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91.
Frabetti PL Cheung HW Cumalat JP Dallapiccola C Ginkel JF Greene SV Johns WE Nehring MS Butler JN Cihangir S Gaines I Garren L Garbincius PH Gourlay SA Harding DJ Kasper P Kreymer A Lebrun P Shukla S Bianco S Fabbri FL Sarwar S Zallo A Culbertson R Gardner RW Greene R Wiss J Alimonti G Bellini G Caccianiga B Cinquini L Di Corato M Giammarchi M Inzani P Leveraro F Malvezzi S Menasce D Meroni E Moroni L Pedrini D Perasso L Sala A Sala S Torreta D Vittone M Buchholz D Claes D Gobbi B O'Reilly B 《Physical review letters》1993,70(14):2058-2061
92.
Frabetti PL Cheung HW Cumalat JP Dallapiccola C Ginkel JF Greene SV Johns WE Nehring MS Butler JN Cihangir S Gaines I Garren L Garbincius PH Gourlay SA Harding DJ Kasper P Kreymer A Lebrun P Shukla S Bianco S Fabbri FL Sarwar S Zallo A Culbertson R Gardner RW Greene R Wiss J Alimonti G Bellini G Caccianiga B Cinquini L Di Corato M Giammarchi M Inzani P Leveraro F Malvezzi S Menasce D Meroni E Moroni L Pedrini D Perasso L Sala A Sala S Torretta D Vittone M Buchholz D Claes D Gobbi B O'Reilly B 《Physical review letters》1993,70(10):1381-1384
93.
Frabetti PL Cheung HW Cumalat JP Dallapiccola C Ginkel JF Greene SV Johns WE Nehring MS Butler JN Cihangir S Gaines I Garren L Garbincius PH Gourlay SA Harding DJ Kasper P Kreymer A Lebrun P Shukla S Bianco S Fabbri FL Sarwar S Zallo A Culbertson R Gardner RW Greene R Wiss J Alimonti G Bellini G Caccianiga B Cinquini L Di Corato M Giammarchi M Inzani P Leveraro F Malvezzi S Menasce D Meroni E Moroni L Pedrini D Perasso L Sala A Sala S Toretta D Vittone M Buchholz D Claes D Gobbi B O'Reilly B 《Physical review letters》1993,70(12):1755-1758
94.
95.
Photodegradation of Polychlorinated Dibenzo-p-dioxins in Liquid Samples by Near UV Light Irradiation
Photodegradation of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) in hexane solution was studied under controlled near-UV light exposure in the spectral region from 325 to 269 nm. GC-MS was used to detect the amount of unreacted dioxin and to characterize the relevant degradation products. Irradiation experiments carried out at a constant light energy (700 mJ) showed that the percentage of 1,2,3,4-TCDD left in the solution after irradiation changed from about 55 to 75%, with a minimum of 55% at 310 nm. Further irradiation experiments carried out at two wavelengths, namely 310 and 269 nm, and light energy ranging from 0 to 4000 mJ, showed that the photodegradation reaction of the TCDD always followed a pseudo-first-order kinetic, with a rate constant of 8 × 10−4and 5 × 10−4mJ−1, respectively. These experiments also showed that trichloro- and dichloro-dibenzo-p-dioxins were produced with less than 15% of the initial quantity of TCDD, leading to the conclusion that the dechlorination process is a minor photolysis pathway. 相似文献
96.
Trichochromes, the peculiar pigments of red human hair, featuring the Delta(2,2)(')-bi(2H-1,4-benzothiazine) skeleton, are known to arise from cysteinyldopas, mainly the 5-S-isomer (5). However, the mode of formation and the direct precursors have remained largely undefined. To fill this gap, we investigated the oxidation of 5 in air or with chemical and enzymatic agents under biomimetic conditions. In the presence of zinc ions, which occur in epidermal tissues at significant concentrations, the reaction course is diverted toward the formation of a labile 3-carboxy-2H-1,4-benzothiazine intermediate (11), which was identified by direct NMR analysis. Structural formulation was supported by characterization of the analogous compound 13 isolated from oxidation of the model 5-methyl-3-S-cysteinylcatechol (12) after methylation. In the further stages of the oxidation, diastereomeric 2,2'-bi(2H-1,4-benzothiazine) 15 and 14 were obtained from 5 and 12, respectively, the reaction proceeding at a higher rate and to a greater extent in the presence of acids. The dimers were shown to readily convert to each other in the presence of acids. In the case of the methylated dimers 14, a 2,2'-bi(4H-1,4-benzothiazine) intermediate (16) was isolated and characterized. In acidic media, trichochrome C (1a), the most abundant in red human hair, was smoothly formed from aerial oxidation of 15, and under similar conditions, trichochrome-related products (17 and 18) were obtained from 14 prior to or after methylation. The presence of 1a and precursors 5 and 15 was investigated by HPLC analysis of red hair samples following mild proteolytic digestion. On the basis of these data, a likely biosynthetic route to trichochrome pigments of red human hair is depicted. 相似文献
97.
