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31.
Grzegorz Mlosto Jaroslaw Romaski Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》1995,78(6):1499-1510
1,3-Dipoles with a Central S-Atom from the Reaction of Azides and Thiocarbonyl Compounds: An Unexpected MeS Migration in the Trapping Product of a ‘Thiocarbonyl-aminide’ with Methyl Dithiobenzoate Reaction of PhN3 with O-methyl thiobenzoate ( 11a ) and thioacetate ( 11c ) as well as with the dithio esters 11b,d at 80° yields the corresponding imidates and thioimidates 12 (Scheme 3). The formation of 12 is rationalized by a 1,3-dipolar cycloaddition of the azide and the C?S group followed by successive elimination of N2 and S. In the three-component reaction of 11b , PhN3, and the sterically crowded thioketone 1a , 1,2,4-trithiolane 13a and 1,4,2-dithiazolidine 3a are formed in addition to 12b (Scheme 4). The heterocycles 13a and 3a are trapping products of 1a and ‘thiocarbonyl-thiolate’ 5a and ‘thiocarbonyl-aminide’ 2a (Ar?Ph), respectively (Scheme 6). These 1,3-dipoles are formed as reactive intermediates. Surprisingly, in the presence of catalytic amounts of acids, the major product is the (methyldithio)cyclobutyl thioimidate of type 14 (Scheme 5), formed by an acid-catalyzed MeS migration in dithiazolidine 17 . A reaction mechanism is proposed in Scheme 7. 相似文献
32.
Agnieszka Majchrzak Grzegorz Mlosto Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》2006,89(5):1042-1061
The reactions of 3‐chloro‐3‐(chlorosulfanyl)‐2,2,4,4‐tetramethylcyclobutan‐1‐one ( 2 ) with N, O, S, and P nucleophiles occur by substitution of Cl at the S‐atom. Whereas, in the cases of secondary amines, alkanols, phenols, thiols, thiophenols, and di‐ and trialkyl phosphates, the initially formed substitution products were obtained, the corresponding products with allyl and propargyl alcohols undergo a [2,3]‐sigmatropic rearrangement to give allyl and allenyl sulfoxides, respectively. Analogous substitution reactions were observed when 3‐chloro‐3‐(chlorodisulfanyl)‐2,2,4,4‐tetramethylcyclobutan‐1‐one ( 3 ) was treated with N, O, and S nucleophiles. The reaction of 3 with Et3P led to an unexpected product via cleavage of the S? S bond (cf. Scheme 13). In the reactions of 2 with primary amines and H2O, the substitution products react further via elimination of HCl to yield the corresponding thiocarbonyl S‐imides and the thiocarbonyl S‐oxide, respectively. Whereas the latter could be isolated, the former were not stable but could be intercepted by MeOH (Scheme 4) or adamantanethione (Scheme 5). The structures of some of the substitution products were established by X‐ray crystallography. 相似文献
33.
Martin Kgi Grzegorz Mlosto Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》1994,77(5):1299-1312
Reaction of Ethyl Diazoacetate with 1,3-Thiazole-5(4H)-thiones Reaction of ethyl diazoacetate ( 2a ) and 1,3-thiazole-5(4H)-thiones 1a,b in Et2O at room temperature leads to a complex mixture of the products 5–9 (Scheme 2). Without solvent, 1a and 2a react to give 10a in addition to 5a–9a . In Et2O in the presence of aniline, reaction of 1a,b with 2a affords the ethyl 1,3,4-thiadiazole-2-carboxylate 10a and 10b , respectively, as major products. The structures of the unexpected products 6a, 7a , and 10a have been established by X-ray crystallography. Ethyl 4H-1,3-thiazine-carboxylate 8b was transformed into ethyl 7H-thieno[2,3-e][1,3]thiazine-carboxylate 11 (Scheme 3) by treatment with aqueous NaOH or during chromatography. The structure of the latter has also been established by X-ray crystallography. In the presence of thiols and alcohols, the reaction of 1a and 2a yields mainly adducts of type 12 (Scheme 4), compounds 5a,7a , and 9a being by-products (Table 1). Reaction mechanisms for the formation of the isolated products are delineated in Schemes 4–7: the primary cycloadduct 3 of the diazo compound and the C?S bond of 1 undergoes a base-catalyzed ring opening of the 1,3-thiazole-ring to give 10 . In the absence of a base, elimination of N2 yields the thiocarbonyl ylide A ′, which is trapped by nucleophiles to give 12 . Trapping of A ′, by H2O yields 1,3-thiazole-5(4H)-one 9 and ethyl mercaptoacetate, which is also a trapping agent for A ′, yielding the diester 7 . The formation of products 6 and 8 can be explained again via trapping of thiocarbonyl ylide A ′, either by thiirane C (Scheme 6) or by 2a (Scheme 7). The latter adduct F yields 8 via a Demjanoff-Tiffeneau-type ring expansion of a 1,3-thiazole to give the 1,3-thiazine. 相似文献
34.
