) [L = 1, 4‐bis(pyridine‐2‐ylmethoxy)benzene] was synthesized by the reaction of the flexible bidentate ligand and silver nitrate. It was characterized by elemental analysis, IR spectroscopy, TG, and single‐crystal X‐ray analysis. Complex 1 is reported as the first cage‐like cluster constructed by four nitrate anions bridging two [2+2] macrocycles. A blue luminescent emission and luminescent enhancement effect are observed in complex 1 .  相似文献   
8.
The Schiff base ligand, 1‐phenyl‐3‐methyl‐5‐hydroxypyrazole‐4‐methylene‐8′‐quinolineimine, and its CuII, ZnII, and NiII complexes were synthesized and characterized. The crystal structure of the ZnII complex was determined by single‐crystal X‐ray diffraction, indicating that the metal ions and Schiff base ligand can form mononuclear six‐coordination complexes with 1:1 metal‐to‐ligand stoichiometry at the metal ions as centers. The binding mechanism and affinity of the ligand and its metal complexes to calf thymus DNA (CT DNA) were investigated by UV/Vis spectroscopy, fluorescence titration spectroscopy, EB displacement experiments, and viscosity measurements, indicating that the free ligand and its metal complexes can bind to DNA via an intercalation mode with the binding constants at the order of magnitude of 105–106 M –1, and the metal complexes can bind to DNA more strongly than the free ligand alone. In addition, antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for hydroxyl radical in vitro, indicating that the compounds show stronger antioxidant activities than some standard antioxidants, such as mannitol. The ligand and its metal complexes were subjected to cytotoxic tests, and experimental results indicated that the metal complexes show significant cytotoxic activity against lung cancer A 549 cells.  相似文献   
9.
Polyacrylonitrile‐based carbon fibers with different graphite degrees were oxidative ablated at 500 and 600 °C in air. By Thermal gravimetric (TG), Raman spectroscopy, X‐ray diffraction, and SEM, the mass loss, microstructure, and surface morphology of carbon fibers were investigated. The mass loss of carbon fiber increases linearly with increasing oxidative ablated time under 500 and 600 °C. The carbon fiber with higher graphite degree shows higher oxidative resistance, and the surface roughness increases gradually because of chemical ablation during the whole oxidation. A gloss morphology appears on the surface primarily because of physical denudation for carbon fibers with lower graphite degree and then burn off according to carbon and oxygen reaction. The crystallite size (La) decreases significantly, while interlayer spacing(d002) remains nearly unchanged. SEM observation suggests the two kinds of ablation mechanisms for carbon fibers with different graphite degrees indicating that CC band in sp3 hybridization prefers to be attacked by oxygen molecule more than that in sp2 hybridization during oxidation ablation in air. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   
10.
A simple and economical CE method has been developed for the analysis of four model basic proteins by employing N‐methyl‐2‐pyrrolidonium methyl sulfonate ionic liquid (IL) as the dynamic coating material based on the interaction of both between electrostatic attraction and hydrogen bond, and between the organic cations of IL and the inner surface of bare fused‐silica capillary. The N‐methyl‐2‐pyrrolidonium‐based IL modified capillary not only generated a stable suppressed electroosmotic flow, but also effectively eliminated the wall adsorption of proteins. Several important parameters such as the IL concentration, pH values, and concentrations of the background electrolyte were optimized to improve the separation of basic proteins. Consequently, under the optimum separation conditions, a satisfied separation of basic proteins including lysozyme, cytochrome c, ribonuclease A, and α‐chymotrypsinogen A with theoretical plates ranging from 2.09 × 105 to 4.48 × 105 plates/m had been accomplished within 15 min. The proposed method first illustrated the effect of hydrogen bond between coating material and inner capillary surface on the coating, which should be a new strategy to design and select more effective coating materials to form more stable coatings in CE.  相似文献   
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