全文获取类型
收费全文 | 5678篇 |
免费 | 178篇 |
国内免费 | 28篇 |
专业分类
化学 | 4078篇 |
晶体学 | 47篇 |
力学 | 144篇 |
综合类 | 1篇 |
数学 | 322篇 |
物理学 | 1292篇 |
出版年
2021年 | 58篇 |
2020年 | 66篇 |
2019年 | 65篇 |
2018年 | 56篇 |
2017年 | 50篇 |
2016年 | 127篇 |
2015年 | 114篇 |
2014年 | 127篇 |
2013年 | 267篇 |
2012年 | 312篇 |
2011年 | 331篇 |
2010年 | 190篇 |
2009年 | 162篇 |
2008年 | 312篇 |
2007年 | 306篇 |
2006年 | 318篇 |
2005年 | 296篇 |
2004年 | 282篇 |
2003年 | 238篇 |
2002年 | 244篇 |
2001年 | 152篇 |
2000年 | 132篇 |
1999年 | 91篇 |
1998年 | 73篇 |
1997年 | 55篇 |
1996年 | 65篇 |
1995年 | 54篇 |
1994年 | 52篇 |
1993年 | 60篇 |
1992年 | 66篇 |
1991年 | 47篇 |
1990年 | 41篇 |
1989年 | 50篇 |
1988年 | 49篇 |
1987年 | 46篇 |
1986年 | 40篇 |
1985年 | 97篇 |
1984年 | 91篇 |
1983年 | 26篇 |
1982年 | 58篇 |
1981年 | 45篇 |
1980年 | 48篇 |
1979年 | 88篇 |
1978年 | 58篇 |
1977年 | 69篇 |
1976年 | 59篇 |
1975年 | 41篇 |
1974年 | 31篇 |
1973年 | 21篇 |
1972年 | 22篇 |
排序方式: 共有5884条查询结果,搜索用时 46 毫秒
71.
Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the CC bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this CC bond formation. 相似文献
72.
Hidemasa Yamaguchi Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1970,8(6):1467-1479
Optically active N-bornylmaleimide (NBMI) was copolymerized with styrene, methyl methacrylate, and vinylidene chloride with a free-radical catalyst to obtain optically active copolymers. The monomer reactivity ratios for the radical copolymerization of NBMI (M2) with styrene, methyl methacrylate, and vinylidene chloride were: ST-NBMI, r1 = 0.13, r2 = 0.05; MMA-NBMI, r1 = 2.02, r2 = 0.16; VCl2-NBMI, r1 = 1.15, r2 = 0.47. The Q-e values for NBMI were Q2 = 0.48 and e2 = +1.47. The specific rotation and optical rotatory dispersion of these copolymers were measured. The correlation between the specific rotation and composition of these copolymers was not linear. The value of λc for each copolymer was independent of the copolymer composition and the comonomer, being 260 mμ for the St-NBMI system, 262 mμ for the MMA-system, and 260 mμ for the VCl2-NBMI system. The effects of solvents and temperature on the specific rotation of these copolymers were investigated. 相似文献
73.
Kazukiyo Kobayashi Hiroshi Sumitomo 《Journal of polymer science. Part A, Polymer chemistry》1969,7(5):1287-1294
Adducts (X, Y, and Z) between triethylaluminum and β-cyanopropionaldehyde (CPA) have been prepared and characterized. It was found that an equimolar amount of triethylaluminum undergoes Grignard type addition reaction with aldehyde group of CPA to give aluminum alkoxide and that another equimolar quantity of triethylaluminum undergoes coordination with the nitrile group of CPA (adduct X, in which the molar ratio of CPA to aluminum is 1:2). The coordinated triethylaluminum in adduct X may be changed to aluminum alkoxide by the addition of further equimolar amount of CPA (adduct Y, molar ratio = 1:1); on the other hand, heating at 130°C affords mixtures of aluminum aldimine and aluminum ketenimine structures (adduct Z, molar ratio = 1:2). From the cryoscopic measurement, adduct Z may be regarded as a coordinated polymer joined through bridged structures I and II. In the polymerization of CPA at ?78°C, the stereoregularity of the resulting poly-(cyanoethyl)oxymethylene was found to increase in the order: X < triethylaluminum < Y < Z. The polymerizations with triethylaluminum, X, and Y are considered to be initiated by NCCH2CH2CH(C2H5)? O? Al(C2H5)2. The degree of association of the species may influence the stereoregularity of the polymer. 相似文献
74.