Claudio Tavagnacco Gabriele Balducci Giacomo Costa Karl Tschler Wolfgang von Philipsborn 《Helvetica chimica acta》1990,73(5):1469-1480
In four series of strictly related organocobalt complexes, derived from cobaloximes by replacement of the O…H…O with O…-BF2…O and/or (CH2)3 groups, the trends of 59Co-NMR shielding and electrochemical data are discussed. A largely parallel behaviour of the plots of E1/2(I) values for the first Co(III)/Co(II) electron transfer vs. the 59Co chemical shifts reflects the similar sensitivity of the two parameters to a change in electron affinity of the central metal ion due to a variation of the organic group R. E1/2(II) values for the second Co(II)/CO(I) electron transfer are less sensitive to the change of R, but the trend of the plot vs. δ(59Co) is still parallel in the four series. Consistent deviations from a roughly linear dependence of E1/2(I) on pKa of the hydrocarbon acid corresponding to R, on Taft constant s?* and on 59Co shielding are noticed for the isopropyl derivatives and attributed to a steric effect. This was confirmed in a series of R? Co(DMG)pyridine complexes in which 59Co shielding decreases steadily with increasing steric parameter Es (Taft) of the alkyl group. There is experimental evidence from X-ray data that δ(59Co) decreases with an increase of the Co? C bond length, illustrating steric hindrance in alkyl coordination to be responsible for the decreased shielding of the 59Co nucleus. The relative displacements of the graphic displays for the different series reflect the effect of changes in electron affinity of the redox center, due to the equatorial ligand, which, in turn, is caused by variations in the electron-withdrawing power due to the introduction of the BF2 group and by the change from ?2 to ?1 valence of the (CH2)3-capped ligands. 相似文献
98.
Paolesse R Monti D La Monica L Venanzi M Froiio A Nardis S Di Natale C Martinelli E D'Amico A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2476-2483
Porphyrin diad 1 was synthesized by reaction of the acyl chloride of porphyrin 2 and trans-1,2-dithiane-4,5-diol. The Co complex of this diad was studied as a potential enantioselective receptor for chiral recognition in solution and in the solid state. In solution both enantiomers of limonene induce significant changes in the visible and circular dichroism (CD) spectra of [Co2(1)], while a different behavior is observed in the case of the enantiomeric pair of trans-1,2-diaminocyclohexane. A different efficiency of [Co2(1)] chiral recognition is obtained for these compounds, with a remarkable degree of enantiodiscrimination observed in the case of limonene. Self-assembled monolayers of [Co2(1)] were deposited onto the gold electrodes of quartz crystal microbalances to be used as sensing materials of nanogravimetric sensors operating in the gas phase. The enantiodiscrimination properties of these sensors towards the enantiomeric pairs of chiral analytes have been studied. While in the case of analytes bearing donor ligand atoms we did not observe a remarkable enantioselectivity, a significant degree of chiral discrimination was observed in the case of limonene; this result is particularly encouraging for the potential development of enantioselective chemical sensors for use in an array configuration. 相似文献
99.
Francesco Malatesta Giacomo Carrara Maria Perla Colombini Ambrogio Giacomelli 《Journal of solution chemistry》1993,22(8):733-749
The activity coefficients of Co(en)3Cl3 and K2SO4 were measured by means of a cell with ion-exchange liquid membranes following the method described in paper I. The results prove that this method is even more valuable with multicharged salts than with 1-1 electrolytes. The values obtained are precise and reliable down to dilution limits never before accessible, e.g., 4×10–5 mol-kg–1 in Co(en)3Cl3. High dilution levels are of particular importance when dealing with highly charged electrolytes since the trend at higher concentrations often leads to errors both in extrapolation to infinite dilution and in the absolute activity coefficients. As an application, the activity coefficients of [Co(en)3]2(SO4)3-suspected to be wrongly evaluated in past literature-were measured, and their values at low concentrations were actually lower than those quoted before. 相似文献
100.
The reductive alkylation of amine with carbonyl compounds usingsodium hydrogen telluride has been investigated in recent years.Application of this method to the synthesis of N-alkyl derivativesof biologically important amino acids and their esters is described. 相似文献