全文获取类型
收费全文 | 1313篇 |
免费 | 40篇 |
国内免费 | 4篇 |
专业分类
化学 | 1098篇 |
晶体学 | 12篇 |
力学 | 16篇 |
数学 | 28篇 |
物理学 | 203篇 |
出版年
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 12篇 |
2020年 | 12篇 |
2019年 | 15篇 |
2018年 | 12篇 |
2017年 | 6篇 |
2016年 | 21篇 |
2015年 | 28篇 |
2014年 | 30篇 |
2013年 | 77篇 |
2012年 | 68篇 |
2011年 | 59篇 |
2010年 | 39篇 |
2009年 | 31篇 |
2008年 | 68篇 |
2007年 | 89篇 |
2006年 | 86篇 |
2005年 | 63篇 |
2004年 | 76篇 |
2003年 | 61篇 |
2002年 | 62篇 |
2001年 | 38篇 |
2000年 | 25篇 |
1999年 | 25篇 |
1998年 | 22篇 |
1997年 | 20篇 |
1996年 | 18篇 |
1995年 | 11篇 |
1994年 | 16篇 |
1993年 | 15篇 |
1992年 | 25篇 |
1991年 | 16篇 |
1990年 | 11篇 |
1989年 | 14篇 |
1988年 | 11篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 21篇 |
1984年 | 19篇 |
1983年 | 9篇 |
1982年 | 14篇 |
1981年 | 23篇 |
1980年 | 11篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1977年 | 9篇 |
1976年 | 5篇 |
1975年 | 9篇 |
1973年 | 4篇 |
排序方式: 共有1357条查询结果,搜索用时 15 毫秒
991.
Mori M Tanaka K Helaleh MI Xu Q Ikedo M Ogura Y Sato S Hu W Hasebe K 《Journal of chromatography. A》2003,997(1-2):191-197
This paper describes an ion-exclusion chromatographic system for the rapid and selective determination of ammonium ion. The optimized ion-exclusion chromatographic system was established with a polymethacrylate-based weakly basic anion-exchange resin column (TSKgel DEAE-5PW) as the separation column, an aqueous solution containing 0.05 mM tetramethylammonium hydroxide (pH 9.10) as eluent with conductimetric detection for the analyte determination. Under the optimum chromatographic conditions, ammonium ion was determined within 2.3 min with a detection limit (S/N=3) better than 0.125 microM. Ammonium ion in rain and river waters was precisely determined using this ion-exclusion chromatographic system. 相似文献
992.
Eight new plant growth-promoting steroids (brassinolide, castasterone, dolicholide, dolichosterone, homodolicholide, homodolichosterone, 6-deoxocastasterone and 6-deoxodolichosterone) were synthesized by the regio- and stereoselective ring-opening reactions of 23,24-epoxides prepared from stigmasterol. 相似文献
993.
Kazuhiko Ishihara Naoshi Hamada Shinji Kato Isao Shinohara 《Journal of polymer science. Part A, Polymer chemistry》1984,22(1):121-128
To control the swelling of polymer membrane by photoirradiation amphiphilic azoaromatic polymer membranes were prepared and a photoinduced change in the swelling degree of water was investigated. The azobenzene moiety in the side chain of the polymer was isomerized from trans form to cis form by ultraviolet (UV) irradiation and reverse isomerization was found by visible light irradiation. The swelling degree of the polymer membrane for water in the dark was decreased by UV radiation, and when visible light irradiation was carried out in the polymer membrane the degree of swelling recovered to the original level. The swelling degree decreased with an increase in the mole fraction of the azobenzene moiety in the dark and under UV irradiation. The deswelling degree of the polymer membrane by UV irradiation also decreased with an increase in the mole fraction of the azobenzene moiety. This reversible change in the swelling degree was considered to be caused by the photoisomerization of the azobenzene moiety in the polymer membrane. 相似文献
994.
Hiroshi Sumitomo Kazuhiko Hashimoto 《Journal of polymer science. Part A, Polymer chemistry》1969,7(5):1331-1338
Anionic polymerization of β-cyanopropionaldehyde was studied with use of benzophenone-monosodium, -disodium, and -dilithium complexes as initiators. The resulting poly(cyanoethyl)oxymethylene was compared with that obtained by cationic and coordinated initiators previously reported. Polymer of higher stereoregularity but lower molecular weight was formed in the present system. The marked influence of the initiator concentration on the polymer yield and stereoregularity is explained on the basis of the difference in the degree of association of the alcoholate ion pair, i.e., the associated ion pair may form stereoregular polymer and the nonassociated or less-associated ion pair may form a large amount of amorphous atactic polymer. The initiation with benzophenone-dialkali metal complex was found to be bond-formation type. Chain transfer with active hydrogen of β-cyanopropionaldehyde frequently occurs. 相似文献
995.
