全文获取类型
收费全文 | 12681篇 |
免费 | 1073篇 |
国内免费 | 725篇 |
专业分类
化学 | 8348篇 |
晶体学 | 132篇 |
力学 | 555篇 |
综合类 | 67篇 |
数学 | 1908篇 |
物理学 | 3469篇 |
出版年
2023年 | 142篇 |
2022年 | 304篇 |
2021年 | 374篇 |
2020年 | 403篇 |
2019年 | 413篇 |
2018年 | 359篇 |
2017年 | 318篇 |
2016年 | 482篇 |
2015年 | 463篇 |
2014年 | 518篇 |
2013年 | 854篇 |
2012年 | 883篇 |
2011年 | 965篇 |
2010年 | 604篇 |
2009年 | 545篇 |
2008年 | 715篇 |
2007年 | 565篇 |
2006年 | 554篇 |
2005年 | 510篇 |
2004年 | 407篇 |
2003年 | 395篇 |
2002年 | 405篇 |
2001年 | 337篇 |
2000年 | 270篇 |
1999年 | 207篇 |
1998年 | 156篇 |
1997年 | 116篇 |
1996年 | 179篇 |
1995年 | 123篇 |
1994年 | 150篇 |
1993年 | 109篇 |
1992年 | 120篇 |
1991年 | 98篇 |
1990年 | 99篇 |
1989年 | 74篇 |
1988年 | 73篇 |
1987年 | 69篇 |
1986年 | 64篇 |
1985年 | 91篇 |
1984年 | 85篇 |
1983年 | 45篇 |
1982年 | 92篇 |
1981年 | 78篇 |
1980年 | 81篇 |
1979年 | 72篇 |
1978年 | 64篇 |
1977年 | 61篇 |
1976年 | 57篇 |
1975年 | 43篇 |
1973年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
161.
氯氧化镁在水中的溶解行为 总被引:3,自引:0,他引:3
用pH法和氯电位法测定氯氧化镁不同温度下在水中的溶解过程。一定间隔时间分析液样中的Mg^2+、Cl^-、OH^-的浓度,用物化方法鉴定固相。得出不同温度下的相转化、溶解的C ̄t曲线及动力学方程。计算了它们的Ksp和热力学函数。 相似文献
162.
The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level. 相似文献
163.
Inrecentyears,thenewsedricrystallinepolymersyndiotacticp0lystyrene(sPS)hasat-ITactedmuchattentionduetoitsg0odchendcalresistanceandenhancedmechanicalperformanceatelevatedtemPeratUre.'H0wever,itexhibitshighbrittlenessandpoorimPact-resistanceandtCar-resistance.2Therefore,itisnecessarytomodifyitwithtougheningpolyIners.AsimPlemeth0dto0verc0methedriscibilityofatwo-phaseblendofsPSandatougheningpolymristotwrovetheinterfacialaffmity,wheretheadditionofablockcoP0lymerisconsideredtobemosteffective.3… 相似文献
164.
A parallel solution combustion synthesis technique was developed for combinatorial materials studies. The vigorous combustion reactions were successfully limited in the microreactors by using a substrate-net-mask microreactor system and the lowest adoptable furnace temperature. Using this technique, a luminescent materials library of Y3Al5O12/Tb(chi) was synthesized with the aid of an ink-jet delivery system. Structure and luminescence characterizations were implemented using X-ray diffraction and UV/X-ray spectroscopies, respectively. The results show that this technique is reliable and applicable to combinatorial study of powder materials with high synthesis temperature. 相似文献
165.
Ascorbic acid (AA) is determined by amperometric detection based on the photochemical reduction of Methylene Blue (MB(+)) in 0.1 M phthalate buffer at pH 3.8. In this medium, MB(+) using flow-injection analysis. The carrier stream is 1 mM MB(+) is reduced quasi-reversibly at a glassy carbon electrode at -0.34 V vs. Ag/AgCl, while AA is oxidized irreversibly at about 0.3 V. The reactor is irradiated with a 500 W halogen lamp to facilitate the development of the photochemical reaction. A laboratory-built wall-jet electrode system was used. The Leucomethylene Blue formed in the reaction is detected at +0.050 V. At 2.2 ml min(-1) and using a sample loop of 43 mul, the method allows the determination of AA in the range 5.0-90.0 mug ml(-1), with a relative standard deviation of 1.3-4.8%, a detection limit of 1.9 mug ml(-1) and a sampling frequency of 45-50 h(-1). 相似文献
166.
Immobilization of protein on ferromagnetic Dacron 总被引:1,自引:0,他引:1
A. M. A. Carneiro LeÃo E. A. Oliveira L. B. Carvalho 《Applied biochemistry and biotechnology》1991,31(1):53-58
Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant. 相似文献
167.
Cantat T Jaroschik F Nief F Ricard L Mézailles N Le Floch P 《Chemical communications (Cambridge, England)》2005,(41):5178-5180
New samarium carbene complexes have been synthesized and characterized by X-ray diffraction analysis; the carbenic nature was assessed by reactivity studies. 相似文献
168.
Bao Shan Huang Mary Jane Lauzon James C. Parham 《Journal of heterocyclic chemistry》1979,16(4):811-813
Alkylation of 4(5)-nitroimidazole-5(4)-sulfonamide with benzyl bromide occurred on both ring nitrogens. The structures of the products could be assigned by comparison of the chemical shifts of the sulfonamide hydrogens in the nmr spectra with those of the isomeric methyl derivatives, which were prepared by differing routes. Uv and nmr spectral data are reported for a number of bromo-, nitro-, mercapto-, sulfamyl- and amino- substituted imidazoles as well as for both of the isomeric methylated derivatives of the series. 相似文献
169.
环己烷中苯甲酰苯胺的双重荧光--分子内电荷转移的直接光谱证据 总被引:2,自引:0,他引:2
自从O Connell等[1]报道苯甲酰苯胺(BA)在EPA玻璃体中异常的长波长荧光发射特性以来, 已有众多学者尝试解释该"异常"荧光的发射态性质[2~12]. Kasha等[2~7]认为长波长荧光是质子转移(PT)和电荷转移(CT)两种激发态发射的叠加, 而Azumaya等[8]则认为发射态只包含分子内扭转电荷转移(TICT)态. 应该指出的是, 在上述研究中, 电荷转移态的指认并无有力的实验事实, 而主要是依据与具有CT双重荧光的对二甲氨基苯甲氰[13,14]的类比. 显然, 有关苯甲酰苯胺的长波长荧光发射态的准确性质仍待实验阐明 相似文献
170.
4-Hydroxythiazoles and N-acylimino 4-thiazolidinones show similar tautomeric behaviour to azlactones. However, the mechanism of their reaction with dimethylacetylenedicarboxylate or with ethyl vinyl ether differs fundamentally. In the thiazole series, the first step is the quaternization of the nitrogen atom. The mesoionic thiazole intermediate is then trapped by a second molecule of the dipolarophile. 相似文献