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21.
Alberto Bargagna Gaetano Bignardi Pietro Schenone Mario Longobardi 《Journal of heterocyclic chemistry》1983,20(4):839-843
The polar 1, 4-cycloaddition of phenylsulfene (generated in situ from phenylmethanesulfony] chloride and triethylamine) to N, N-disubstituted (E)-2-aminomethylenecyclohexanones I gave in general a mixture of N, N-disubstituted cis- and trans-4-amino-3, 4, 5, 6, 7, 8-hexahydro-3-phenyl-1, 2-benzoxathiin 2, 2-dioxides III and IV, which were separated by column chromatography and whose structural and conformational features were determined from uv, ir and nmr spectral data. In the case of N, N-diisopropylamino enaminone 1c, the cyclo-addition took place with elimination of an alkyl group as propene to give the adduct III?. 相似文献
22.
Monfrecola G Procaccini EM D'Onofrio D Roberti G Liuzzi R Staibano S Manco A De Rosa G Santoianni P 《Journal of photochemistry and photobiology. B, Biology》2002,68(2-3):147-155
Photodynamic therapy (PDT) with 5-aminolaevulinic acid (ALA) is an alternative tool for the treatment of superficial non-melanoma skin cancers. Recently ALA-PDT has been employed with encouraging results also for warts, condylomata and psoriasis. In this study the effects of topical ALA plus irradiation with visible light on intact human skin have been evaluated. Five skin areas (A, B, C, D, and E) on the inner upper part of the arms of five healthy volunteers (skin types III and IV) were treated with (A) ALA 20% in base cream without irradiation, (B) only the vehicle (base cream) without ALA, (C, D and E) ALA cream at the concentrations of 5, 10 and 20%, respectively; all treatments were applied with an occlusive dressing. Four hours after ALA or vehicle application areas B, C, D and E were irradiated with a fixed dose of 40 J/cm(2). ALA penetration through the intact skin was evaluated by in vivo fluorescence determination. The effects on healthy skin were evaluated by clinical and chromometric examinations, light microscopy, immunohistochemistry and electron microscopy. RESULTS: (1) in vivo fluorescence demonstrated that ALA is able to penetrate through the intact skin, when applied with occlusive dressing and induces a classical fluorescence peak due to Protoporphyrin IX (PpIX) formation, which is the active photosensitiser. (2) Skin areas receiving ALA plus irradiation showed erythema and swelling just after the irradiative session and hyperpigmentation 48-72 h later. (3) Colourimetric data confirmed significant skin colour changes: values a* (representing the erythematous changes) increased only on the skin areas where ALA+irradiation were applied and during the 48 h after irradiation, thereafter a* began to decrease; values L* (pigmentation) increased during the 2 weeks following treatment. (4) Histopathological, immunohistochemical (S100, HMB-45) and electron microscopic findings showed an absolute increment of the number of melanocytes, which appeared clearly activated. In conclusion the application of ALA cream followed by irradiation is able to induce a pigmentation response in healthy human skin, at least in skin types III and IV. This melanocytic activation could have a potential for the treatment of skin disorders characterised by hypopigmentation. 相似文献
23.
The reaction of sulfene with N,N-disubstituted 3-aminomethylene-2,3-dihydro-4-thiochromanones and-2,3,5,6-tetrahydro-4-thiopyranones gave 1,4-cycloadducts which are derivatives of new heterocyclic systems, namely 3,4-dihydro-5H-[1]benzothiopyrano[3,4-e]-1,2-oxathiin and 3,4,7,8-tetrahydro-5H-thiopyrano[3,4-e]-1,2-oxathiin, respectively. Furthermore, some pyrazole derivatives VII and VIII were prepared from 3-hydroxymethylene-2,3-dihydro-4-thiochromanone or 2,3,5,6-tetrahydro-4-thiopyranone and hydrazines. 相似文献
24.
The polar 1,4-cycloaddition of dichloroketene to N,N-disubstituted (E)-5-aminomethylene-1,5,6,7-tetrahydro-(1-methyl)(1-phenyl)-4H-indazol-4-ones V, prepared from 1,5,6,7-tetrahydro-(1-methyl)(1-phenyl)-4H-indazol-4-ones via the 5-hydroxymethylene derivatives, gave in good yield N,N-disubstituted 4-amino-3,3-dichloro-4,5,6,7-tetrahydro-(7-methyl)(7-phenyl)pyrano[2,3-e]indazol-(3H)ones VI, which are derivatives of the new heterocyclic system pyrano[2,3-e]indazole. Dehydrochlorination of VI with DBN afforded N,N-disubstituted 4-amino-3-chloro-6,7-dihydro(7-methyl)(7-phenyl)pyrano[2,3-e]indazol-2(5H]-ones VII generally in satisfactory yield. Full aromatization with DDQ of VII was tried only in the case of dimethylamino derivatives, giving a moderate yield of 3-chloro-4-dimethylamino(7-methyl)(7-phenyl)pyrano[2,3-e]indazol-2(7H)-ones. Cycloaddition of sulfene to V occurred only in the case of aliphatic N-substitution to give in moderate yield 4-dialkylamino-4,5,6,7-tetrahydro-(7-methyl)(7-phenyl)-3H-1,2-oxathiino[6,5-e]indazole 2,2-dioxides, which are derivatives of the new heterocyclic system 1,2-oxathiino[6,5-e]indazole. 相似文献
25.
