全文获取类型
收费全文 | 836篇 |
免费 | 34篇 |
国内免费 | 8篇 |
专业分类
化学 | 753篇 |
晶体学 | 5篇 |
力学 | 4篇 |
数学 | 47篇 |
物理学 | 69篇 |
出版年
2023年 | 5篇 |
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 9篇 |
2019年 | 9篇 |
2018年 | 10篇 |
2017年 | 7篇 |
2016年 | 11篇 |
2015年 | 18篇 |
2014年 | 16篇 |
2013年 | 50篇 |
2012年 | 34篇 |
2011年 | 49篇 |
2010年 | 17篇 |
2009年 | 28篇 |
2008年 | 53篇 |
2007年 | 64篇 |
2006年 | 56篇 |
2005年 | 68篇 |
2004年 | 48篇 |
2003年 | 54篇 |
2002年 | 35篇 |
2001年 | 12篇 |
2000年 | 12篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 10篇 |
1983年 | 16篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1980年 | 13篇 |
1979年 | 15篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 6篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1971年 | 3篇 |
排序方式: 共有878条查询结果,搜索用时 15 毫秒
1.
Yasushi Seike Ryoko Fukumori Yukiko Senga Hiroki Oka Kaoru Fujinaga Minoru Okumura 《Analytical sciences》2004,20(1):139-142
A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively. 相似文献
2.
Ryohei Tsuda Sayaka Kaino Hisashi Kokubo Shin-Ichiro Imabayashi Masayoshi Watanabe 《Colloids and surfaces. B, Biointerfaces》2007,56(1-2):255-Optics
Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGEn-b-EOm) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EOm without the thermo-responsive EGEn segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGEn segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments. 相似文献
3.
Md. Nur Alam Per B. Zetterlund Masayoshi Okubo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4995-5004
Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007 相似文献
4.
Masayoshi Senba 《Hyperfine Interactions》1994,87(1):959-964
A study has been made of highly nitrogenated pure iron and iron-aluminum alloy powder containing 2 wt.% Al (Fe-2Al) using Mössbauer spectroscopy and X-ray diffraction. The samples were prepared by high-temperature, high-pressure diffusion of nitrogen. They were prepared in a hot-isostatic-pressure (HIP) furnace at 1000 °C at nitrogen pressures up to 200 MPa. The alloy powders contained up to 8 at.% nitrogen as determined by vacuum fusion analysis. XRD analysis indicates that for the pure iron powders, the lattice spacing remained independent of nitrogen concentration, but that for the Fe-2Al powders, it decreased with increasing nitrogen concentration. Mössbauer analysis showed that for the pure iron powders, most of the nitrogen was associated with the formation of the iron nitride Fe4N. For the alloy powders containing less than 5 at.% nitrogen, all of the nitrogen was contained interstitially. The presence of nitrogen completely eliminated the conduction-electron spin-density oscillations observed in many ferromagnetic alloys. 相似文献
5.
Influence of shell strength on shape transformation of micron-sized,monodisperse, hollow polymer particles 总被引:1,自引:0,他引:1
Micron-sized, monodisperse, non-spherical polymer particles with "rugby ball" and "red blood corpuscle"-like shapes were produced by seeded polymerization of the dispersion of (divinylbenzene/vinylbiphenyl/xylene)-swollen polystyrene particles prepared by utilizing the dynamic swelling method which the authors proposed in 1991. Their non-spherical shapes were based on buckling of the shell of the resultant hollow particles. In this article, the reversible shape transformation of the hollow composite polymer particle between spherical and such non-spherical shapes was studied in detail by controlling the shell strength. A part of the shell was buckled by external pressure which was caused by evaporation of xylene from the hollow when the shell had the tensile modulus below the critical value calculated from the pressure-buckling relationship of a spherical shell proposed by Uemura. The plasticization of the shell by a good solvent was one of key factors for the shape transformation. 相似文献
6.
