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41.
Lydia J. Martinez Robert H. Sik Colin F. Chignell† 《Photochemistry and photobiology》1998,67(4):399-403
The fluoroquinolone antibacterial agents possess photo-sensitizing properties that lead to phototoxic responses in both human and animal subjects. The phototoxicity order reported in humans is: fleroxacin > lomefloxacin, pefloxacin > ciprofloxacin ? enoxacin, norfloxacin and ofloxacin. Studies both in vivo and in vitro have related this phototoxicity to the generation of reactive oxygen species including hydrogen peroxide and the hydroxyl radical. We determined the quantum yields of singlet oxygen generation (φΔ,) by detection of the singlet oxygen (1O2) luminescence at 1270 tun for several fluoroquinolones, naphthyridines and other structurally related compounds. All the fluoroquinolones examined have low φΔ values ranging from 0.06 to 0.09 in phosphate buffer at pD 7.5. We also determined the 1O2 quenching constants for these compounds and their values were on the order of 106M?1 s1, except for lomefloxacin whose rate constant was 1.8 × 107M?1 s?1. The φΔ values were significantly decreased in a solvent of lower polarity such as methanol (0.007 ≤φΔ≤ 0.02). The production of 1O2 by these antibiotics did not correlate with the order reported for their phototoxicity. We also measured the photogeneration (λ > 300 nm) of superoxide by these antibacterials in dimethylsulfoxide using electron paramagnetic resonance and the spin trap 5,5-dimethyl-l-pyrroiine N-oxide. Although there is not a one-to-one correspondence between the relative rates of superoxide generation and the phototoxicity ranking of the fluoroquinolones, the more phototoxic compounds tended to produce superoxide at a faster rate. Nevertheless, the magnitudes of the observed differences do not appear sufficient to explain the range of fluoroquinolone phototoxicity potencies in human and animal subjects in general and the high activity of fleroxacin and lomefloxacin in particular. For these latter drugs the photoinduced loss of the F8 atom as fluoride and the concomitant generation of a highly reactive carbene at C-8 provide a more plausible mechanism for their potent phototoxic and photocarcinogenic properties. 相似文献
42.
The Thorpe-Ziegler reaction has been used in the preparation of enaminonitriles and cyclic ketones for many years. A wide variety of bases1 have been employed to acomplish this reaction, the most effective being the alkali metal salts of aralkyl amines. The reaction conditions vary from room temperature to toluene reflux temperature for long periods of time1. 相似文献
43.
44.
The synthesis and anion recognition properties of four novel [2]rotaxane host architectures containing additional alkyl functionality integrated within macrocyclic and axle components to shield the binding cavity from the solvent are described. The rotaxane species containing a tetra(methyl)-functionalised macrocycle component is found to be a weaker anion complexant than the equivalent unfunctionalised receptor, which is likely due to steric hindrance restricting the anion's access to the interlocked cavity. Rotaxane molecules containing tetra(methyl)-functionalised axle components are also investigated, and the additional alkyl functionality serves to enhance anion binding affinity and selectivity when incorporated within the axle's flexible ethylene linkages. Moreover, the equivalent unfunctionalised rotaxane displays a rare preference for oxoanions over chloride guest species. 相似文献
45.
[structure: see text] Chitin synthase (CS) polymerizes UDP-GlcNAc to form chitin (poly-beta(1,4)-GlcNAc), a key component of fungal cell wall biosynthesis. Little is known about the substrate specificity of chitin synthase or the scope of substrate modification the enzyme will tolerate. Following a previous report suggesting that 6-O-dansyl GlcNAc is biosynthetically incorporated into chitin, we became interested in developing an assay for CS activity based on incorporation of a fluorescent substrate. We describe the synthesis of two fluorescent UDP-GlcNAc analogues and their evaluation as chitin synthase substrates. 相似文献
46.
Detlefsen (1986) reads Hilbert's program as a sophisticated defense of instrumentalism, but Feferman (1998) has it that Hilbert's program leaves significant ontological questions unanswered. One such question is of the reference of individual number terms. Hilbert's use of admittedly “meaningless” signs for numbers and formulae appears to impair his ability to establish the reference of mathematical terms and the content of mathematical propositions ( and ). The paper traces the history and context of Hilbert's reasoning about signs, which illuminates Hilbert's account of mathematical objectivity, axiomatics, idealization, and consistency. 相似文献
47.
Lydia McGrew 《Acta Analytica》2014,29(4):491-505
I offer an account of ad hocness that explains why the adoption of an ad hoc auxiliary is accompanied by the disconfirmation of a hypothesis H. H must be conjoined with an auxiliary (or set of auxiliaries) a′, which is improbable antecedently given H, while ~H does not have this disability. This account renders it unnecessary to require, for identifying (bad) ad hocness, that either a′ or H have a posterior probability less than or equal to 0.5; there are also other reasons for abandoning that condition. I distinguish between formal ad hocness, which is bad in the probabilistic sense that it results in disconfirmation of H, and argumentative ad hocness, which actually involves bad reasoning on the part of a subject. The latter is what I call “not counting the cost.” This distinction allows us to see why the 0.5 condition appeared attractive in the first place. The concept of not counting the cost also has implications for other areas of research, including both a Bayesian concept of unfalsifiability and the classic epistemological question of the problem of the external world. 相似文献
48.
Lazare Saladin Victor Breton Ophélie Dal Pra Dr. Andrey S. Klymchenko Dr. Lydia Danglot Prof. Pascal Didier Dr. Mayeul Collot 《Angewandte Chemie (International ed. in English)》2023,62(4):e202215085
We herein present a new concept to produce dual-color photoconvertible probes based on a mechanism called Directed Photooxidation Induced Conversion (DPIC). As a support of this mechanism, styryl-coumarins ( SCs ) bearing Aromatic Singlet Oxygen Reactive Moieties (ASORMs) like furan and pyrrole have been synthesized. SCs are bright fluorophores, which undergo a hypsochromic conversion upon visible light irradiation due to directed photooxidation of the ASORM that leads to the disruption of conjugation. SC-P , a yellow emitting probe bearing a pyrrole moiety, converts to a stable blue emitting coumarin with a 68 nm shift allowing the photoconversion and tracking of lipid droplet in live cells. This new approach might pave the way to a new generation of photoconvertible dyes for advanced bioimaging applications. 相似文献
49.
A. Kandasamy R. Mohan M. Lydia Caroline S. Vasudevan 《Crystal Research and Technology》2008,43(2):186-192
Nucleation parameters such as solubility, induction period, interfacial energy and metastable zone width have been investigated for the aqueous solution growth of a semi‐organic nonlinear optical (NLO) material of L‐Proline cadmium chloride monohydrate (L‐PCCM) single crystal. Metastable zone width and induction period values were determined experimentally in order to optimize the growth parameters. The grown crystals are transparent (dimensions: 16 x 8 x 5 mm3) and characterized by powder X‐Ray Diffraction and dielectric studies. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
50.