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61.
Yoshio Iwakura Keikichi Uno Shigeyoshi Hara Shigeru Kurosawa 《Journal of polymer science. Part A, Polymer chemistry》1968,6(12):3381-3393
A new ring-opening reaction of 1,3,4-oxadiazole by methylating reagents was developed in fuming sulfuric acid or polyphosphoric acid and then, by applying this reaction to poly-p-phenylene-1,3,4-oxadiazole, a high molecular weight poly-N-methylterephthalylhydrazide was obtained. Various methylating reagents were investigated as ring-opening reagents. The degrees of ring-opening in polymers were estimated and related to the properties of the polymers. 相似文献
62.
Sayo Ito Yoshihiro Ishikawa Satoshi Nishino Teruyuki Kobayashi Shigeru Ohba Yuzo Nishida 《Polyhedron》1998,17(25-26)
We have prepared several new iron(III) complexes with ligands which contain a phenol group; these are tetradentate [(X-phpy)H, X and H(phpy) represent the substituents on the phenol ring and N,N-bis(2-pyridylmethyl)-N-(2-hydroxybenzyl)amine, respectively] and pentadentate ligands [(R-enph-X)H; R=ethyl(Et) or methyl(Me) derivative and H(Me-enph) denotes N,N-bis(2-pyridylmethyl)-N″-methyl-N″-(2″-hydroxyl-benzylamine)ethylenediamine] and have determined the crystal structures of Fe(phpy)Cl2, Fe(5-NO2-phpy)Cl2, and Fe(Me-enph)ClPF6, which are of a mononuclear six-coordinate iron(III) complex with coordination of one or two chloride ion(s). These compounds are highly colored (dark violet) due to the coordination of phenol group to an iron(III) atom. When hydrogen peroxide was added to the solution of the iron(III) complex, a color change occurs with bleaching of the violet color, indicating that oxidative degradation of the phenol moiety occurred in the ligand system. The bleaching of the violet color was also observed by the addition of t-butylhydroperoxide. The rate of the disappearance of the violet color is highly dependent on the substituent on the phenol ring; introduction of an electron-withdrawing group in the phenol ring decreases the rate of bleaching, suggesting that disappearance of the violet band should be due to a chemical reaction between the phenol group and a peroxide adduct of the iron(III) species with an η1-coordination mode and that in this reaction the peroxide adduct acts as an electrophile towards phenol ring. The intramolecular interaction between the phenol moiety and an iron(III)-peroxide adduct may induce activation of the peroxide ion, and this was supported by several facts that the solution containing an iron(III) complex and hydrogen peroxide exhibits high activities for degradation of nucleosides and albumin. 相似文献
63.
A quartz crystal microbalance (QCM) immunosensor was developed for the detection of 2,3,7,8-tetrachlorodibenzo-p-dioxins (TCDD) in environmental pollutants. An anti-TCDD antibody was immobilized on the gold surface of the QCM via chemical coupling, and its immunologic activity was then maintained by treatment with an artificial stabilizing reagent such as poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate). A competitive immunoreaction with TCDD conjugated ovalbumin (TCDD-ovalbumin) was used to detect TCDD. A calibration curve was obtained through the competitive immunoreaction, and linearity was shown from 100 ng mL(-1) to 0.1 ng mL(-1). Also, the cross-reactivities of the anti-TCDD monoclonal antibody were thoroughly evaluated with several TCDD derivatives. The relationships between GC-MS, ELISA, and QCM were compared using fly ash samples from a municipal solid waste, which were prepared using an accelerated solvent extractor. For 23 samples, the experimental relationship between the TCDD concentration by QCM vs. the TCDD concentration by ELISA was y= 1.07x + 2.70, r= 0.99, and the TCDD concentration by QCM vs. the toxic equivalent quantity (TEQ) value by GC-MS was y= 2.46x - 14.98, r= 0.89. 相似文献
64.
On-line sample preconcentration by a dynamic pH junction in conjunction with multiplexed capillary electrophoresis (CE) and UV detection represents a sensitive and high-throughput format for future metabolomic research, such as purine analysis. The optimization of purine focusing can be rapidly assessed by systematically altering the sample matrix properties, such as the buffer co-ion, pH and ionic strength using a 96-capillary array format. This method permits focusing of large sample injection volumes, resulting in over a 50-fold improvement in the concentration sensitivity. The limit of detection (S/N = 3) for purine metabolites was less than 8.0 x 10(-8) M under optimum conditions when using UV absorbance. Dynamic pH junction multiplexed CE demonstrated excellent linearity over a hundred-fold concentration range, as well as low inter-capillary precision in terms of normalized migration times and peak areas. The potential for clinically relevant high-throughput analyses of micromolar amounts of purine metabolites in urine was also demonstrated. 相似文献
65.