Phase separation in the formation of hollow particles by suspension polymerization for divinylbenzene/toluene droplets dissolving polystyrene 总被引:1,自引:0,他引:1
Phase-separation behavior within polymerizing divinylbenzene/toluene droplet dissolving polystyrenes (PS) was investigated to clarify the formation mechanism of the hollow polymer particles by suspension polymerization. No hollow particles were obtained at a low content of low-molecular-weight PS where phase separation occurred at high conversion. On the other hand, hollow particles were obtained at a high content of high-molecular-weight PS where phase separation occurred at low conversion. The phase separation in an early stage of the polymerization, which was promoted by the presence of PS and cross-links of polydivinylbenzene, was a key factor for the formation of the hollow structure. 相似文献
7.
Nishiura M Hou Z Wakatsuki Y Yamaki T Miyamoto T 《Journal of the American Chemical Society》2003,125(5):1184-1185
Various terminal alkynes have been cleanly dimerized into the corresponding head-to-head (Z)-enynes by use of the half-metallocene lutetium alkyl complexes Me2Si(C5Me4)(NAr)Lu(CH2SiMe3)(THF) (Ar = Ph, C6H3Me2-2,6, C6H2Me3-2,4,6) as catalysts. Aromatic C-Cl, C-Br, and C-I bonds, which are known to be extremely susceptible to reductive cleavage by transition metals, survived in the present reactions. The corresponding dimeric alkynide species [Me2Si(C5Me4)(NAr)Lu(mu-CCR)]2 are thought to be the true catalysts, some of which have been isolated and structurally characterized. These alkynide species were thermally stable and soluble at the reaction temperatures (80-110 degrees C), but they precipitated upon cooling to room temperature after completion of the reaction. Therefore, this catalyst system works homogeneously but can be separated and reused, thus constituting the first example of a recyclable catalyst system for the dimerization of terminal alkynes and also the first example of (Z)-selective head-to-head dimerization of aromatic terminal alkynes. 相似文献
8.
Masahiro?Okada Takumi?Matoba Masayoshi?OkuboEmail author 《Colloid and polymer science》2003,282(2):193-197
The influence of nonionic emulsifier, included inside styrene-methacrylic acid copolymer [P(S-MAA)] particles during emulsion copolymerization, on the formation of multihollow structure inside the particles via the alkali/cooling method (proposed by the authors) was examined in comparison to emulsifier-free particles. It was clarified that the nonionic emulsifier included inside the P(S-MAA) particles eased the formation of multihollow structure.Part CCL of the series studies on suspension and emulsion 相似文献
9.
Production of polyacrylonitrile particles by precipitation polymerization in supercritical carbon dioxide 总被引:2,自引:0,他引:2
Masayoshi?OkuboEmail author Syuji?Fujii Hiroshi?Maenaka Hideto?Minami 《Colloid and polymer science》2003,281(10):964-972
Polyacrylonitrile particles were produced by precipitation polymerization of acrylonitrile (AN) without any colloidal stabilizer in supercritical carbon dioxide as a polymerization medium at about 30 MPa for 24 h at 65 °C at different initiator concentrations (0.8–45.2 mmol/l) and at different AN concentrations (10–40% w/v). An increase in the initiator concentration led to increases in the conversion and in the degree of coagulation and to a decrease in the molecular weight. At AN concentration of 20% w/v, micron-sized, relatively monodisperse polyacrylonitrile particles with clean and uneven surfaces were produced. 相似文献
10.
Tomoya Kinumi Kazuo Tsujimoto Mamoru Ohashi Reiko Hara Tomiyuki Hara Koichi Ozaki Miho Saka Yuko Katsuta Akimori Wada Masayoshi Ito 《Photochemistry and photobiology》1993,58(3):409-412
Abstract— 3, 7-Dimethyl-2, 4, 6, 8, 10-dodecapentaenal was synthesized for reconstitution of the retinochrome analog. Its opsin shift was 1000 cm 1 smaller than that of native retinochrome, whose chromophore contains the same number of double bonds. The conformational change from 6-s-trans to 6-s-cis , as figured in a retinal molecule, plays an important role in the formation of the retinochrome analog, based on the estimation of opsin shifts for retinal analogs locked in the 6-s conformation. Thus the conformation of the 6–7 single bond in the native retinochrome was suggested to be 6 -cis . Analysis of the circular dichroic spectra of retinochrome analogs revealed that the 6-s conformation is independent of the appearance of the β-band. The stereoselectivity in the photoisomerization of the retinal analogs by a retinochrome template depends on the hydrophobic binding in the region of the β-ionone ring. 相似文献