全文获取类型
收费全文 | 2413篇 |
免费 | 73篇 |
国内免费 | 20篇 |
专业分类
化学 | 1844篇 |
晶体学 | 47篇 |
力学 | 24篇 |
综合类 | 1篇 |
数学 | 156篇 |
物理学 | 434篇 |
出版年
2021年 | 19篇 |
2020年 | 24篇 |
2019年 | 39篇 |
2018年 | 27篇 |
2017年 | 19篇 |
2016年 | 41篇 |
2015年 | 47篇 |
2014年 | 47篇 |
2013年 | 149篇 |
2012年 | 87篇 |
2011年 | 151篇 |
2010年 | 67篇 |
2009年 | 80篇 |
2008年 | 130篇 |
2007年 | 130篇 |
2006年 | 129篇 |
2005年 | 115篇 |
2004年 | 134篇 |
2003年 | 107篇 |
2002年 | 92篇 |
2001年 | 68篇 |
2000年 | 42篇 |
1999年 | 39篇 |
1998年 | 39篇 |
1997年 | 29篇 |
1996年 | 31篇 |
1995年 | 28篇 |
1994年 | 21篇 |
1993年 | 20篇 |
1992年 | 20篇 |
1991年 | 25篇 |
1990年 | 29篇 |
1989年 | 20篇 |
1988年 | 30篇 |
1987年 | 29篇 |
1986年 | 18篇 |
1985年 | 44篇 |
1984年 | 41篇 |
1983年 | 26篇 |
1982年 | 28篇 |
1981年 | 25篇 |
1980年 | 20篇 |
1979年 | 26篇 |
1978年 | 19篇 |
1977年 | 18篇 |
1976年 | 18篇 |
1975年 | 13篇 |
1974年 | 10篇 |
1972年 | 11篇 |
1967年 | 12篇 |
排序方式: 共有2506条查询结果,搜索用时 31 毫秒
131.
Using p,p'-dimethoxydiphenyldiazomethane (DMDM) as initiator, the polymerization of methyl methacrylate (MMA) in benzene or in bulk was carried out. The initial rate of polymerization, Rp, was found to be expressed by the following equation: Rp = k[DMDM]0.53 [MMA]0.84 The polymerization was confirmed to proceed by a radical mechanism. The over-all activation energy for the polymerization in benzene was calculated as 19.3 kcal/mole. The rate of thermal decomposition of DMDM was also measured in benzene and the rate equation was obtained as follows: kd (sec?1) = 1.0 × 1015 exp (?29.1 kcal/RT) (for 50-80°C) Explanations of these observations are discussed in connection with those of the preceding papers. 相似文献
132.
Abstract The binary system of tetramethyl tetrazene (TMT) and Co(II) chloride was used as initiator of acrylonitrile (AN) in dimethylformamide. The initial rate of polymerization (Rp) was found to be expressed by Rp = k[TMT]0.62[Co(II) chloride]0.57 [AN]2.00 The polymerization was confirmed to proceed via a radical mechanism. The over-all activation energy for the polymerization was estimated as 15.1 kcal/mole. On the basis of these results and the product analysis of the reaction between the catalyst components in the absence of monomer, the initiation mechanism of the polymerization is discussed. 相似文献
133.
Tatsuro Ouchi Shinji Kitazaki Akinobu Kobayashi Minoru Imoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(7):1045-1059
The radical polymerization of methyl methacrylate (MMA) was carried out with the system of imidazole (Im), copper(n) chloride, and water at 85°C. The effects of the amount of each component on the conversion of MMA were investigated. The polymerization proceeded through a radical mechanism. The overall activation energy was estimated to be 28.7 kJ/mole. The conversion of MMA showed a maximum at pH 8-9 of the aqueous solution. The formation of a complex of CuCl2 with Im, water, and MMA was confirmed by electronic spectra. An initiation mechanism was proposed. 相似文献
134.
Copolymerization of an optically active N-(1-menthyl carboxylatomethyl)citraconimide (MCMCI) was carried out with methyl methacrylate (MMA) with azobisisobutyronitrile as the initiator in benzene at 50°C. All the copolymers obtained were optically active. After the removal of the optically active menthyl group, the hydrolyzed poly(MCMCI-co-MMA)'s still showed optical activity. The asymmetric induction to the copolymer main chain and the mechanism are discussed based on the measurements of optical rotatory dispersion and circular dichroism of the original and hydrolyzed copolymers. 相似文献
135.
