全文获取类型
收费全文 | 4292篇 |
免费 | 111篇 |
国内免费 | 12篇 |
专业分类
化学 | 3052篇 |
晶体学 | 52篇 |
力学 | 66篇 |
综合类 | 1篇 |
数学 | 224篇 |
物理学 | 1020篇 |
出版年
2023年 | 23篇 |
2022年 | 20篇 |
2021年 | 39篇 |
2020年 | 58篇 |
2019年 | 66篇 |
2018年 | 51篇 |
2017年 | 31篇 |
2016年 | 67篇 |
2015年 | 76篇 |
2014年 | 92篇 |
2013年 | 193篇 |
2012年 | 186篇 |
2011年 | 230篇 |
2010年 | 146篇 |
2009年 | 142篇 |
2008年 | 232篇 |
2007年 | 261篇 |
2006年 | 259篇 |
2005年 | 191篇 |
2004年 | 166篇 |
2003年 | 171篇 |
2002年 | 159篇 |
2001年 | 118篇 |
2000年 | 134篇 |
1999年 | 84篇 |
1998年 | 60篇 |
1997年 | 57篇 |
1996年 | 47篇 |
1995年 | 43篇 |
1994年 | 44篇 |
1993年 | 59篇 |
1992年 | 50篇 |
1991年 | 49篇 |
1990年 | 38篇 |
1989年 | 49篇 |
1988年 | 49篇 |
1987年 | 42篇 |
1986年 | 35篇 |
1985年 | 54篇 |
1984年 | 58篇 |
1983年 | 48篇 |
1982年 | 48篇 |
1981年 | 31篇 |
1980年 | 34篇 |
1979年 | 49篇 |
1978年 | 43篇 |
1977年 | 48篇 |
1975年 | 26篇 |
1974年 | 32篇 |
1967年 | 16篇 |
排序方式: 共有4415条查询结果,搜索用时 15 毫秒
161.
Junpei Naito Yoko Yamamoto Megumi Akagi Satoshi Sekiguchi Masataka Watanabe Nobuyuki Harada 《Monatshefte für Chemie / Chemical Monthly》2005,60(1):411-445
The CD exciton chirality method was applied to various phenylacetylene alcohols to determine their absolute configurations; the long axis polarized –* transition (max=252nm) of the 4-methoxyphenylacetylene chromophore couples with the transition (max=257nm) of the 4-methoxybenzoate group to generate intense exciton split CD Cotton effects, from the signs of which the absolute configurations of phenylacetylene alcohols were unambiguously determined. As an extension of the results, a new methodology for determining the absolute configurations of acetylene alcohols having the HCCCH(OH)-moiety by combination of the Sonogashira reaction and the CD exciton chirality method has been developed and applied. Since the –* transition of acetylene triple bond is located below 180nm, it is difficult to observe ideal bisignate CD Cotton effects due to the exciton coupling between acetylene and benzoate chromophores. To observe the ideal exciton split Cotton effects necessary for the unambiguous determination of absolute configuration, the terminal acetylene group was converted, by the Sonogashira reaction, to the 4-methoxyphenylacetylene moiety, which exhibits an intense –* absorption band polarized along the long axis of the chromophore at 252nm. As a partner of exciton coupling, 4-methoxybenzoate showing a –* band at 257nm was introduced into the alcohol moiety, and the benzoates formed showed intense bisignate CD Cotton effects, from the signs of which the absolute configurations of original acetylene alcohols could be determined in an unambiguous manner. 相似文献
162.
Vilsmeier–Haack‐type cyclization of 1H‐indole‐4‐propanoic acid derivatives was examined as model construction for the A–B–C ring system of lysergic acid ( 1 ). Smooth cyclization from the 4 position of 1H‐indole to the 3 position was achieved by Vilsmeier–Haack reaction in the presence of K2CO3 in MeCN, and the best substrate was found to be the N,N‐dimethylcarboxamide 9 (Table 1). The modified method can be successfully applied to an α‐amino acid derivative protected with an N‐acetyl function, i.e., to 27 (Table 2); however, loss of optical purity was observed in the cyclization when a chiral substrate (S)‐ 27 was used (Scheme 5). On the other hand, the intramolecular Pummerer reaction of the corresponding sulfoxide 20 afforded an S‐containing tricyclic system 22 , which was formed by a cyclization to the 5 position (Scheme 3). 相似文献
163.
164.
S. Watanabe N. S. Ishioka T. Sekine A. Osa M. Koizumi H. Shimomura K. Yoshikawa H. Muramatsu 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):495-498
Ion implantation was applied to the production of endohedral 133Xe-fullerene. Using an isotope separator, 133Xe ions were implanted into a fullerene target of C60 and C70 produced by vacuum evaporation on a Ni backing. An HPLC analysis following dissolution of the fullerene targets in o-dichlorobenzene corroborated the formation of 133Xe@C60 and 133Xe@C70, showing a strong correlation between C60/C70 and 133Xe. The observed tailing following 133Xe peaks in the elution curves suggests a possibility of the isolation of endohedral 133Xe-fullerene from empty fullerene. 相似文献
165.