35.
Szmytkowski C Piotrowicz M Domaracka A Kłosowski L Ptasińska-Denga E Kasperski G 《The Journal of chemical physics》2004,121(4):1790-1795
Absolute total cross sections (TCSs) for electron scattering from boron trifluoride (BF(3)) and phosphorus trifluoride (PF(3)) molecules have been measured using a linear transmission method. The electron energy ranges from 0.6 to 370 eV for BF(3) and from 0.5 to 370 eV for PF(3). The TCS energy dependence for BF(3) exhibits two very pronounced enhancements: resonantlike narrow feature located near 3.6 eV with the maximum value of 19.2 x 10(-20) m(2), and intermediate energy very broad enhancement with two humps, one centered around 21 eV (18.8 x 10(-20) m(2) in the maximum) and the other near 45 eV (19.5 x 10(-20) m(2)). For PF(3) the TCS has quite different low-energy dependence: at 0.5 eV it has a high value of 70 x 10(-20) m(2) and decreases steeply towards higher energies. Beyond the minimum near 5.5 eV, the TCS reveals two distinct humps: the resonant one centered near 11 eV with the peak value of 32.9 x 10(-20) m(2) and the second one much broader around 35 eV (27.9 x 10(-20) m(2)). The present TCSs for trifluorides are compared to each other as well as to previous TCS data for selected perfluorides and to results for their perhydrided counterparts. The differences and similarities in the shape and magnitude of TCSs are pointed out. 相似文献
36.
Anna Katafias Olga Impert Przemysław Kita Grzegorz Wrzeszcz 《Transition Metal Chemistry》2004,29(8):855-860
Oxidation of the trans-[Cr(cyca)(OH)2]+ complex, where cyca = meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, by [Fe(CN)6 ]3- ion in strongly alkaline media, leading to [CrV O(cycaox )]3+ ion, has been studied using electronic and e.p.r. spectroscopy. The kinetics of the CrIII → CrIV transformation have been studied using a large excess of the reductant and OH- ion over the oxidant. The reaction is a second order process: first order in [CrIII] and [FeIII] at constant [OH-]. The second order rate constant is higher than linearly dependent on the OH- concentration. The mechanism of the reaction has been discussed. A relatively inert intermediate chromium(V) species was detected based on characteristic bands in the visible region and the e.p.r. signal at giso = 1.987 for the systems where an excess of oxidant was used. The hyperfine structure of the main e.p.r. signal is consistent with the d1 -electron interactions with four equivalent nitrogen nuclei and [CrV = O(cycaox)]3+ formula, where cycaox = oxidized cyca, can be postulated for the intermediate CrV complex. 相似文献
37.
Alicja Boryło Bogdan Skwarzec Grzegorz Romańczyk Janusz Siebert 《Journal of Radioanalytical and Nuclear Chemistry》2013,298(3):1685-1691
The determination of polonium 210Po in human blood samples is presented and discussed in this paper. The human blood samples were collected from patients of Medical University of Gdańsk with ischaemic heart disease (morbus ischaemicus cordis, MIC). The polonium concentrations in analyzed human blood samples are very differentiated. 210Po is of particular interest in public health and although is present in the environment in extremely low amounts, it is easily bioaccumulated to the human body. The study shows that the amount of 210Po that is incorporated into the human body depends on the food habits and some difference in its levels could be observed between smokers and non-smokers. 相似文献
38.
39.
Grzegorz Mlostoń Aneta Wróblewska Emilia Obijalska Heinz Heimgartner 《Tetrahedron: Asymmetry》2013,24(15-16):958-965
Starting with (S)-1-benzylprolinamine and α-hydroxyimino ketones, enantiomerically pure bisheterocyclic imidazole N-oxides bearing the (S)-configured N-benzyl(pyrrolidin-2-yl)methyl residue were prepared. These N-oxides reacted with 2,2,4,4-tetramethylcyclobutane-1,3-dithione to give the corresponding optically active imidazole-2-thione derivatives via a sulfur transfer reaction. Reduction of the N-oxides with Raney-nickel led to deoxygenation, whereas catalytic hydrogenation (Pd/C) in ethanol occurred with simultaneous deoxygenation and debenzylation, leading to optically active 1-(pyrrolidin-2-yl)methyl-1H-imidazoles. Alkylation of the prepared imidazole N-oxides and their respective imidazoles with butyl and hexyl bromide and subsequent anion exchange gave optically active N-alkoxy- and N-alkylimidazolium tetrafluoroborates, respectively, with the properties of ‘room temperature ionic liquids’. 相似文献
40.
We comment on a recent paper [J Opt Laser Technol 43 (2011) 430–436] in which the authors introduce dispersion and attenuation models of spatially multiplexed channels in step index multimode fibers. We consider the theoretical explanation of the model given in the paper incorrect. 相似文献