136.
Tatsuro Ouchi Kazuo Hagita Hiroshi Sakamoto Minoru Imoto Tsutomu Iwamoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1651-1665
Abstract The polymerization of some kinds of vinyl monomer was found to occur in aqueous solutions of poly(ethylene glycol) diglycolic acid (PEG Acid) or sodium poly(ethylene glycol) diglycolate (PEG Acid Na) through radical mechanisms without any further initiator, as a so-called “uncatalyzed polymerization.” Although the initiating radical species for PEG Acid was determined to be the same as that for PEG Acid Na by means of the spin-trapping technique, the initiating ability of PEG Acid was higher than that of PEG Acid Na. These results are assumed to be attributable to the difference in the initiation mechanisms of the two systems and in the incorporating abilities of monomer into the hydrophobic areas formed by PEG Acid and PEG Acid Na. 相似文献
137.
Tatsuro Ouchi Hiroshi Sakamoto Masayasu Kubo Yoshifumi Hosaka Minoru Imoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):111-123
The radical polymerization of vinyl monomers initiated with several kinds of hydrophilic macromolecule was carried out in a magnetic field. The magnetic field promoted the polymerization; the conversion of monomers and the molecular weight of the polymers obtained increased with increasing field strength in the range of 0–0.1 T. The dependence of the composition and tacticity of the mother polymer on the magnitude of the magnetic field was studied. Using graft or block copolymers, which consisted of hard and soft segments, the effect of a magnetic field was further investigated. The degree of hardness and tightness of the hydrophobic areas (reaction areas) formed by the mother polymer in the aqueous solution was found to affect the magnetic field effect on the uncatalyzed polymerization. The overall activation energy obtained in the magnetic field was almost equal to that obtained without a magnetic field. 相似文献
138.
Katsumi Katoh Seiichiro Nagayama Eiko Higashi Katsuyuki Nakano 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1239-1244
In the hydrosilylation of 1,6-divinyl(perfluorohexane) (FDV) with trichlorosilane (TCS) in the presence of catalytic chloroplatinic acid (Pt-Cat) under an air atmosphere (0.99 MPa), a runaway reaction accompanied by a severe pressure release occurred when Fe2O3 was present as an impurity in the system. In this study, we investigated the mechanism of action of Fe2O3 on this hydrosilylation by monitoring the thermal behavior of TCS/FDV/Pt-Cat/Fe2O3 mixtures with various compositions, using an accelerating rate calorimeter (ARC). In the case of TSC/FDV/Pt-Cat, a typical hydrosilylation composition in the industrial process, heat release, possibly due to hydrosilylation, began at 90 °C. On the other hand, for TCS/FDV/Pt-Cat/Fe2O, the heat release due to hydrosilylation was hardly observed, but abrupt heat and pressure releases occurred at higher temperatures (>170 °C). Like TCS/FDV/Pt-Cat/Fe2O3, TCS/FDV, which contain neither Pt-Cat nor Fe2O3, released heat and pressure at high temperatures (>210 °C), while the heat and pressure release rates were comparatively low. From these results, the runaway reaction may occur when hydrosilylation is prevented, and Fe2O3 behaves as a negative catalyst for hydrosilylation. In the FT-IR spectrum of TCS/FDV/Pt-Cat/Fe2O3 after heating, an absorption peak at approximately 1,710 cm?1, which may be attributed to a carbonyl group, was observed. Thus, it is considered that the runaway reaction observed during the hydrosilylation results from the action of Fe2O3 as a negative catalyst for hydrosilylation as well as as an oxidation catalyst for the by-product generated from the reaction between TCS and FDV. 相似文献
139.
Katsumi Katoh Nobuyuki Saeki Eiko Higashi Yuki Hirose Masahiko Sugimoto Katsuyuki Nakano 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1275-1279
As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts. 相似文献
140.
Makoto Kunisada Taro Masaki Ryusuke Ono Hironobu Morinaga Eiji Nakano Flandiana Yogianti Kunihiro Okunishi Hiroshi Sugiyama Chikako Nishigori 《Photochemistry and photobiology》2013,89(3):649-654
The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage. 相似文献