全文获取类型
收费全文 | 1946篇 |
免费 | 255篇 |
国内免费 | 153篇 |
专业分类
化学 | 2182篇 |
晶体学 | 8篇 |
力学 | 3篇 |
综合类 | 15篇 |
数学 | 2篇 |
物理学 | 144篇 |
出版年
2024年 | 4篇 |
2023年 | 16篇 |
2022年 | 59篇 |
2021年 | 51篇 |
2020年 | 104篇 |
2019年 | 81篇 |
2018年 | 58篇 |
2017年 | 51篇 |
2016年 | 109篇 |
2015年 | 114篇 |
2014年 | 94篇 |
2013年 | 244篇 |
2012年 | 82篇 |
2011年 | 81篇 |
2010年 | 88篇 |
2009年 | 66篇 |
2008年 | 72篇 |
2007年 | 77篇 |
2006年 | 75篇 |
2005年 | 74篇 |
2004年 | 75篇 |
2003年 | 75篇 |
2002年 | 183篇 |
2001年 | 58篇 |
2000年 | 36篇 |
1999年 | 29篇 |
1998年 | 31篇 |
1997年 | 43篇 |
1996年 | 47篇 |
1995年 | 52篇 |
1994年 | 15篇 |
1993年 | 17篇 |
1992年 | 30篇 |
1991年 | 7篇 |
1990年 | 14篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1972年 | 4篇 |
1971年 | 1篇 |
排序方式: 共有2354条查询结果,搜索用时 0 毫秒
1.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons 下载免费PDF全文
Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
2.
K. C. Kumara Swamy E. Balaraman M. Phani Pavan N. N. Bhuvan Kumar K. Praveen Kumar N. Satish Kumar 《Journal of Chemical Sciences》2006,118(6):495-501
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated
acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature
of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction. 相似文献
3.
着生刚毛藻处理富营养化湖泊水 总被引:8,自引:0,他引:8
分别研究了室内和露天条件下在鹅卵石上着生的刚毛藻Cladophora oligoclona对富营养化湖水中氮(N)和磷(P)的净化效果及其对水华藻类生长的抑制能力,同时对处理后湖水的藻类生长潜力进行了测试.结果显示,刚毛藻在原始浓度总氮(TN)10.512 mg/L和总磷(TP)0.856 mg/L的富营养化湖水中能维持正常的生长代谢,并能有效去除水体中的N、P养分.在室内12 d培养期间,刚毛藻对TN、氨氮(NH4-N)、TP和无机磷(PO4-P)的平均去除率分别达53.13%,44.40%,35.71%和30.53%.在室外6 d培养期间,刚毛藻对TN、NH4-N、TP和PO4-P的日均减少量分别为1.643 5±0.413 9,1.350 3±0.352 4,0.113 7±0.041 1,0.074 2±0.033 0 mg/L,总去除率分别高达93.81%,94.62%,79.67%和77.66%.刚毛藻对水华微囊藻生长的抑制率达99.63%,处理后湖水的藻类生长潜力较原湖水下降了40.17%.据此认为,刚毛藻在净化污染水体、修复受损湖泊及防治水体富营养化等方面具有潜在的应用前景. 相似文献
4.
5.
6.
Duygu Avci Aylin Ziylan Albayrak 《Journal of polymer science. Part A, Polymer chemistry》2003,41(14):2207-2217
Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003 相似文献
7.
In this paper, based on known crystal structures of square pyramid (SP) and trigonal bipyramid (TBP) penta coordinated phosphorus compounds containing amino acid side chains, such as amino, carboxyl, hydroxyl or thiol, a software for survey the P(5)-structure of phosphorylated proteins was derived. By this software, it was found that 382 of 398 phosphorus related kinases (96%) from current PDB could go through the penta-coordinated phosphorus transition state or intermediate. 相似文献
8.
Mitsuru Ueda Tetsuya Abe Mitsuo Oda 《Journal of polymer science. Part A, Polymer chemistry》1992,30(9):1993-1998
Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc. 相似文献
9.
A. S. Romakhin I. M. Zaripov Yu. G. Budnikova Yu. M. Kargin E. V. Nikitin A. P. Tomilov Yu. A. Ignat'ev 《Russian Chemical Bulletin》1992,41(6):1036-1040
The mechanism of the electrosynthesis of phosphate esters from white phosphorus was investigated. It was shown that the reaction takes place by two paths, i.e., monomeric (with the participation of dissolved phosphorus) and polymeric (with the participation of phosphorus on the surface of an emulsion drop). It was established that in an alcohol solution of tetraethylammonium iodide the main part of the final product is formed through an intermediate polymeric compound. It was noticed that by studying the dynamics of the accumulation of the dissolved product during electrolysis it is possible to trace the mechanism of reaction of the phosphorus at the individual stages of the process.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420028 Kazan'. V. I. Ul'yanov-Lenin Kazan' State University, 420028 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1328–1333, June, 1992. 相似文献
10.
General purpose poly(styrene) is a large
volume commodity polymer widely used in a range of applications. For many
of these the presence of an additive to impart some flammability resistance
is required. Most commonly, brominated aromatics are used for this purpose.
As the polymer undergoes combustion these compounds decompose to generate
bromine atoms and/or hydrogen bromide which escape to the gas phase and trap
flame propagating radicals. While these species are effective in inhibiting
flame propagation they present the opportunity for loss of halogen to the
atmosphere. For this reason, the use of these compounds is being limited in
some parts of the world. Phosphorus compounds, on the other had, impart a
flame retarding influence by promoting char formation at the surface of the
burning polymer. This prevents heat feedback to the polymer and consequent
pyrolysis to generate fuel fragments. The combination of both bromine and
phosphorus present in a single compound might generate a superior flame-retarding
additive in that both modes of retardancy might be promoted simultaneously.
Should this be the case smaller amounts of additive might be necessary to
achieve a satisfactory level of flame retardancy. A series of such additives,
brominated aryl phosphates, has been synthesized and fully characterized spectroscopically.
Blends of these additives, at various levels, with poly(styrene) have been
examined by DSC, TG and in the UL-94 flame test. The flammability of the polymer
is dramatically diminished by the presence of the additive. 相似文献