全文获取类型
收费全文 | 224篇 |
免费 | 9篇 |
国内免费 | 5篇 |
专业分类
化学 | 130篇 |
力学 | 11篇 |
数学 | 48篇 |
物理学 | 49篇 |
出版年
2022年 | 2篇 |
2020年 | 2篇 |
2019年 | 3篇 |
2018年 | 6篇 |
2017年 | 2篇 |
2016年 | 9篇 |
2014年 | 4篇 |
2013年 | 8篇 |
2012年 | 7篇 |
2011年 | 11篇 |
2010年 | 5篇 |
2009年 | 6篇 |
2008年 | 12篇 |
2007年 | 18篇 |
2006年 | 5篇 |
2005年 | 8篇 |
2004年 | 9篇 |
2003年 | 12篇 |
2002年 | 7篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1964年 | 1篇 |
1963年 | 2篇 |
1940年 | 2篇 |
1938年 | 2篇 |
1932年 | 2篇 |
排序方式: 共有238条查询结果,搜索用时 312 毫秒
61.
Let sC3 denote the disjoint union of s copies of C3. For each integer t≥2 it is shown that the disjoint union C5∪(2t)C3 has a strong vertex-magic total labeling (and therefore it must also have a strong edge-magic total labeling). For each integer t≥3 it is shown that the disjoint union C4∪(2t−1)C3 has a strong vertex-magic total labeling. These results clarify a conjecture on the magic labeling of 2-regular graphs, which posited that no such labelings existed. It is also shown that for each integer t≥1 the disjoint union C7∪(2t)C3 has a strong vertex-magic total labeling. The construction employs a technique of shifting rows of (newly constructed) Kotzig arrays to label copies of C3. The results add further weight to a conjecture of MacDougall regarding the existence of vertex-magic total labeling for regular graphs. 相似文献
62.
63.
Electrocatalytic oxidation of guanine in DNA was detected at tin-doped indium oxide electrodes modified with nylon and nitrocellulose polymers. The catalytic oxidation occurs via oxidation at the electrode of the complex Ru(bpy)
3
2+
to the 3+ state, which is then reduced back to the 2+ state by guanine in DNA (bpy = 2,2-bipyridine). Catalysis is observed as a current enhancement in the cyclic voltammogram of Ru(bpy)
3
2+
when DNA is immobilized in the film. As seen in solution, the catalytic enhancement in the nitrocellulose film is lower at 800 mM NaCl than without added salt because electrostatic binding of the Ru(bpy)
3
2+
to the DNA at low salt increases the catalytic rate constant. The cyclic voltammogram of Os(bpy)
3
2+
, which does not oxidize guanine, exhibits less current in the presence of DNA because binding to the immobilized DNA precludes communication of the metal complex with the electrode. Electrodes modified with poly[C] gave no enhancement; however, catalytic current was observed upon hybridization to poly[G]. Exposure of the poly[C] electrode to random single-stranded DNA gave no catalytic current. Glassy carbon electrodes modified with the membranes behaved in a manner similar to that of the metal oxide electrodes. 相似文献
64.
L.?E.?RodgersEmail author P.?J.?Holden R.?B.?Knott K.?S.?Finnie J.?R.?Bartlett L.?J.?R.?Foster 《Journal of Sol-Gel Science and Technology》2005,33(1):65-69
The application of small angle neutron scattering (SANS) to the characterisation of sol–gel hosts containing biomolecules offers the opportunity to explore the relationship between gel structure and catalyst. A model system involving the immobilisation of Candida antarctica lipase B (CALB) was investigated.Gels were produced by fluoride-catalysed hydrolysis of fixed ratios of tetramethylorthosilicate (TMOS) and methyltrimethoxysilane (MTMS). Phase separation between the enzyme and the evolving sol–gel matrix was minimised by incorporating glycerol into the sol–gel precursor solution. The potential stabilising effect of the NaF catalyst upon the enzyme was also investigated. Scattering studies were conducted on both immobilised lipase, and lipase in free solution. Scattering studies on free enzyme provided evidence of multiple populations of enzyme aggregates and showed that choice of solvent affected the degree of aggregation. Both NaF and glycerol affected neutron scattering, indicating changes in lipase conformation. Increasing glycerol concentration increased the degree of aggregation and produced differences in solvent packing on the surface of protein molecules. Initial evidence from SANS data indicated that the presence of the enzyme during gel formation conferred structural changes on the gel matrix. Modelling the effect of sol–gel encapsulation on lipase requires comparison of data from free enzyme to the immobilised form. Removal of the enzyme from the sol–gel structure, post gelation, is necessary to better characterise the modified matrix. This methodological problem will be the subject of future investigations. 相似文献
65.
