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31.
Singlet oxygen (1O2) is unique amongst reactive oxygen species formed in cells in that it is an excited state molecule with an inherent upper lifetime of 4 micros in water. Whether the lifetime of 1O2 in cells is shortened by reactions with cellular molecules or reaches the inherent maximum value is still unclear. However, even with the maximum lifetime, the diffusion radius is only approximately 220 nm during three lifetimes (approximately 5% 1O2 remaining), much shorter than cellular dimensions indicating that the primary reactions of 1O2 will be subcellularly localized near the site of 1O2 formation. This fact has raised the question of whether spatially resolved cellular responses to 1O2 occur, i.e. whether responses can be initiated by generation and reaction of 1O2 at a particular subcellular location that would not have been produced by 1O2 generation at other subcellular sites. In this paper, we discuss examples of spatially resolved responses initiated by 1O2 as a function of distance from the site of generation of 1O2. Three levels are recognized, namely, a molecular level where the primary oxidation product directly modifies the behavior of a cell, an organelle level where the initial photo-oxidation products initiate mechanisms that are unique to the organelle and the cellular level where mediators diffuse from their site of formation to the target molecules that initiate the response. These examples indicate that, indeed, spatially resolved responses to 'O2 occur in cells. 相似文献
32.
33.
Simple Zeros of the Riemann Zeta-Function 总被引:1,自引:0,他引:1
Assuming the Riemann Hypothesis, Montgomery showed by meansof his pair correlation method that at least two-thirds of thezeros of Riemann's zeta-function are simple. Later he and Taylorimproved this to 67.25 percent and, more recently, Cheer andGoldston increased the percentage to 67.2753. Here we proveby a new method that if the Riemann and Generalized LindelöofHypotheses hold, then at least 70.3704 percent of the zerosare simple and at least 84.5679 percent are distinct. Our methoduses mean value estimates for various functions defined by Dirichletseries sampled at the zeros of the Riemann zeta-function. 1991Mathematics Subject Classification: 11M26. 相似文献
34.
35.
P A Haynes M Batley R J Peach S O Brennan J W Redmond 《Journal of chromatography. A》1992,581(2):187-193
The characterisation of oligosaccharides present on albumin Casebrook, a glycoprotein variant of human serum albumin, which contains an N-linked oligosaccharide at an attachment site formed by a point mutation of 494 Asp-->Asn, is described. The monosaccharide compositional analysis of purified glycopeptides suggested the presence of complex biantennary carbohydrate structures. The oligosaccharides which were released by N-glycosidase-F appeared to be a single molecular species according to their retention on high-performance anion-exchange chromatography. The structure of the oligosaccharide was suggested by sequential exoglycosidase digestions and confirmed by proton nuclear magnetic resonance spectroscopy. It was concluded that the oligosaccharides were essentially homogeneous and consisted of an alpha(2-6)-desialylated complex biantennary glycan. 相似文献
36.
The type-II photosensitization process is mediated by the formation of singlet oxygen (O2[1deltag]). The short lifetime of this species dictates that chemical reactions with biological substrates can only occur when O2(1deltag) is in very close proximity to the photosensitizer itself. In this study, deuteroporphyrin, a type-II, membrane-localized photosensitizer, was used to generate O2(1deltag) in human lymphoblast WTK-1 cells, and the range of influence was determined by a variety of biological assays. Surprisingly, the initial membrane-confined events were shown, by comet assay, to induce DNA damage in these cells. DNA damage was inhibited both by membrane-localized (alpha-tocopherol acetate) and by cytoplasmic (trolox) free radical scavengers. Comet formation also was inhibited by treatment at low temperature. DNA fragmentation was not influenced by treatment with the pan-caspase inhibitor, benzyloxycarbonyl-Val-Ala-Asp-fluoromethylketone, showing that apoptosis was not responsible for fragmentation. Taken together, these results show that primary photosensitization reactions involving O2(1deltag), even when tightly confined in extranuclear locations, leads to the production of secondary reactive oxygen species, probably as a result of lipid peroxidation, that can act at greater distances from the photosensitizer itself. These experiments were carried out under conditions where cell survival was significant and raise questions regarding DNA damage and mutagenesis pathways, even when extranuclear O2(1deltag)-generating compounds are used. 相似文献
37.