Haruhiko Watanabe Masao Murano 《Journal of polymer science. Part A, Polymer chemistry》1971,9(4):911-918
The γ-ray induced polymerizations of α-chloroacrylic acid, mp 66°C, and α-bromo-acrylic acid, mp 72°C, were investigated in the temperature range from 35°C to 85°C. An analysis of polymerization kinetics was made, and results were similar to those reported in the literature for other vinyl monomers. On heating of the polymer obtained, elimination of hydrogen halide takes place, and intramolecular lactone formation is observed. The rate of lactone formation of poly(α-chloroacrylic acid) obtained in the solid-state polymerization was found to be higher than that in the liquid state, because a highly isotactic configuration of polymers, tends to be formed in the solid-state polymerization, and elimination of hydrogen chloride is facilitated with an isotactic 52 helix structure. 相似文献
166.
Yamanaka N Kawano R Kubo W Kitamura T Wada Y Watanabe M Yanagida S 《Chemical communications (Cambridge, England)》2005,(6):740-742
Use of a new ionic liquid crystal, 1-dodecyl-3-methylimidazolium iodide, and iodine as an electrolyte of dye-sensitized solar cells leads to a high short circuit photocurrent density and a high light-to-electricity conversion efficiency, due to a self-assembled structure of the imidazolium cations, resulting in high conductivity of the electrolyte. 相似文献
167.
Ishikawa T Mukai B Shiraishi S Utoguchi N Fujii M Matsumoto M Watanabe Y 《Chemical & pharmaceutical bulletin》2001,49(2):134-139
To decrease the sensation of roughness when a tablet, which is rapidly disintegrated by saliva (rapidly disintegrating tablet), is orally taken, we prepared rapidly disintegrating tablets using microcrystalline cellulose (Avicel PH-M series), a new type of pharmaceutical excipient that is spherical and has a very small particle size (particle size, 7-32 microm), instead of conventional microcrystalline cellulose (PH-102) used in the formulation of tablets containing acetaminophen or ascorbic acid as model drugs for tableting study. Tablets (200 mg) prepared using spherical microcrystalline cellulose, PH-M-06, with the smallest particle size (mean value, 7 microm) had sufficient crushing tolerance (approximately, 8 kg) and were very rapidly, disintegrated (within 15 s) when the mixing ratio of PH-M-06 to low-substituted hydroxypropylcellulose (L-HPC) was 9:1. Sensory evaluation by volunteers showed that PH-M-06 was superior to PH-102 in terms of the feeling of roughness in the mouth. Consequently, it was found that particle size is an important factor for tablet preparation using microcrystalline cellulose. It is possible to prepare drugs such as acetaminophen and ascorbic acid (concentration of approximately 50%) in the tablet form using PH-NM-06 in combination with L-HPC as a good disintegrant at a low compression force (1-6 kN). To solve the problem of poor fluidity in the preparation of these tablets, we investigated the use of spherical sugar granules (Nonpareil, NP-101 (sucrose and starch, composition ratio of 7:3), NP-103 (purified sucrose), NP-107 (purified lactose) and NP-108 (purified D-mannitol)). Rapidly disintegrating tablets can be prepared by the direct compression method when suitable excipients such as fine microcrystalline cellulose (PH-M-06) and spherical sugar granules (NP) are used. 相似文献
168.
169.
Takeshi Wada Terutaka Watanabe Masaaki Takehisa 《Journal of polymer science. Part A, Polymer chemistry》1971,9(9):2659-2672
The dependence of the dose rate on the rate of radiation-induced polymerization of ethylene in tert-butyl alcohol containing 5 vol-% water was studied. The reaction was carried out by use of a reactor with a capacity of 100 ml under the following conditions: pressure, 200 kg/cm2; temperature, 24 ± 3°C; dose rate, 3.7 × 104?1.6 × 105 rad/hr; amount of medium, 70 ml. The dose rate exponents for rate of the polymerization, the molecular weight, and the number of polymer chain were found to be about 0.8, ?0.1, and 0.9, respectively. These results were well explained with kinetic results (obtained by a novel analytical method) for the polymerization which contain both first-order and second-order terminations for the concentrations of propagating radical. The individual values of the rate constants in each elementary reaction were also obtained. 相似文献
170.
The 7,8-bis(benzyloxy)bicyclo[2.2.2]octa-2,5-diene derivatives have been synthesized via Diels-Alder reaction of optically active 5,6-bis(benzyloxy)cyclohexa-1,3-diene and dienophiles. The corresponding tricarbonyliron complexes have also been synthesized in enantiomerically pure form. 相似文献