Alberto Bargagna Pietro Schenone Francesco Bondavalli Mario Longobardi 《Journal of heterocyclic chemistry》1980,17(1):33-37
Cycloaddition of sulfene to N,N-disubstituted 4-amino-3-methyl-3-buten-2-ones (III) occurred in fair to good yield only in the case of aliphatic N-substitution to give 4-dialkylamino-3,4-dihydro-5,6-dimethyl-1,2-oxathiin 2,2-dioxides, whereas N,N-disubstituted 1-amino-1-penten-3-ones (II) did not react at all. Cycloaddition of dichloroketene to II, III and N,N-disubstituted 4-amino-3-buten-2-ones occurred only in the case of the methylphenylamino derivative, giving in good to moderate yield 6,(5)(di)alkyl-3,3-dichloro-3,4-dihydro-4-methylphenylamino-2-Hpyran-2-ones, which were dehydrochlorinated with DBN to 6,(5)(di)alkyl-3-chloro-4-methylphenylamino-2H-pyran-2-ones. 相似文献
26.
Marotta E Lapolla A Fedele D Senesi A Reitano R Witt M Seraglia R Traldi P 《Journal of mass spectrometry : JMS》2003,38(2):196-205
The Maillard reaction occurring between sugars and amino groups is important in living systems. When amino groups belonging to protein chains are involved, the Maillard reaction has been invoked as responsible for protein cross-linking and the production of 'toxic' compounds. The reaction leads to the production of a heterogeneous group of substances, usually called advanced glycation end products (AGEs). Classical analytical approaches, such as spectroscopic (ultraviolet, fluorescence) and mass spectrometric (matrix-assisted laser desorption/ionization, liquid chromatography/electrospray ionization mass spectrometry) methods, have shown that the digestion mixture is highly complex. However, there are clear differences between the digestion mixtures of glycated and unglycated human serum albumin (HSA). In the former case, possible glycated peptides belonging to the AGE peptide class may be identified. Tandem mass spectrometric experiments on selected species seemed to be promising as regards structural information, but it was thought of interest to undertake the present investigation, based on liquid chromatography/electrospray ionization Fourier transform mass spectrometry, in order to obtain definitive results on their elemental composition. Using this approach, about 20 glycated peptides were detected and their possible structures were postulated by examining the known sequence of HSA. 相似文献
27.
Alberto Ballistreri Domenico Garozzo Mario Giuffrida Pietro Maravigna Giorgio Montaudo 《Journal of polymer science. Part A, Polymer chemistry》1986,24(2):331-346
The thermal fragmentation processes in poly-Schiff bases have been investigated by direct pyrolysis–mass spectrometry. The mass spectral data show that the thermal fragmentation occurring in the polymers under investigation is characterized by hydrogen transfer reactions. In the case of a totally aromatic poly-Schiff base (polymer I ), the thermal fragmentation process involves hydrogen transfer irom the methyne group with formation of fragments bearing nitrile and/or phenyl end groups. In the case of aromatic-aliphatic poly-Schiff bases (polymers II–IV ), the hydrogen transfer process occurs from the aliphatic methylene groups. The latter process involves a lower energy and therefore occurs at lower temperatures with respect to the totally aromatic polymer I , with formation of thermal fragments bearing olefin and/or imine end groups. Beside these fragments, several thermal fragmentation compounds are also evolved by multiple hydrogen transfer reactions. 相似文献
28.
Emilio Toja Giorgio Tarzia Pietro Ferrari Giorgio Tuan 《Journal of heterocyclic chemistry》1986,23(5):1555-1560
A series of 4,7-dihydro-4-oxo-1H-pyrrolo[2,3-b]pyridine-5-carboxylic acids was synthesized from ethyl 5-methyl(or 5H)-2-aminopyrrole-3-carboxylate. The starting pyrroles were obtained by reaction of carbethoxyacetamidine with bromoacetone or chloroacetaldehyde. One compound ( 10 ) showed antibacterial activity in vitro. 相似文献
29.
Pietro Borgna Massimo Pregnolato Anna Gamba Invernizzi Giorgio Mellerio 《Journal of heterocyclic chemistry》1993,30(4):1079-1084
3H-1,2-Dithiolo[3,4-b]pyridine-3-thione ( 10 ) reacts with primary alkylamines to give 1,2-dihydro-2-thioxo-3-pyridinecarbothioamides 11a-g and two minor products. Isothiazolo[5,4-b]pyridine-3(2H)-thiones 12a-g and 3-imino-3H-1,2-dithiolo[3,4-b]pyridines 13a-g were isolated and characterized. Further investigations allowed the synthesis of 12 and 13 in good yield. 相似文献
30.
Dimethylcarbonate (DMC) is a valuable methylating reagent that can replace methyl halides and dimethylsulfate in the methylation of a variety of nucleophiles. It couples tunable reactivity and unprecedented selectivity towards mono-C- and mono-N-methylation. In addition, it is a prototype example of a green reagent, because it is nontoxic, is made by a clean process, is biodegradable, and reacts in the presence of a catalytic amount of base, thereby avoiding the formation of undesirable inorganic salts as by-products. Depending on the reaction conditions, DMC can be reacted under plug-flow, CSTR, or batch conditions. Other remarkable reactions are those where DMC behaves as an oxidant. The reactivity of other carbonates is reported as well. 相似文献