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71.
Christiane Santelli-Rouvier Maurice Santelli Jean-Pierre Zahra 《Tetrahedron letters》1985,26(9):1213-1216
(+)-2-carene heated neat with iron pentacarbonyl leads to α-phellandrene-Fe(CO)3 complex ( ~15 % ), p. cymene ( ~15 % ), (-)-(1S)-3,8,8-trimethylbicyclo (4.1.1) oct-3-ene-7-one ( ~50 % ) and (+)-(1S,7S)-3,8,8-trimethylbicyclo (4.1.1.) oct-3-ene-7-ol ( ~20 % ). 相似文献
72.
Kütt A Movchun V Rodima T Dansauer T Rusanov EB Leito I Kaljurand I Koppel J Pihl V Koppel I Ovsjannikov G Toom L Mishima M Medebielle M Lork E Röschenthaler GV Koppel IA Kolomeitsev AA 《The Journal of organic chemistry》2008,73(7):2607-2620
A general route to functionalized pentakis(trifluoromethyl)phenyl (C6(CF3)5) derivatives, promising building blocks for designing novel stable carbenes, radical species, superacids, weakly coordinating anions and other practically and theoretically useful species, is presented. This pertrifluoromethylation route proceeds via conveniently pregenerated (trifluoromethyl)copper (CF3Cu) species in DMF, stabilized by addition of 1,3-dimethyl-2-imidazolidinone (DMI). These species react with hexaiodobenzene at ambient temperature to give the potassium pentakis(trifluoromethyl)phenoxide along with hexakis(trifluoromethyl)benzene and pentakis(trifluoromethyl)benzene in a combined yield of 80%. A possible reaction pathway explaining the formation of pentakis(trifluoromethyl)phenoxide is proposed. Pentakis(trifluoromethyl)phenol gives rise to easily functionalized pentakis(trifluoromethyl)chlorobenzene and pentakis(trifluoromethyl)aniline. Pertrifluoromethylation of pentaiodochlorobenzene and pentaiodotoluene allows straightforward access to pentakis(trifluoromethyl)chlorobenzene and pentakis(trifluoromethyl)toluene, respectively. XRD structures of several C6(CF3)5 derivatives were determined and compared with the calculated structures. Due to the steric crowding the aromatic rings in all C6(CF3)5 derivatives are significantly distorted. The gas-phase acidities (Delta Gacid) and pKa values in different solvents (acetonitrile (AN), DMSO, water) for the title compounds and a number of related compounds have been measured. The origin of the acidifying effect of the C6(CF3)5 group has been explored using the isodesmic reactions approach. 相似文献
73.
74.
Comprehensive multi-residue method for the target analysis of pesticides in crops using liquid chromatography-tandem mass spectrometry 总被引:1,自引:0,他引:1
A liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS) multi-residue method for the simultaneous target analysis of a wide range of pesticides and metabolites in fruit, vegetables and cereals has been developed. Gradient elution has been used in conjunction with positive mode electrospray ionization tandem mass spectrometry to detect up to 171 pesticides and/or metabolites in different crop matrices using a single chromatographic run. Pesticide residues were extracted/partitioned from the samples with acetone/dichloromethane/light petroleum. The analytical performance was demonstrated by the analysis of extracts from lettuce, orange, apple, cabbage, grape and wheat flour, spiked at three concentration levels ranging from 0.01 to 0.10 mg/kg for each pesticide and/or metabolite. In general, recoveries ranging from 70 to 110%, with relative standard deviations better than 15%, were obtained. The recovery and repeatability data are in good accordance with EU guidelines for pesticide residue analysis. The limit of quantification for all targeted pesticides and metabolites tested was 0.01 mg/kg. The selectivity and robustness of the LC-MS/MS method was demonstrated by a 1-year comparison of its analytical results with those obtained from our validated GC and LC multi-residue methods applied to more than 3500 routine samples. The validated LC-MS/MS method has been implemented in our analytical scheme since 2004, replacing four of the conventional detection methods, i.e. GC-flame-photometric detection (acephate, methamidophos, etc.), GC-nitrogen-phosphorus detection, LC-UV detection (carbendazim, thiabendazole, imazalil and prochloraz) and LC-fluorescence detection (N-methylcarbamate pesticides). During a 3-year period, the LC-MS/MS method has been applied to the analyses of more than 12,000 samples. 相似文献
75.
