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101.
Arikainen EO Boden N Bushby RJ Lozman OR Vinter JG Wood A 《Angewandte Chemie (International ed. in English)》2000,39(13):2333-2336
102.
Yamamoto A Akiba N Kodama S Matsunaga A Kato K Nakazawa H 《Journal of chromatography. A》2001,928(2):139-144
A multi-beam circular dichroism (CD) detector which is easily constructed by inserting inexpensive optics into a conventional photo-diode array detector has an advantage of simultaneous detection of the absorbance and CD. The enantiomeric purity determination of malic acid in beverages was performed by this detection system. Malic acid when complexed with Cu(II) was found to have an absorbance maximum at around 750 nm. The L-malic acid-Cu(II) complex showed a positive Cotton effect in its absorbance band and its anisotropy factor (delta epsilon/epsilon) was relatively large at about 1/170. This complex was retained on a reversed-phase column with the addition of racemic 2-hydroxy-3-methylbutyric acid to the mobile phase as the ligand. A plot of the relative peak areas between the CD and the absorption (delta abs/abs) versus optical purity showed good linearity with a correlation coefficient of 0.999, and the precision expressed as the relative standard deviation of the errors from the regression line was +/-2.7% (2sigma). The accuracy of the proposed method was assessed by capillary electrophoresis. Eight commercially available juice products were analyzed using this method. Five of them were thought to be adulterated with synthetic malic acid. 相似文献
103.
The one-pot cyclocondensation of 2,6-diaminopyrimidin-4-one, an aromatic or aliphatic aldehyde and a beta-ketoester in acetic acid, or dimethyl sulfoxide in the presence of zinc(II) bromide, under thermal conditions provided dihydropyrido[2,3-d]pyrimidin-4(3H)-ones in good yield and with total regiocontrol. 相似文献
104.
Minamide T Mitsubayashi K Jaffrezic-Renault N Hibi K Endo H Saito H 《The Analyst》2005,130(11):1490-1494
Methyl mercaptan (MM) is known as one of the major chemicals of halitosis (bad breath). In this study, a bioelectronic gas sensor (bio-detector) for gaseous MM was developed and was applied to measure halitosis in breath. The bio-detector consisted of a Clark-type dissolved oxygen electrode, a monoamine oxidase type-A (MAO-A) immobilized membrane and a reaction unit that had liquid and gaseous compartments separated by a hydrophobic porous polytetrafluoroethylene (PTFE) diaphragm membrane. The tip of the electrode covered with MAO-A membrane was placed into the liquid compartment as touching to the PTFE diaphragm membrane. In order to amplify the bio-detector output, a substrate regeneration cycle caused by coupling the monooxygenase with l-ascorbic acid as reducing reaction with reagent system, was applied. The results of MM vapor measurements showed the calibration range of the bio-detector for MM vapor was from 0.087 to 11.5 ppm (correlation coefficient: 0.993) and included the human sense of smell level 5 (0.2 ppm). The bio-detector had good selectivity being attributed to enzyme specificity was obtained for several substances (trimethyl amine, ammonia, dimethyl sulfide, etc.). The bio-detector was applied for halitosis measurement. Expired gases in five subjects were sampled every hour and the concentrations of MM in the expired gases were monitored. The output of bio-detector showed behaviour of halitosis level changes in a day such as increasing with passage of time and decreasing after eating. 相似文献
105.
Simultaneous determination of copper, zinc, cadmium and mercury with high sensitivity is possible by neutron activation analysis. After irradiation, the samples are digested and an initial separation of the four elements made by means of an ion-exchange resin. The elements in the separated fractions are then treated to give radio-chemical purity, precipitated, and their activities measured. A purely instrumental technique for the analysis of zinc in samples of biological material is also described. The samples are irradiated for a week and after the activity has decayed for about three months it is measured on a gamma-spectrometer. 相似文献
106.
Badol C Borbon A Locoge N Léonardis T Galloo JC 《Analytical and bioanalytical chemistry》2004,378(7):1815-1827
An automated system for the monitoring of volatile organic compound (VOC) ozone precursors in ambient air is described. The measuring technique consists of subambient preconcentration on a cooled trap followed by thermal desorption and GC/FID analysis. First, the technical development, which permits detection limits below 0.05 ppbv to be reached, proceeded in two steps: (1) the determination of optimum sampling parameters (trap composition and conditioning, outlet split, desorption temperature); (2) the development of a reliable calibration method based on a highly accurate standard. Then, a 4-year field application of the hourly measuring chain was carried out at two urban sites. On the one hand, quality control procedures provided the best VOC identification (peak assignment) and quantification (reproducibility, blank system control). On the other hand, the success and performances of the routine experience (88% of the measurements covered more than 40 target compounds) indicated the high quality and suitability of the instrumentation which is actually applied in several French air quality monitoring networks. Finally, an example of data analysis is presented. Data handling identified important organic compound sources other than vehicle exhaust. 相似文献
107.
The [3,3]-sigmatropic rearrangement took place smoothly during the course of trifluoroacetylation of O-phenyloxime at below room temperature to give the dihydrobenzofuran or benzofuran as a result of concomitant cyclization. 相似文献
108.
Henriques ES Floriano WB Reuter N Melo A Brown D Gomes JA Maigret B Nascimento MA Ramos MJ 《Journal of computer-aided molecular design》2001,15(4):309-322
We present the search for a new model of -factor XIIa, a blood coagulation enzyme, with an unknown experimental 3D-structure. We decided to build not one but three different models using different homologous proteins as well as different techniques and different modellers. Additional studies, including extensive molecular dynamics simulations on the solvated state, allowed us to draw several conclusions concerning homology modelling, in general, and -factor XIIa, in particular. 相似文献
109.
This paper concerns with three series of experiments about dimethylsulfide gas phase oxidation, carried out at increasing NOx level (< 20 ppb, 1 ppm, 10 ppm) to show the relation between the amounts of nitrogen oxides and the molar yields of sulfur containing products. DMSO, DMSO2, HCHO, HCOOH and SO2 were found as main reaction products. From these experiments and from preceding studies, a sensitive decrease in the quantity of total sulfur products in aerosol phase is underlined. This result derives from the reaction of NOx with CH3S(O)O2 and CH3S(O)OO radicals, which leads to stable intermediates as methylsulphonylperoxynitrate, MSPN, with a characteristic PAN-like structure. 相似文献
110.
Claiser N Souhassou M Lecomte C Gillon B Carbonera C Caneschi A Dei A Gatteschi D Bencini A Pontillon Y Lelièvre-Berna E 《The journal of physical chemistry. B》2005,109(7):2723-2732
High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring. 相似文献