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991.
992.
Bushell JA Claybourn M Murphy DM Williams HE 《Magnetic resonance in chemistry : MRC》2006,44(10):929-935
Gamma radiation of poly (lactide-co-glycolide) raw polymers and processed microspheres under vacuum and at 77 K results in the formation of a series of free radicals. The resulting powder electron paramagnetic resonance (EPR) spectrum contains a distribution of several different radicals, depending on the annealing temperature, and is therefore difficult to interpret. By utilising the selectivity of the electron nuclear DOuble resonance (ENDOR) and associated ENDOR induced EPR (EIE) techniques, a more direct approach for the deconvolution of the EPR spectrum can be achieved. Using this approach, the radiolytically induced CH3 *CHC(O)R- chain scission radical was identified at 120 K by simulation of the EIE spectrum. At elevated temperatures (250 K), this radical decays considerably and the more stable radicals -O*CHC(O)-, CH3 *C(OR)C(O)- and CH3 *C(OH)C(O)- predominate. This work demonstrates the utility of the EIE approach to supplement and aid the interpretation of powder EPR spectra of radicals in a polymer matrix. 相似文献
993.
Rigby-Singleton SM Davies MC Harris H O'Shea P Allen S 《Langmuir : the ACS journal of surfaces and colloids》2006,22(14):6273-6279
The effect of the presequence peptide of cytochrome c oxidase subunit IV (p25) on supported phospholipid bilayers (SPBs) was visualized using atomic force microscopy (AFM). The presequence was found to cause the complete disruption of supported bilayers containing neutral lipids. At relatively low concentrations of presequence, the peptide was found to bind to the membrane, coalescing to form microdomains within the liquid-crystalline bilayer that were located predominantly at bilayer-mica boundaries. Further increases in peptide concentration resulted in the formation of holes within the SPB that were spanned by an interpenetrating network of narrower regions of the bilayer, which, at higher applied peptide concentrations, were observed to disappear through a budding process, ultimately leading to the formation of spherical structures at yet higher peptide concentrations. Within this paper, the impact the presequence has upon the structure and order of the membrane is discussed, as is the potential implication of this apparent solubilization process on the translocation of cytochrome c oxidase into the inner mitochondrial membrane. 相似文献
994.
Saracoglu S Soylak M Peker DS Elci L dos Santos WN Lemos VA Ferreira SL 《Analytica chimica acta》2006,575(1):133-137
The present paper proposes a pre-concentration procedure for determination of lead and iron in several samples by flame atomic absorption spectrometry. In it, lead(II) and iron(III) ions are coprecipitated using the violuric acid-copper(II) system as collector. Afterwards, the precipitate is dissolved with 1 M HNO3 solution and the metal ions are determined. The optimization step was performed using factorial design involving the variables: pH, violuric acid mass (VA) and copper concentration (Cu).Using the optimized experimental conditions, the proposed procedure allows the determination these metals with detection limits of 0.18 μg L−1 for iron and 0.16 μg L−1 for lead. The effects of foreign ions on the pre-concentration procedure were also evaluated and the results demonstrated that this method could be applied for determination of iron and lead in several real samples. The proposed method was successfully applied to the analysis of seawater, urine, mineral water, soil and physiological solution samples. The concentrations of lead and iron achieved in these samples agree well with others data reported in the literature. 相似文献
995.
Adsorption properties of the clay mineral montmorillonite in the potassium homoionic form (KMT) was investigated to achieve the extraction and concentration of the herbicides atrazine (AT) and propazine (PROP), as well as the main degradation products of atrazine, namely deethylatrazine (DEA), deisopropylatrazine (DIA) and hydroxyatrazine (ATOH). A batch approach was proposed, with recovery percentages for AT, PROP and DIA higher than 90% at concentrations of 0.50 and 2.50 μg L−1. For DEA and ATOH, however, low recoveries were obtained. For DEA, this fact can be explained by its low Kd with KMT, contrary to ATOH, which interacts strongly with the mineral surface, hindering the complete desorption and hence, generating low recovery percentages. The influence of pH, ionic strength and humic acid was studied, and a comparison with the C18 phase as SPE cartridges was carried out. Montmorillonite showed a similar performance to commercial cartridge for concentrations of AT, DEA and PROP, but better recoveries for DIA was obtained using the clay mineral. For ATOH the recovery was also higher on the clay mineral, although for this compound the most suitable SPE cartridge is constituted by cation exchange resin. After the concentration and elution steps, the 0.50 and 2.50 μg L−1 gave chromatographic peak areas that could be easily quantified with an analytical curve obtained in the concentration range between 7.5 and 100 μg L−1. The obtained concentration factors are suitable to allow the application of the method to the monitoring of triazine residues in drinking water. 相似文献
996.