Emerging fields of biochemical research, such as metabolomics, present challenges to current separation technologies because of the large number of metabolites present in a cell and their often low (submicromolar) concentration. Although capillary electrophoresis (CE) holds great promise as the method of choice for high-resolution separations of biological samples, it suffers from poor concentration sensitivity, especially with the use of UV detection. In CE, sweeping and dynamic pH junction represent two complementary on-line focusing techniques that have been used for sensitivity enhancement of hydrophobic and weakly acidic analytes, respectively. However, the application of either the sweeping or dynamic pH junction technique alone might, in some cases, be less effective for the analysis of certain sample mixtures. Recent work in the development of a hyphenated dynamic pH junction-sweeping technique is presented as an effective on-line method of preconcentration suitable for both hydrophilic (anionic) and hydrophobic (neutral) analytes. Sensitive analyses of flavin metabolites by CE with laser-induced fluorescence (LIF) detection is demonstrated in various biological matrixes, including cell extracts of Bacillus subtilis, pooled human plasma, as well as heat-deproteinized flavoenzymes. Enhanced analyte band narrowing and improved sensitivity is achieved for flavins using dynamic pH junction-sweeping compared to either sweeping or dynamic pH junction alone. This results in over a 1200-fold improvement in sensitivity relative to conventional injection methods, giving a limit of detection (LOD, defined as S/N = 3) of about 4.0 x 10(-12) M. Strategies for sensitive and more comprehensive analyses of other cell metabolites, including nucleotides, coenzymes, and steroids, are also discussed when using on-line focusing techniques in conjunction with multiplexed CE and UV detection. 相似文献
66.
Takayuki Otsu Bunichiro Yamada Shigeru Sugiyama Shigeki Mori 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2197-2207
Radical polymerization and copolymerization of some o-alkylphenyl methacrylates were carried out and the effect of the ortho-substituents on the ability to homopolymerize, on the monomer reactivities, and on the ceiling temperatures of the monomers was studied. The effect of the substituent on tacticities and thermal stabilities of the polymers formed was also discussed. The ability to honiopolymerize and the monomer reactivity were considerably decreased by the introduction of the o-substituent. 2,6-Di-tert-butylphenyl methacrylate formed no methanol-insoluble polymer at 60°C. On the basis of the tacticity determined it was noted that the o-substituted phenyl methacrylates preferred syndiotactic addition in the propagation reaction less than did phenyl methacrylate or methyl methacrylate. The polymers formed from the o-substituted monomers were thermally less stable than poly(phenyl methacrylate), and, consistent with this finding, ceiling temperatures of the o-substituted phenyl methacrylates seemed to be lower than that of phenyl methacrylate. The effects observed were characteristic of the o-substituents conformationally close to the carbon-carbon double bond of the monomer or the carbon carrying the unpaired electron of the polymer radical. 相似文献
67.
Photocatalytic reactions occurring at semiconductor particles/solution interfaces can be applied to organic syntheses. In this review article, examples of photocatalytic syntheses of cyclic amino acids by suspended semiconductor particles, e.g., titanium(IV) oxide or cadmium(II) sulfide are introduced and interpreted. Different from the photocatalytic decomposition of pollutants under aerobic conditions, selective conversion of organic compounds can be driven by the photocatalytic reactions under deaerated conditions. 相似文献
68.
In this article, it was demonstrated that a subsecond separation of cellular metabolites such as riboflavin (RF), flavin mononucleotide (FMN), and flavin-adenine dinucleotide (FAD) was achieved using microchip capillary electrophoresis with laser-induced fluorescence detection. The influences of crucial parameters that governed analysis time (e.g., channel length and electric field for separation) and separation resolution (e.g., sample size) were investigated, both in theoretical aspects and experimental practice. Quantitative analyses were performed that exhibited linear dynamic range of two orders of magnitude, with calculated detection limits of 34, 201, and 127 nM for RF, FAD, and FMN, respectively. To test the validity of the method, it was successfully applied to characterize several recombinant flavin-binding domains in a human neuronal nitric oxide synthase. 相似文献
69.
A reversible cyclic voltammogram for the one-electron reduction of ferrocene in 1,2-dimethoxyethane is recorded under experimental conditions that enable the ferrocene anion to exist for a few minutes. The formal rate constant of the ferrocene0/? electrode, determined by cyclic voltammetry at ?45°C, ca. 10?3 cm s?1, is in striking contrast with that of ferrocene+/0, > 10?1 cm s?1. The distortion of the ferrocene molecule caused by reduction may be a reason for this difference in electron-transfer rate. 相似文献
70.
Geochemical record of U and Th isotopes in bottom sediments of Lake Kawaguchi at the foot of Mt. Fuji, Central Japan 总被引:1,自引:0,他引:1
A. Sakaguchi M. Yamamoto T. Shimizu S. Koshimizu 《Journal of Radioanalytical and Nuclear Chemistry》2004,262(3):617-628
Sediment cores from Lake Kawaguchi at the foot of Mt. Fuji in Japan were analyzed for U and Th isotopes (238U, 234U, 232Th, 230Th and 228Th) in the light of the linkage to paleoenvironmental changes. These isotopic concentrations and their ratios varied widely with depth of sediment core. A marked disequilibrium (1.1–1.5) higher than the value of 1.0 was observed for 234U/238U activity ratios, indicating that U from lake water with high 234U/238U ratio (ca. 1.6) was transferred to the bottom sediment by adsorption and/or adhesion onto the settling particles. By using model equations, the U found in the sediment core was separated into lithogenous and autogenous U fractions. These depth profiles were compared with parameters such as organic matter and biogenic-SiO2 contents and amount of rainfall. Some variations of selected parameters with depth coincided with those of lithogenous or autogenous U. The results obtained suggest that variation in the lithogenous and/or autogenous U in the sediment with depth might be helpful in tracing the geochemical behavior of U and the past environmental changes in the area surrounding Lake Kawaguchi.The authors would like to express their gratitude to Dr. Y. Ohtsuka of Department of Radioecology, Institute for Environmental Sciences and Dr. K. Sasaki of Department of Cultural Properties and Heritage, Kanazawa Gakuin University for sampling of water and rock samples at Lake Kawaguchi. 相似文献