The regioselectivity of tether-directed Bingel-type biscyclopropanations of [60]fullerene was switched depending on the leaving groups at tethered active methylene moieties; the reactions of [60]fullerene with unhalogenated tethered bis(active methylene) derivatives/I2 and with brominated derivatives in the presence of 1,7-diazabicyclo[5.4.0]undec-7-ene gave trans-4-adducts predominantly, while the reactions with chlorinated derivatives afforded equatorial-adducts almost exclusively. 相似文献
996.
Kazuhiko Nakamura Yuki Ohnishi Eiji Horikawa Takeo KonakaharaMasato Kodaka Hiroaki Okuno 《Tetrahedron letters》2003,44(29):5445-5448
A novel linker possessing selenocyanate and masked carboxylic acid was developed for the solid-phase synthesis of dehydropeptides. This linker was used to demonstrate the synthesis of the model compound of RGD-conjugated dehydropeptide. 相似文献
997.
Noboru Matsumura Osamu Mori Toshio Takeguchi Yasuyuki Okumura Kazuhiko Mizuno 《Journal of heterocyclic chemistry》2004,41(6):873-876
Photoirradiation of acetone solutions of 2,3‐diallyl‐6,7‐dihydro‐5H‐2a‐thia(2a‐SIV)‐2,3,4a, 7a‐tetraazacyclopent[cd]indene‐ 1,4(2H,3H)‐dithione ( 1 ) in the presence of excess thioacetic acid and thiobenzoic acid afforded addition products, 2,3‐bis(3‐acetylthiopropyl)‐ and 2,3‐bis(3‐benzoylthiopropyl)‐6,7‐dihydro‐5H‐2a‐thia(2a‐SIV)2,3,4a, 7a‐tetraazacyclopent[cd]indene‐1,4(2H,3H)‐dithiones, respectively, in good yields. These photoaddition reactions were facilitated by the addition of oxygen. 相似文献
998.
Teramura K Maeda K Saito T Takata T Saito N Inoue Y Domen K 《The journal of physical chemistry. B》2005,109(46):21915-21921
The formation and structural characteristics of Ru species applied as a cocatalyst on (Ga(1)(-)(x)()Zn(x)())(N(1)(-)(x)()O(x)()) are examined by scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. RuO(2) is an effective cocatalyst that enhances the activity of (Ga(1)(-)(x)()Zn(x)())(N(1)(-)(x)()O(x)()) for overall water splitting under visible-light irradiation. The highest photocatalytic activity is obtained for a sample loaded with 5.0 wt % RuO(2) from an Ru(3)(CO)(12) precursor followed by calcination at 623 K. Calcination is shown to cause the decomposition of initial Ru(3)(CO)(12) on the (Ga(1)(-)(x)()Zn(x)())(N(1)(-)(x)()O(x)()) surface (373 K) to form Ru(IV) species (423 K). Amorphous RuO(2) nanoclusters are then formed by an agglomeration of finer particles (523 K), and the nanoclusters finally crystallize (623 K) to provide the highest catalytic activity. The enhancement of catalytic activity by Ru loading from Ru(3)(CO)(12) is thus shown to be dependent on the formation of crystalline RuO(2) nanoparticles with optimal size and coverage. 相似文献
999.
A guanine radical cation produced by one-electron DNA oxidation migrates over long distances through the DNA pi-stack. Fundamental questions regarding the likelihood of charge transport in genomic DNA, the effects of protein binding, and its biological consequences arise as the next issues of study. Electronic effects of protein binding on the efficiency of charge transport were investigated for the endonuclease BamHI-DNA complex. Direct contact of a positively charged guanidium group of BamHI to guanines in the recognition sequence 5'-GGATCC-3' completely suppressed one-electron oxidation of the guanine in the protein binding site and dramatically lowered the charge transport efficiency through the sequence. Electronically insulated guanines, by the hydrogen bonding contact of a guanidium group in BamHI, no longer function as a stepping stone in the charge transport through the DNA pi-stack. 相似文献
1000.
Transmetallation of a zinc methylene complex [ZnI(tmeda)]2(μ-CH2) with a titanium(iii) chloride [TiCl3(tmeda)(thf)] produced a titanium methylene complex. The X-ray diffraction study displayed a dinuclear methylene structure [TiCl(tmeda)]2(μ-CH2)(μ-Cl)2. Treatment of an ester with the titanium methylene complex resulted in methylenation of the ester carbonyl to form a vinyl ether. The titanium methylene complex also reacted with a terminal olefin, resulting in olefin-metathesis and olefin-homologation. Cyclopropanation by methylene transfer from the titanium methylene proceeded by use of a 1,3-diene. The mechanistic study of the cyclopropanation reaction by the density functional theory calculations was also reported.Transmetallation of a zinc methylene complex [ZnI(tmeda)]2(μ-CH2) with a titanium(iii) chloride [TiCl3(tmeda)(thf)] produced a titanium methylene complex. 相似文献