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31.
[reaction: see text]. A procedure for the chemical synthesis of [3-15N]-labeled pseudouridine and a methylated derivative was developed. A suitably protected pseudouridine precursor was nitrated at N3 followed by treatment with 15NH4Cl to afford the 15N-labeled product in six steps with a 20% yield. This methodology will allow for the production of RNAs with [3-15N]pseudouridine and [3-15N-methyl]pseudouridine at specific locations. 相似文献
32.
The synthesis of 3-methylpseudouridine (m(3)Psi) phosphoramidite, 5'-O-[benzhydryloxybis(trimethylsilyloxy)silyl]-2'-O-[bis(2-acetoxyethoxy)methyl]-3-methylpseudouridine-3'-(methyl-N,N-diisopropyl)phosphoramidite, is reported. Selective pivaloyloxymethyl protection of the Psi N1 followed by methylation at N3 was used to generate the naturally occurring pseudouridine analogue. The m(3)Psi phosphoramidite was used in combination with pseudouridine (Psi) and standard base phosphoramidites to synthesize a 19-nucleotide RNA representing helix 69 of Escherichia coli 23S ribosomal RNA (rRNA) (residues 1906-1924), containing a single m(3)Psi at position 1915 and two Psi's at positions 1911 and 1917. Our synthesis of the fully modified helix 69 RNA demonstrates the ability to make milligram quantities of RNA that can be used for further high-resolution structure studies. Site-selective introduction of the methyl group at the N3 position of pseudouridine at position 1915 causes a slight increase in the thermodynamic stability of the RNA hairpin relative to pseudouridine; RNAs containing either uridine or 3-methyluridine at position 1915 have similar stability. One-dimensional imino proton NMR and circular dichroism spectra of the modified RNAs reveal that the methyl group does not cause any substantial changes in the RNA hairpin structure. 相似文献
33.
Heteroatom variants of the type 2 intramolecular Diels-Alder reaction provide an efficient method for the preparation of bridged bicyclic heterocycles. The type 2 variant of the intramolecular N-acylnitroso Diels-Alder reaction is an effective method for the synthesis of bridged bicyclic oxazinolactams. Structural studies of the cycloadducts have allowed for quantification of the deformations of the bridgehead functionalities and provided a strategy for the stereoselective synthesis of substituted seven- and eight-membered ring lactams. Diastereoselective cycloadditions followed by cleavage of the oxazine ring afford azepin-2-ones or azocin-2-ones. 相似文献
34.
The mechanism of sorption of ions by polyurethanes has been investigated through detailed studies of the extraction of cobalt(II) thiocyanate and the salts of several organic acids. Polyether-based polyurethanes. particularly those containing poly(ethylene oxide), were found to be distinctly superior to polyesters in the sorption of salts and performed much better than might be expected by analogy with monomeric liquid solvents. The results were judged to be inconsistent with several possible mechanisms, including adsorption, solvent extraction, weak or strong base anion-exchange, and complexation of metal anions by the polymer. A new proposal, termed the cation chelation mechanism (CCM), was advanced to account for the observations. In this view, a number of cations (including those of the alkali metals, alkaline earth metals, some transition metals, NH(+)(4), RNH(+)(3) and perhaps H(3)O(+)) may be multiply complexed (chelated) by portions of the polymer, thus facilitating the sorption of accompanying anions. As predicted by the mechanism, moderately strong and selective complexation of several cations was observed to occur with the following order of selectivity: Li(+) < Na(+) < Cs(+) < Rb(+) < K(+) approximately NH(+)(4) < Ag(+) approximately Tl(+) < Ba(2+) < Hg(2+) < Pb(2+). Such behaviour parallels that known for many crown and non-cyclic polyethers and is therefore identified with the polyether portions of the polymer, which are thought to adopt helical conformations surrounding the complexed cations. The cation-chelation mechanism may be widely applicable to the sorption of ions of several types by polyether-based polyurethanes, particularly when large, hydrophobic anions (such as anionic metal complexes) are accompanied by an excess of chelatable cations. 相似文献
35.
Preconcentration of phosphate as molybdoantimonylphosphoric acid on polyurethane foam has been combined with X-ray fluorescence measurement of antimony for the indirect determination of phosphate. The extraction is optimum between pH 1 and 3.6 and no interference is observed from silicate. The precision is 5% RSD at the 0.25-mug ml level and the detection limit is 20 ng ml for 100 ml of sample solution. 相似文献
36.
Conditions for the extraction of the thiocyanate complex of palladium by polyether-type polyurethane foam are reported. Distribution ratios of more than 10(6) with a capacity of about 0.8 mole per kg of foam were obtained. The palladium could be rapidly recovered from the foam with high efficiency by use of ammonia solution. The efficiency of palladium extraction depends on how well the cation associated with the complex fits into the polyether segment of the polyurethane foam. 相似文献
37.
Ying Wang Sheng‐Ping Yang Jian‐Min Yue Sharon Chow William Kitching 《Helvetica chimica acta》2003,86(7):2424-2433
Four novel sesquiterpenes, namely 7α,8β,13‐trihydroxy‐5,13‐marasmanolide ( 2 ), isoplorantinone ( 5 ), 4,8,14‐trihydroxyilludala‐2,6,8‐triene ( 6 ), and 8‐hydroxy‐8,9‐secolactara‐1,6‐dien‐5,13‐olide ( 10 ), together with six known ones, 7α,8β‐dihydroxy‐5,13‐marasmanolide ( 1) , 7α,8α‐dihydroxy‐5,13‐marasmanolide ( 3 ), isolactarorufin ( 4 ), blennin A ( 7 ), blennin D ( 8 ), and lactarorufin ( 9 ), were isolated from the ethanolic extract of Lactarius piperatus. The structures of these sesquiterpenes, representing diversified structural types, were determined mainly by spectroscopic methods, especially 2D‐NMR techniques. The structure of 6 was further confirmed by a single‐crystal X‐ray‐diffraction determination. 相似文献
38.
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40.
Wong EL Chow E Gooding JJ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6957-6965
The effect of the surface chemistry of DNA recognition interfaces on DNA hybridization at a gold surface was investigated using both electrochemistry and the quartz crystal microbalance (QCM) technique. Different DNA recognition interfaces were prepared using a two-component self-assembled monolayer consisting of thiolated 20-mer probe single-stranded DNA (ss-DNA) containing either a 3'-mercaptopropyl or a 3'-mercaptohexyl linker group and an alcohol-terminated diluent layer with 2-, 6-, or 11-carbon length. The influence of the interfacial design on the hybridization efficiency, the affinity constant (Ka) describing hybridization, and the kinetics of hybridization was assessed. It was found that the further the DNA was above the surface defined by the diluent layer the higher the hybridization efficiency and Ka. The kinetics of DNA hybridization was assessed using both a QCM and an electrochemical approach to ascertain the influence of the interface on both the initial binding of target DNA to the surface and the formation of a complete duplex. These measurements showed that the length of the diluent layer has a large impact on the time taken to form a perfect duplex but no impact on the initial recognition of the target DNA by the immobilized probe DNA. 相似文献