A simple synthesis of 3,3,3-trifluoropropenyl compounds by means of the TBAF-mediated Horner reaction is described. The reagent, 2,2,2-trifluoroethyldiphenylphosphine oxide, was readily prepared either by Arbuzov reaction of ethyl diphenylphosphinite with 2,2,2-trifluoroethyl iodide or by treating chlorodiphenylphosphine with trifluoroacetic acid and water. Treatment of the phosphine oxide with aromatic aldehydes in the presence of TBAF at room temperature afforded the corresponding 3,3,3-trifluoropropenyl compounds in good yields. The present method is very convenient for preparing 3,3,3-trifluoropropenyl compounds from aromatic aldehydes in terms of availability of the reagent, operational simplicity, and good yields of the products. 相似文献
75.
Akio Nara Nobuko Kobayashi Kazuko Hasegawa Katsuko Honba Shigeo Baba 《Microchemical Journal》1975,20(4):440-448
For the conductometric titration of fluoride with calcium acetate, solvent system in sample solution and titrant, concentration, and acidity of sample solution were examined to establish the titration conditions. Results of these examinations were transferred to the microdetermination of fluorine in organic compounds using oxygen flask combustion method.Comparative examination between quartz and Pyrex flasks for the combustion of fluorine samples indicated that good results were obtained by the use of the former flask, whereas the use of the latter one gave negative values of 1.0–1.6% due to the formation of boron fluoride during the combustion. 相似文献
76.
Poly(N-isopropylacrylamide) (PNIPAM) has a low critical solution temperature (LCST) at 32°C in water and the hydrophilicity changes through the LCST. The microspheres whose surface was composed of PNIPAM exhibited phase transition behavior around 32°C. Therefore, the interactions between PNIPAM micropheres and granulocytes depended on the temperature. That is, the oxygen consumption and active oxygen production by cells in contact with PNIPAM-containing microspheres and adhesion of the microspheres to the cell surface were more enhanced above the LCST of PNIPAM than below it, whereas no significant temperature dependence of cell–microspheres interaction was observed in nonthermosensitive microsphere systems. It was suggested that the function of cells could be controlled with temperature using the temperature-sensitive microspheres. 相似文献
77.
Yoh Kodera Ayako Ajima Katsunobu Takahashi Ayako Matsushima Yuji Saito Yuji Inada 《Photochemistry and photobiology》1988,47(2):221-223
Abstract— Hematoporphyrin, having two carboxylic groups, was coupled with α-(3-aminopropyl)-ω-methoxypoly(oxyethylene), PEG-NH2 , through acid-amide bond formed with carbodtimide. PEG-modified hematoporphyrin was readily soluble not only in neutral aqueous solution but also in organic solvents. Its absorption spectrum showed a sharp band at 376 nm in neutral aqueous solution and at 403 nm in benzene. Modified hematoporphyrin acted as a photosensitizer; imidazole and indole were photooxidized in organic solvents such as benzene or chloroform, and uric acid was also photooxidized in neutral aqueous solution. 相似文献
78.
[structure in text] The absolute configurations at 12 chiral centers in amphidinolide C (1), a potent cytotoxic 25-membered macrolide isolated from a marine dinoflagellate Amphidinium sp., were determined to be 3S, 4R, 6R, 7R, 8R, 12R, 13S, 16S, 20R, 23R, 24R, and 29S by combination of NMR analyses, degradation experiments, and synthesis of the C-1-C-7 segment. 相似文献
79.
Yoshitaka Ogiwara Hitoshi Kubota Yuji Kimura 《Journal of polymer science. Part A, Polymer chemistry》1978,16(11):2865-2873
The influence of ferric acetylacetonate [Fe(acac)3] on the photodegradation of model compounds of polyethylene (PE) was examined. By studying electron-spin-resonance (ESR) spectra of photoirradiated compounds such as 1-octene and 1,7-octadiene, which contain carbon double bonds, Fe(acac)3 was found to accelerate the formation of allyl radical by contact with them. On the other hand, Fe(acac)3 suppressed the radical formation based on Norrish type I reaction in a carbonyl group of compounds such as 2-octanone and 3-octanone. Based on the study of ultraviolet (UV) spectra as well as ESR spectra on photoirradiated samples, the influence of Fe(acac)3 on the photodecomposition of model compounds of PE was discussed. Finally, the discussion turned to the mechanism of photodecomposition of PE in the presence of ferric salt. 相似文献
80.
[structure: see text] Absolute stereochemistry of amphidinolides G (1) and H (2), potent cytotoxic 27- and 26-membered macrolides, respectively, isolated from a marine dinoflagellate Amphidinium sp., was determined by X-ray diffraction analysis, synthesis of a degradation product (3) of 2, and interconversion between 1 and 2. 相似文献