Mourad MC Devid EJ van Schooneveld MM Vonk C Lekkerkerker HN 《The journal of physical chemistry. B》2008,112(33):10142-10152
Colloidal platelets of hydrotalcite, a layered double hydroxide, have been prepared by coprecipitation at pH 11-12 of magnesium nitrate and aluminum nitrate at two different magnesium to aluminum ratios. Changing the temperature and ionic strength during hydrothermal treatment, the platelets were tailored to different sizes and aspect ratios. Amino-modified polyisobutylene molecules were grafted onto the platelets following a convenient new route involving freeze-drying. Organic dispersions in toluene were prepared of the particles with the largest size and highest aspect ratio. The colloidal dispersions prepared in this way showed isotropic-nematic phase transitions above a limiting concentration in a matter of days. The number density at the transition and the width of the biphasic region were determined and compared to theory. The orientation of the platelets in nematic droplets (tactoids) and at the isotropic-nematic interface were analyzed by polarization microscopy. It was observed that sedimentation induces a nematic layer in samples that are below the limiting concentration for isotropic-nematic phase separation. No nematic phase was observed in the initial aqueous suspensions of the ungrafted particles. 相似文献
76.
Discrimination of bacteria from Jamaican bauxite soils using laser-induced breakdown spectroscopy 总被引:1,自引:0,他引:1
Lewis DE Martinez J Akpovo CA Johnson L Chauhan A Edington MD 《Analytical and bioanalytical chemistry》2011,401(7):2225-2236
Soil bacteria are sensitive to ecological change and can be assessed to gauge anthropogenic influences and ecosystem health.
In recent years, there has been a significant increase in the focus on new technologies that can be applied to the evaluation
of soil quality. Laser-induced breakdown spectroscopy (LIBS) is a promising technique that has been used for the investigation
and characterization of explosives, solids, liquids, gases, biological and environmental samples. In this study, bacteria
from un-mined and a chronosequence of reclaimed bauxite soils were isolated on Luria–Bertani agar media. Polymerase chain
reaction amplification of the bacterial 16S rDNA, sequencing, and phylogenetic analysis were applied to each isolated soil
bacteria from the sample sites resulting in the identification and classification of the organisms. Femtosecond LIBS performed
on the isolated bacteria showed atomic and ionic emission lines in the spectrum containing inorganic elements such as sodium
(Na), magnesium (Mg), potassium (K), zinc (Zn), and calcium (Ca). Principal component analysis and partial least squares regression
analysis were performed on the acquired bacterial spectra demonstrating that LIBS has the potential to differentiate and discriminate
among bacteria in the un-mined and reclaimed chronosequence of bauxite soils. 相似文献
77.
78.
Maurice M. Bursey Donald J. Harvan J. Ronald Hass Ernest I. Becker Byron H. Arison 《Journal of mass spectrometry : JMS》1985,20(3):194-196
A correlation of fragment ion intensity with critical energy found in the collisional activation spectra of [C4Ph]+˙ ions produced by electron impact can also be found in the unimolecular mass-analysed ion kinetic energy spectra of these ions. The P(E) functions of the unimolecular and collisionally activated ions should differ not only in width but also in structure and therefore, the hypothesis that P(E) functions do not have an important effect on these correlations is tested successfully. 相似文献
79.
Ion-molecule reactions with the trimethylsilyl ion were used to distinguish between cis- and trans-1,2-cyclopentanediol isomers. The ion kinetic energy of [Si(CH3)3]+ was varied from 0 eV to 15 eV (center of mass frame of reference). At low ion kinetic energies (<4 eV), there are significant differences in the relative stabilities and decomposition behavior of the adduct ions [M + Si(CH3)3]+. The cis-1,2-cyclopentanediol isomer favors decomposition of [M + Si(CH3)3]+ to yield the hydrated trimethylsilyl ion [Si(CH3)3OH2]+ at m/z 91. For the trans isomer, the formation of the hydrated trimethylsilyl ion is an endothermic process with a definite threshold ion kinetic energy. 相似文献
80.
cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H5)]2 efficiently catalyses the Heck reaction of β-substituted enol ethers with aryl bromides. Employing β-methoxystyrene, 3-ethoxyacrylonitrile or methyl 3-methoxyacrylate, the regioselective α-arylation of these enol ethers was observed in all cases, and mixtures of Z and E isomers were generally obtained, which in many cases yielded a single ketone product after acid treatment. The stereoselectivity of this reaction depends on steric and electronic factors, and better stereoselectivities in favour of Z isomers were observed with electron-rich or sterically congested aryl bromides. Better yields were obtained for this reaction with electron-rich or sterically congested aryl bromides than with electron-poor aryl bromides. This observation suggests that with these β-substituted enol ethers the rate-limiting step of the catalytic cycle is not the oxidative addition of the aryl bromide to the palladium complex. 相似文献