PHOTOPHYSICAL AND PHOTOSENSITIZING PROPERTIES OF BENZOPORPHYRIN DERIVATIVE MONOACID RING A (BPD-MA)*
The photophysical properties of benzoporphyrin derivative monoacid ring A (BPD-MA), a second-generation photosensitizer currently in phase II clinical trials, were investigated in homogeneous solution. Absorption, fluorescence, triplet-state, singlet oxygen (O2(1Δg)) sensitization studies and photobleaching experiments are reported. The ground state of this chlorin-type molecule shows a strong absorbance in the red (λ≈ 688 nm, ?≈ 33 000 M?1 cm?1 in organic solvents). For the singlet excited state the following data were determined in methanol: energy level, Es= 42.1 kcal mol?1, lifetime, Φf= 5.2 ns and fluorescence quantum yield, Φf= 0.05 in air-saturated solution. The triplet state of BPD-MA has a lifetime, τf >. 25 ns, an energy level, ET= 26.9 kcal mol?1 and the molar absorption coefficient is ?T= 26 650 M?1 cm?1 at 720 nm. A dramatic effect of oxygen on the fluorescence (φf) and intersystem crossing (φT) quantum yields has been observed. The BPD-MA presents rather high triplet (φT= 0.68 under N2-saturated conditions) and singlet oxygen (φΔ= 0.78) quantum yields. On the other hand, the presence of oxygen does not significantly modify the photobleaching of this photostable compound, the photodegradation quantum yield (φPb) of which was found to be on the order of 5 × 10?5 in organic solvents. 相似文献
38.
Pedro F. Aramendia Robert W. Redmond Santiago Nonell Wolfang Schuster Silvia E. Braslavsky Kurt Schaffner Emanuel Vogel 《Photochemistry and photobiology》1986,44(5):555-559
Porphycene and a tetra-n-propyl derivative remained unaltered on irradiation in toluene at room temperature. Quantum yields of fluorescence, S T intersystem crossing, and singlet molecular oxygen sensitization, as well as lifetimes of the singlet and triplet excited states were measured. In view of their structural relationship to porphyrin, their high absorption above 620 nm, their stability towards photooxidation, and their high quantum yields of fluorescence and singlet oxygen sensitization, these compounds qualify as potential agents for tumor marking and photodynamic therapy. 相似文献
39.
Quantum Zeno and anti-Zeno paradoxes 总被引:1,自引:0,他引:1
Continuous observation of a time independent projection operator is known to prevent change of state (the quantum Zeno paradox).
We discuss the recent result that generic continuous measurement of time dependent projection operators will in fact ensure
change of state: an anti-Zeno paradox. 相似文献
40.
Modular Construction of Fluoroarenes from a New Difluorinated Building Block by Cross‐Coupling/Electrocyclisation/Dehydrofluorination Reactions 下载免费PDF全文
Prof. Dr. Jonathan M. Percy Helena Emerson James W. B. Fyfe Dr. Alan R. Kennedy Sergej Maciuk David Orr Lucie Rathouská Dr. Joanna M. Redmond Dr. Peter G. Wilson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):12166-12175
Palladium‐catalysed coupling reactions based on a novel and easy‐to‐synthesise difluorinated organotrifluoroborate were used to assemble precursors to 6π‐electrocyclisations of three different types. Electrocyclisations took place at temperatures between 90 and 240 °C, depending on the central component of the π‐system; nonaromatic trienes were most reactive, but even systems that required the temporary dearomatisation of two arenyl subunits underwent electrocyclisation, albeit at elevated temperatures. Photochemical conditions were effective for these more demanding reactions. The package of methods delivered a structurally diverse set of fluorinated arenes, spanning a 20 kcal mol?1 range of reactivity, by a flexible route. 相似文献