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131.
Phoenix S Reddy MS Deslongchamps P 《Journal of the American Chemical Society》2008,130(42):13989-13995
A full account of the total synthesis of (+)-cassaine ( 1) using the transannular Diels-Alder (TADA) reaction as the pivotal construction is described. The strategy began from Evans' oxazolidine 8, the only chiral source used for the total stereochemical outcome of the target molecule. The key intermediate 3 was obtained from 8 in 10 steps in 40% overall yield. Following extensive optimization, the coupling of 3 on both ends with another densely functional partner 2 followed by TADA reaction on macrocycle 4 cleanly furnished the tricycle 5. The stereochemical outcome in 5 was expected via a least-energetic transition state T4. A stereoselective reduction, hydroboration, and methyl cuprate 1,4-addition along with a few other functional interconversions transformed 5 into the key intermediate 37. Final tethering of dimethylaminoethyloxycarbonyl along with epimerization at C8 and alcohol deprotection at C3 yielded the natural product 1. 相似文献
132.
Pascal Gosselin Serge Masson Monique Saquet André Thuillier 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):103-104
Abstract A new synthesis of dithioesters, starting from phenylisothiocyanate is described (scheme I) and this method is convenient for the preparation of β-olefinic dithioesters (e. g. 1, scheme II). 相似文献
133.
Jean-Pierre Majoral René Mathieu Anne-Marie Caminade Serge Attali Michel Sanchez 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):443-446
Abstract A new entry to non classical phosphorus complexes is reported. 相似文献
134.
Emmanuel Mikros George Labrinidis Serge Pérez 《Journal of carbohydrate chemistry》2013,32(9):1319-1349
ABSTRACT Relaxed-residue energy maps based on the MM3 force field were computed for the methyl glycosides of eight C-linked D-glucosyl disaccharides: the two-bond axial-equatorial linked disaccharides β-kojibioside [(1→2)α–], β-nigeroside [(1→3)α–] and β-maltose [(1→4)α–], the two-bond equatorial-equatorial linked disaccharides β-sophoroside [(1→2)β–], β–laminarabioside [(1→3)β-], β–cellobioside [(1→4)β–] and the three-bond-linked (1→6) disacharides C-isomaltoside and C-gentiobioside. Optimized structures were calculated on a 20° grid spacing of the torsional angles about the C-glycosidic bonds and the final isoenergy surfaces were based on 11664 conformations, for the two-bond-linked disaccharides and 69984 conformations for the three-bond-linked disaccharides. Boltzmann-weighted 3J coupling constants were calculated and compared to the experimental values. They are satisfactory except for maltose where hydrogen bonds cause an over-estimation of the energy differences between the conformers. The energy maps are similar to maps of the corresponding O-disaccharides, but there are differences in the locations and the relative energies of the minima. The preferred conformations of the C-glycosidic bonds are as if they were conforming to the exo-anomeric effect but are closer to staggered conformations than shown by the MM3 results for the O-linkages. 相似文献
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136.
The influence of the increase of the solution ionic strength on the flocculation of charged latex particles in the presence of cationic polymers is reported. Empirical flocculation rate constants are experimentally determined using particle counting and for two cationic polymers, one linear and the second with two branches. Comparisons are made with a solution containing monovalent salt only at different ionic concentrations in the absence of polymers. In all cases, polymer-induced flocculation is significantly more efficient than charge screening effects using salt only. Analysis of zeta potential measurements indicates that the charge neutralization and surface charge variations dictate the stability of the latex suspensions. Moreover, the addition of a small amount of salt in the polymer–particle mixtures results in a dramatic decrease of the polymer efficiency which is more pronounced for the linear polymeric flocculant. By increasing further the ionic strength, the rates of polymer flocculation are found to increase again but remain smaller than in the absence of salt. 相似文献
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140.
Wilk A Grajkowski A Bull TE Dixon AM Freedberg DI Beaucage SL 《Journal of the American Chemical Society》2002,124(7):1180-1181
The determination of the absolute configuration of deoxyribonucleoside cyclic N-acylphosphoramidites at phosphorus toward the synthesis of P-stereodifined phosphorothioated oligodeoxyribonucleotides is easily accomplished with computer-assisted molecular modeling and M-GOESY NMR spectroscopy. Specifically, computer-modeling diasteromeric phosphoramidite 3 has identifed a proximal (2.55 A) through-space interaction between benzylic H-5 and sugar H-2' ', which can predictably be detected by M-GOESY NMR in SP-3 but not in RP-3 because of being too distant (5.85 A). Consistent with computer-assisted modeling predictions, M-GOESY NMR spectra of SP-3 and RP-3 revealed NOE signals generated from nuclei near the selectively excited H-2' ' that are common to both SP-3 and RP-3, namely those of H-2', H-4', H-3', and H-1'. In addition, a diagnostic NOE signal at 5.5 ppm (benzylic H-5) is, as predicted, only detected in SP-3 and thus provides an unequivocal assessment of the configuration of the diastereomer at phosphorus. M-GOESY NMR data also confirm that the condensation of deoxyribonucleoside cyclic N-acylphosphoramidites with base-activated nucleosidic or nucleotidic 5'-hydroxyls proceeds via a single nucleophilic event. 相似文献