Holmberg RC Tierney MT Ropp PA Berg EE Grinstaff MW Thorp HH 《Inorganic chemistry》2003,42(20):6379-6387
A phosphoramidite containing Os(bpy)(3)(2+) (Os; bpy, 2,2'-bipyridine) with a three-carbon linker was synthesized and used to prepare oligonucleotides with the Os redox catalyst appended to the 5'-end. The electrogenerated Os(III) is capable of oxidizing 7,8-dihydro-8-oxo-guanine (8G), but 8G is not electrochemically reactive at indium tin oxide electrodes because of poor electrode kinetics for the direct reaction. The hairpin-forming oligonucleotide Os-5'-ATG TCA GAT TAG CAG GCC TGA CAT 8G was synthesized and characterized by thermal denaturation and native gel electrophoresis both in the hairpin form and when hybridized to its Watson-Crick complement. The redox potential in both forms of the appended Os(III/II) couple was 0.63 V (all potentials vs Ag/AgCl), which is identical to that for the free complex. The diffusion coefficients of the hairpin form (10.2 x 10(-)(7) cm(2)/s) and the duplex form (8.7 x 10(-)(7) cm(2)/s) were consistent with values expected from studies of noncovalently bound redox labels, which suggest that the measured diffusion coefficient should be that of the appended DNA molecule. The oligonucleotide was designed such that in the duplex form, the 8G is far from the Os(III/II) couple, but in the hairpin form, the 8G is situated close to the redox center. For the duplex form, cyclic voltammetry studies showed that mediated oxidation of the 8G nucleobase occurred only through bimolecular reaction of the electrogenerated Os(III) of one duplex with the 8G of another duplex. However, in the hairpin form, intramolecular electron transfer from 8G to Os(III) in the same molecule was apparent in both chronoamperometry and cyclic voltammetry. 相似文献
66.
Electrocatalytic oxidation of the oligonucleotide 5'- GAA GAG GTT TTT CCT CTT CTT TTT CTT CTC C (TS) by Ru(bpy)(3)(2+) was studied by cyclic voltammetry. This oligonucleotide forms either an intramolecular triplex, hairpin, or single strand, depending on the pH (Plum, G. E.; Breslauer, K. J. J. Mol. Biol. 1995, 248, 679-695). In the triplex form, the guanine doublet in TS is buried inside the folded structure, and as such is less susceptible to oxidation by electrogenerated Ru(bpy)(3)(3+). Digital simulations of the catalytic voltammograms gave a rate constant of 3.5 +/- 0.2 x 10(2) M(-1) s(-1) for oxidation of the triplex form, while oxidation of the duplex and single-stranded forms occurred with much faster rate constants of (3.5-9.1) x 10(4) M(-1) s(-1). Experiments using a truncated form of TS that lacked the third strand of the triplex were consistent with these measurements. The Ru(bpy)(3)(3+) complex was also generated by photolyzing Ru(bpy)(3)(2+) in the presence of Fe(CN)(6)(3-). This reaction produced strand scission following piperidine treatment, which was visualized using high-resolution gel electrophoresis. These experiments showed decreased reactivity for the triplex form, and also gave an unusual reversal of a common selectivity for the 5'-G of GG doublets generally seen in B-form DNA. This reversal was ascribed to strain caused by the location of the GG doublet adjacent to the hairpin loop. 相似文献
67.
