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排序方式: 共有396条查询结果,搜索用时 250 毫秒
1.
Alfons Pascual 《Helvetica chimica acta》1989,72(3):556-569
Preparation of Substituted 2-Aminooxazole-4-carbonitriles During our synthetic programme to convert 4-isoxazolylthioureas 3 into the corresponding carbodiimides 5 , a side reaction leading to the hitherto unknown 2-aminooxazole-4-carbonitriles 6 was observed. By selecting appropriate reaction conditions, it was possible to improve the yields of the carbodiimides 5 as well as of the novel oxazole-carbonitriles 6 at will, thus allowing the synthesis of 6 to be conducted in very good yields. To overcome the difficulty of isolating unstable carbodiimides, the synthesis of 6 is best carried out in a one-pot procedure. A limited mechanistic study showed that the formation of 6 proceeds via 5 as the only intermediate. The stability of the N?C?N bonds against base attack (depending strongly on both sterical hindrance and electronic-density factors) forms the only limitation of this new synthetic pathway to oxazole-4-carbonitriles. 相似文献
2.
Arthur Maki Robert L. Sams Jeffrey Barber Engelene t.H. Chrysostom Alfons Weber 《Journal of Molecular Spectroscopy》2004,225(2):109-122
Several new infrared absorption bands for 32S16O3 have been measured and analyzed. The principal bands observed were ν1+ν2 (at 1561 cm−1), ν1+ν4 (at 1594 cm−1), ν3+ν4 (at 1918 cm−1), and 3ν3 (at 4136 cm−1). Except for 3ν3, these bands are very complicated because of (a) the Coriolis coupling between ν2 and ν4, (b) the Fermi resonance between ν1 and 2ν4, (c) the Fermi resonance between ν1 and 2ν2, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A1′ and A2′ levels of ν3+ν4. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν3 band was an essential aid in fitting the ν3+ν4 transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A1′ vibrational level is 3.50 cm−1 above the A2′ level, i.e., r34=1.75236(7) cm−1. In the case of the 3ν3 band, the spectral analysis is straightforward and a weak Δk=±2, Δl3=±2 interaction between the l3=1 and l3=3 substates locates the latter A1′ and A2′ “ghost” states 22.55(4) cm−1 higher than the infrared accessible l3=1 E′ state. 相似文献
3.
Oleinikova A Smolin N Brovchenko I Geiger A Winter R 《The journal of physical chemistry. B》2005,109(5):1988-1998
The formation of spanning hydrogen-bonded water networks on protein surfaces by a percolation transition is closely connected with the onset of their biological activity. To analyze the structure of the hydration water at this important threshold, we performed the first computer simulation study of the percolation transition of water in a model protein powder and on the surface of a single protein molecule. The formation of an infinite water network in the protein powder occurs as a 2D percolation transition at a critical hydration level, which is close to the values observed experimentally. The formation of a spanning 2D water network on a single rigid protein molecule can be described by adapting the cluster analysis of conventional percolation studies to the characterization of the connectivity of the hydration water on the surface of finite objects. Strong fluctuations of the surface water network are observed close to the percolation threshold. Our simulations also furnish a microscopic picture for understanding the specific values of the experimentally observed hydration levels, where different steps of increasing mobility in the hydrated powder are observed. 相似文献
4.
Delayed luminescence (in the microsecond time range) of the chlorophyll (Chl) a“dry” form as well as hydrated dimers located in a polyvinylalcohol film was measured from room temperature down to 8 K. In the same matrix the delayed luminescence of rhodamine 6G (Rhod) was investigated. The delayed emission both of Chl a and Rhod is probably due to the formation and delayed recombination of a radical pair. It seems that this process occurs without participation of triplet states, as it does not reflect their well-known sensitivity to oxygen. The temperature dependence of the delayed luminescence of vanous Chl forms is different. In the region around 678 nm (dry monomer) delayed luminescence needs a thermal activation energy of about 0.03 eV, whereas at 740 nm (wet aggregates) delayed luminescence intensity increases linearly with decreasing temperature. Its assignment as a-type delayed luminescence from the low-lying triplet state can consistently be excluded from both the weak temperature dependence of the delayed fluorescence and its large intensity as compared to the prompt fluorescence. Delayed luminescence of Rhod is almost independent of temperature between 8 K and 300 K. The dependence of delayed luminescence intensity on exciting light intensity is linear at lower intensities and tends to saturation at higher. Therefore the delayed luminescence is not related to exciton annihilation. Positions and intensities of the Chl delayed luminescence bands show that it is not phosphorescence (β-type delayed luminescence). The aggregation of both Chl and Rhod molecules strongly influences delayed luminescence since it differs in several properties if excited in the monomer or in the aggregate absorption range. Every aggregational form of dye emits its characteristic delayed luminescence band. 相似文献
5.
Keresszegi C Grunwaldt JD Mallat T Baiker A 《Chemical communications (Cambridge, England)》2003,(18):2304-2305
In situ, time-resolved XAS studies on a Bi-Pd/Al2O3 catalyst indicate that Pd, and Bi located on the Pd surface, are in a reduced, metallic state during the oxidation of 1-phenylethanol with molecular oxygen--a key for understanding the role of promoter in the reaction mechanism. 相似文献
6.