Ketoreductase (KR) activities help determine the stereochemistry of the products of modular polyketide synthases (PKSs). For example, domains eryKR(1) and eryKR(2), contained, respectively, in the first and second extension modules of the erythromycin-producing PKS, reduce 3-ketoacyl-thioester intermediates with opposite stereospecificity. Amino acid motifs that correlate with stereochemical outcome have been identified in KRs. We have used saturation mutagenesis of these motifs in eryKR(1) and eryKR(2), and a microplate-based screen of such mutants for activity against (9R, S)-trans-1-decalone, to identify candidate enzymes potentially altered in stereocontrol. Active mutants were reassayed with (2R, S)-2-methyl-3-oxopentanoic acid N-acetylcysteamine thioester, and the alcohol products were analyzed by chiral HPLC. Variant enzymes were found with either altered substrate selectivity for the (2R) or (2S) substrate or altered stereospecificity of reduction, or both, further highlighting the importance of these motifs in stereochemical control. 相似文献
997.
Barbara Gehrhus Peter B. Hitchcock Helen Jansen 《Journal of organometallic chemistry》2006,691(4):811-816
Reaction of the thermally stable silylene Si[(NCH2But)2C6H4-1,2] (1) [abbrev. as Si(NN)] with SiX4 (X = Cl or Br) afforded the disilanes (NN)SiX(SiX3) and [(NN)SiX]2 (X = Br only), the trisilane (NN)SiX-[(SiX3)Si(NN)] and the monosilane (NN)SiX2 (X = Br only), whereas treatment of 1 with MCl4 (M = Ge or Sn) yielded (NN)SiCl2 and MCl2. [(NN)SiBr]2 and (NN)SiBr2 were also obtained by reaction of 1 with Br2. Reaction of 1 with PhSiCl3 yielded the disilane (NN)SiCl(SiCl2Ph) and trisilane [(NN)SiCl]2SiClPh, whereas the disilane (NN)SiCl(SiCl2Me) was obtained with MeSiCl3. The trisilane (NN)SiCl-[(SiCl3)Si(NN)] was thermally labile and converted to [(NN)SiCl]2SiCl2. 相似文献
998.
L.S. Cavalcante A.Z. Simões M.R.M.C. Santos J.A. Varela 《Journal of solid state chemistry》2006,179(12):3739-3743
Ca(Zr0.05Ti0.95)O3 (CZT) thin films were grown on Pt(1 1 1)/Ti/SiO2/Si(1 0 0) substrates by the soft chemical method. The films were deposited from spin-coating technique and annealed at 928 K for 4 h under oxygen atmosphere. CZT films present orthorhombic structure with a crack free and granular microstructure. Atomic force microscopy and field-emission scanning electron microscopy showed that CZT present grains with about 47 nm and thickness about 450 nm. Dielectric constant and dielectric loss of the films was approximately 210 at 100 kHz and 0.032 at 1 MHz. The Au/CZT/Pt capacitor shows a hysteresis loop with remnant polarization of , and coercive field of 18 kV/cm, at an applied voltage of 6 V. The leakage current density was about at 3 V. Dielectric constant-voltage curve is located at zero bias field suggesting the absence of internal electric fields. 相似文献
999.
1000.
3-Phosphinyl 1-aza-1,3-butadienes 2 are obtained by aldol condensation between hydrazonoalkyl phosphine oxides and N,N-dimethylformamide dimethyl acetal. Transamination reaction of these azadienes with amines yields functionalized 1-aza-1,3-butadienes 3. Cycloaddition processes of these azadienes 2a with electron-poor dienophiles to give phosphorylated pyridine derivatives 9 and 15 are also reported, while intramolecular cyclization reaction of heterodiene 2b affords phosphorylated pyrazole 17. 相似文献