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A series of pyrazinoporphyrazine macrocycles carrying externally appended 2-thienyl rings, represented as [Th(8)TPyzPzM], where Th(8)TPyzPz = tetrakis-2,3-[5,6-di(2-thienyl)pyrazino]porphyrazinato anion and M = Mg(II)(H(2)O), Zn(II), Co(II), Cu(II), or 2H(1), were prepared and isolated as solid air-stable hydrated species. All of the compounds, completely insoluble in water, were characterized by their UV-visible spectra and electrochemical behavior in solutions of dimethylformamide (DMF), dimethyl sulfoxide, and pyridine. Molecular aggregation occurs at concentrations of ca. 10(-4) M, but monomers are formed in more dilute solutions of 10(-5) M or less. The examined octathienyl compounds [Th(8)TPyzPzM] behave as electron-deficient macrocycles, and UV-visible spectral measurements provide useful information about how the peripheral thienyl rings influence the electronic distribution over the entire macrocyclic framework. Cyclic voltammetric and spectroelectrochemical data confirm the easier reducibility of the compounds as compared to the related phthalocyanine analogues, and the overall redox behavior and thermodynamic potentials for the four stepwise one-electron reductions of the compounds are similar to those of the earlier examined octapyridinated analogues [Py(8)TPyzPzM]. Quantum yields (Φ(Δ)) for the generation of singlet oxygen, (1)O(2), the cytotoxic agent active in photodynamic therapy (PDT), and fluorescence quantum yields (Φ(F)) were measured for the Zn(II) and Mg(II) complexes, [Th(8)TPyzPzZn] and [Th(8)TPyzPzMg(H(2)O)], and the data were compared to those of corresponding octapyridino macrocycles [Py(8)TPyzPzZn] and [Py(8)TPyzPzMg(H(2)O)] and their related octacations [(2-Mepy)(8)TPyzPzZn](8+) and [(2-Mepy)(8)TPyzPzMg(H(2)O)](8+). These measurements were carried out in DMF and in DMF preacidified with HCl (ca. 10(-4) M). All of the examined Zn(II) compounds behave as excellent photosensitizers (Φ(Δ) = 0.4-0.6) both in DMF and DMF/HCl solutions, whereas noticeable fluorescence activity (Φ(F) = 0.36-0.43) in DMF/HCl solutions is shown by the Mg(II) derivatives; these data might provide perspectives for applications in PDT (Zn(II)) and imaging response and diagnosis (Mg(II)).  相似文献   
105.
We exploited the ability of photocatalytic titanium dioxide (TiO(2)) as an agent for the biofilm control. Two photocatalytic systems were investigated: a 3 g L(-1) suspension of TiO(2) nanopowder in demineralized water and glass slides coated with a TiO(2) thin film, achieved by sol-gel deposition. A running protocol for the photoactivation of TiO(2) was set up using the dye rhodamine B. The microorganisms studied were Pseudomonas stutzeri, Pseudomonas aeruginosa and a Bacillus cereus-group as planktonic cells. P. aeruginosa biofilms were also studied at both the solid-liquid and the solid-air interface. The TiO(2) nanopowder produced 1-log reduction of Bacillus sp. planktonic cells in 24 h, 2-log reduction of P. stutzeri planktonic cells in 30 min and 1-log reduction of P. aeruginosa planktonic cells in 2 h compared with non-photo-activated TiO(2). TiO(2) thin film produced almost a complete eradication of P. aeruginosa planktonic cells (initial concentration 10(8) cells mL(-1)) in 24 h compared to a 3-log reduction caused by UV-A light alone. In contrast, neither the photocatalytic treatment with TiO(2) film nor that with TiO(2) nanopowder had any effect on P. aeruginosa biofilms at all the interfaces investigated. Possible explanations for these findings, and for the discrepancy between this work and literature data, are discussed.  相似文献   
106.
Although it is well known that any material degrades faster when exposed to an aggressive environment as well as that "aggressive" cannot be univocally defined as depending also on the chemical-physical characteristics of material, few researches on the identification of the most significant parameters influencing the corrosion of metallic object are available.A series of ancient coins, coming from the archaeological excavation of Palazzo Valentini (Rome) were collected together with soils, both near and far from them, and then analysed using different analytical techniques looking for a correlation between the corrosion products covering the coins and the chemical-physical soil characteristics. The content of soluble salts in the water-bearing stratum and surfacing in the archaeological site, was also measured.The obtained results stress the influence of alkaline soils on formation of patina. Cerussite, probably due to the circulation of water in layers rich in marble and plaster fragments, was the main corrosion product identified by X-ray Diffraction (XRD). Copper, lead and vanadium were found in soil surrounding coins. By measuring conductivity, pH and soluble salts content of the washing solutions from both coins and soils, we could easily separate coins coming from different stratigraphic units of the site.Data were treated by cluster and multivariate analysis, revealing a correlation between part of the coins and the nearby soil samples.  相似文献   
107.
The synthesis of several isoearboslyrils is reported, including lorrnyl derivatives at (1-4, like nareiclasie aldehyde (I) and the homologous aldehyde (XV).  相似文献   
108.
Amorphous drug nanosuspensions are prone to particle growth due to Ostwald ripening. By incorporating a second component of extremely low aqueous solubility, Ostwald ripening can be inhibited. These studies indicate that to inhibit ripening, the drug/inhibitor mixture (in the particles) must form a single phase. The drug/inhibitor mixture can be characterized by the interaction parameter chi using the Bragg-Williams theory, in which single phase mixtures are obtained for chi < 2. The chi parameter can be calculated from the (crystalline) solubility of the drug in the inhibitor, provided the inhibitor is a liquid, and the melting entropy and temperature of the drug.  相似文献   
109.
The Banach-Mazur game as well as the strong Choquet game are investigated on the Wijsman hyperspace from the nonempty player's (i.e. α's) perspective. For the strong Choquet game we show that if X is a locally separable metrizable space, then α has a (stationary) winning strategy on X iff it has a (stationary) winning strategy on the Wijsman hyperspace for each compatible metric on X. The analogous result for the Banach-Mazur game does not hold, not even if X is separable, as we show that α may have a (stationary) winning strategy on the Wijsman hyperspace for each compatible metric on X, and not have one on X. We also show that there exists a separable 1st category metric space such that α has a (stationary) winning strategy on its Wijsman hyperspace. This answers a question of Cao and Junnila (2010) [6].  相似文献   
110.
This paper is about the minimization of Lipschitz-continuous and strongly convex functions over integer points in polytopes. Our results are related to the rate of convergence of a black-box algorithm that iteratively solves special quadratic integer problems with a constant approximation factor. Despite the generality of the underlying problem, we prove that we can find efficiently, with respect to our assumptions regarding the encoding of the problem, a feasible solution whose objective function value is close to the optimal value. We also show that this proximity result is the best possible up to a factor polynomial in the encoding length of the problem.  相似文献   
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