Dagobert Achatz Markus A. Lang Alfons Vlkl Wolf Peter Fehlhammer Wolfgang Beck 《无机化学与普通化学杂志》2005,631(12):2339-2346
Carbonyl Complexes of Chromium, Molybdenum and Tungsten with Isocyano Acetate. Reactions of Coordinated Isocyanoacetate. Stabilization of Isocyanoacetic Acid and Isocyanoacetyl Chloride at the Metal Atom. Isocyanopeptides The reactions of [(OC)5MCNCH2CO2Et] (M = Cr, W) with Na[N(SiMe3)2] or with KOH afford the isocyanoacetate complexes [(OC)5MCNCH2CO2]? ( 1,2 ). Similarly, the complex [(OC)3Mo(CNCH2CO2?Li+)3] ( 4 ) was obtained from [(OC)3Mo(CNCH2CO2Et)3] ( 3 ) and LiOH. Protonation of 1 and 2 affords the sublimable isocyanoacetic acid complexes [(OC)5MCNCH2CO2H] ( 5 , 6 ; M = Cr, W) in which the functional isocyanide is stabilized at the metal atom. Reactions of [(OC)5WCNCH2CO2?K+] and of [(OC)3Mo(CNCH2CO2?Li+)3] with oxalyl dichloride give the isocyanoacetyl chloride compounds [(OC)5WCNCH2COCl] ( 9 ) (sublimable) and [(OC)3Mo(CNCH2COCl)3] ( 10 ); the latter ( 10 ) was not isolated. Complexes 9 and 10 were reacted in situ with β‐alanine, glycine, phenylalanine and methionine esters as well as the peptide esters GlyGlyOEt, PhePheOMe, Phe‐β‐AlaOMe, and GlyGlyGlyOMe to form the isocyanoacetyl amino acid esters ( 11 ‐ 14 ) and the isocyanoacetyl peptide esters ( 15 ‐ 18 ) which are stabilized at the molybdenum atom. 相似文献
7.
Olivier Schwalm Jacques Weber Bruno Minder Alfons Baiker 《Journal of Molecular Structure》1995,330(1-3)
The enantioselective hydrogenation of α-ketoesters to α-hydroxyesters over Pt/Al2O3 catalysts modified by cinchona alkaloids is an interesting model reaction for the investigation of heterogeneous catalysis capable of producing optically active products. The aim of the present theoretical study is to rationalize the interaction between protonated cinchona alkaloids (modifiers) and methyl pyruvate (substrate) by investigating the possible weak complexes formed by these two species. For this purpose we use molecular mechanics and the AM1 semiempirical method. The optimization leads to two stable forms of the complexes, where the substrate is bound to the modifier via hydrogen bonding between the oxygen of the α-carbonyl of pyruvate and the quinuclidine nitrogen of the alkaloid. In such complexes the methyl pyruvate is transformed into a half-hydrogenated species which can be adsorbed on the platinum surface and, after hydrogenation, leads to methyl lactate product. The results show that adsorption of the complex leading to (R)-methyl lactate is more favorable than that of the corresponding system yielding (S)-methyl lactate, which may be the key for the enantio-differentiation. 相似文献
8.
Huygens A Huyghe D Bormans G Verbruggen A Kamuhabwa AR Roskams T de Witte PA 《Photochemistry and photobiology》2003,78(6):607-614
The aim of this study was to investigate the in vitro cellular accumulation, distribution and photocytotoxic effect of hypericin in two-dimensional (2-D) and three-dimensional (3-D) cultured RT-112 transitional cell carcinoma cells of the bladder. In addition, two iodinated derivatives of hypericin were incorporated to investigate whether these analogs, with their increased lipophilicity and heavy-atom effect, display a different biological behavior and optimized photodynamic effect. The results indicate that hypericin and mono-iodohypericin behave similarly in terms of cellular accumulation, spheroidal distribution and photocytotoxic effect. In contrast, di-iodohypericin concentrated to a higher extent in monolayers and spheroids, but the accumulation was restricted to the outermost part of the spheroid. An inverse correlation therefore seems to exist between the extent of cellular uptake under 2-D conditions and the penetration of the compounds in multicellular systems. Moreover, a less pronounced photocytotoxic effect was observed for di-iodohypericin in both 2-D and 3-D cell culture systems. It can be concluded that iodinated derivatives of hypericin do not show an increased cytotoxic effect upon irradiation in either monolayers or spheroids. Moreover, this study shows that when new photosensitizers are preclinically developed, the use of 3-D cell aggregates is critical for a correct evaluation of their efficacy. 相似文献
9.
In situ characterization of catalysts by means of complementary spectroscopic techniques can be regarded as the first step towards rational catalyst design. Spurred by the growing interest of catalytic reactions in supercritical fluids and by several industrial reactions traditionally performed at high pressure (>10 bar), new demands and challenges are put to in situ spectroscopic characterization of heterogeneous catalytic reactions. In this article, we discuss the development and the use of spectroscopic and related techniques suitable for elucidating such high-pressure reactions. Selected examples from phase behaviour studies with a view cell, investigations with transmission and attenuated total reflection (ATR) infrared spectroscopy as well as X-ray absorption spectroscopy (EXAFS, XANES), are presented to show the strategies, opportunities and limitations of such high pressure in situ studies. Different facets appear to be important to gain insight into catalytic reactions in supercritical fluids: the identification of the phase behaviour of the reaction mixture, the behaviour of the fluid inside the porous catalyst, the processes occurring at the solid-fluid interface, the possible dissolution of active species and, similar as in gas-solid reactions, the establishment of structure-activity relationships. 相似文献
10.
Friedrich Boberg Maria Ruhr Karl-Heinz Garburg Alfons Garming 《Journal of heterocyclic chemistry》1986,23(3):759-766
Dihydro-1,2-oxazines 8 and 12-oxazines 12 are formed by the reaction of the nitronic acids of the adducts of α-nitroolefins and β-dicarbonyl compounds ( 6 ) by two ways: A ) The nitronic acids 6 are heated in a boiling solution of urea in ethanol or methanol. B ) The nitronic acids 6 are reduced with an aqueous solution of ammoniachloride and sodium sulfide. 1H-nmr and 13C-nmr investigations prove the constitutions. The mechanism is discussed. 相似文献