Krystyna M. L. Holden Keith D. Bartle Susan R. Hall 《Journal of separation science》1999,22(3):159-163
Conventional operation of the GC Atomic Emission Detector (AED) system involves backflushing of the microwave induced plasma (MIP) during the elution of small volumes of solvent from the GC column. When performing multi-dimensional, on-line LC-GC-AED, significantly larger solvent volumes are introduced into the system and must subsequently be removed. Thus solvent venting procedures are required and the backflushing of the plasma must be extended to facilitate solvent but not solute removal. This study demonstrates the significance of memory effects imparted upon the MIP of the AED if solvent venting is incomplete. Comparison of conventional GC-AED and multi-dimensional LC-GC-AED is made with respect to a fossil fuel sample. 相似文献
68.
Wenyi Li Feng Lin Andrew Hung Anders Barlow Marc-Antoine Sani Rita Paolini William Singleton James Holden Mohammed Akhter Hossain Frances Separovic Neil M. O'Brien-Simpson John D. Wade 《Chemical science》2022,13(8):2226
Antimicrobial peptides (AMPs) are host defense peptides, and unlike conventional antibiotics, they possess potent broad spectrum activities and, induce little or no antimicrobial resistance. They are attractive lead molecules for rational development to improve their therapeutic index. Our current studies examined dimerization of the de novo designed proline-rich AMP (PrAMP), Chex1-Arg20 hydrazide, via C-terminal thiol addition to a series of bifunctional benzene or phenyl tethers to determine the effect of orientation of the peptides and linker length on antimicrobial activity. Antibacterial assays confirmed that dimerization per se significantly enhances Chex1-Arg20 hydrazide action. Greatest advantage was conferred using perfluoroaromatic linkers (tetrafluorobenzene and octofluorobiphenyl) with the resulting dimeric peptides 6 and 7 exhibiting potent action against Gram-negative bacteria, especially the World Health Organization''s critical priority-listed multidrug-resistant (MDR)/extensively drug-resistant (XDR) Acinetobacter baumannii as well as preformed biofilms. Mode of action studies indicated these lead PrAMPs can interact with both outer and inner bacterial membranes to affect the membrane potential and stress response. Additionally, 6 and 7 possess potent immunomodulatory activity and neutralise inflammation via nitric oxide production in macrophages. Molecular dynamics simulations of adsorption and permeation mechanisms of the PrAMP on a mixed lipid membrane bilayer showed that a rigid, planar tethered dimer orientation, together with the presence of fluorine atoms that provide increased bacterial membrane interaction, is critical for enhanced dimer activity. These findings highlight the advantages of use of such bifunctional tethers to produce first-in-class, potent PrAMP dimers against MDR/XDR bacterial infections.Homodimerization of a proline-rich antimicrobial peptide via bioconjugation to perfluoroaromatic linkers confers increased antimicrobial, antibiofilm and immunomodulatory activity. The dimers are promising new therapeutic leads against WHO priority multidrug resistant bacteria. 相似文献
69.
Christopher M. Timperley Robin M. Black Michael Bird Ian Holden Joanna L. Mundy Robert W. Read 《Phosphorus, sulfur, and silicon and the related elements》2013,188(9):2027-2046
Syntheses of diols of structure [HOCH2CH2S]2(CH2)n in 86–95% yield from the sodium salt of 2-mercaptoethanol and Br(CH2)nBr (n = 1 to 5) or in 60–90% yield from 2-chloroethanol and NaS(CH2)nSNa (n = 2 to 5) are described. The diol [HOCH2CH2SCH2CH2]2O was prepared in 82% yield from the sodium salt of 2-mercaptoethanol and [ClCH2CH2]2O, and in 88% yield from 2-chloroethanol and [HSCH2CH2]2O. Mono- and bis-sulfoxides and bis-sulfones of these species were prepared in generally high yield by treatment with an equivalent of KIO4 in aqueous methanol, two equivalents of NaIO4 in aqueous methanol, or four equivalents of H2O2 in trifluoroacetic acid respectively. The compounds are important analytical standards for investigating the fate of the chemical warfare agents sesquimustard Q and oxygen mustard T in environmental samples. 相似文献
70.
We illustrate the use of white noise analysis in the solution of stochastic partial differential equations by explicitly solving the stochastic Neumann boundary-value problem LU(x)–c(x)U(x)=0, xDR
d
,(x)U(x)=–W(x), xD, where L is a uniformly elliptic linear partial differential operator and W(x), xR
d
, is d-parameter white noise. 相似文献