全文获取类型
收费全文 | 233篇 |
免费 | 10篇 |
专业分类
化学 | 205篇 |
晶体学 | 1篇 |
数学 | 15篇 |
物理学 | 22篇 |
出版年
2022年 | 7篇 |
2021年 | 8篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 8篇 |
2017年 | 10篇 |
2016年 | 12篇 |
2015年 | 3篇 |
2014年 | 10篇 |
2013年 | 21篇 |
2012年 | 10篇 |
2011年 | 14篇 |
2010年 | 7篇 |
2009年 | 13篇 |
2008年 | 11篇 |
2007年 | 9篇 |
2006年 | 5篇 |
2005年 | 5篇 |
2004年 | 4篇 |
2003年 | 3篇 |
2002年 | 4篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1974年 | 3篇 |
排序方式: 共有243条查询结果,搜索用时 328 毫秒
1.
Karolina Kula Agnieszka Kcka-Zych Agnieszka apczuk-Krygier Zbigniew Wzorek Anna K. Nowak Radomir Jasiski 《Molecules (Basel, Switzerland)》2021,26(5)
The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism. 相似文献
2.
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
3.
The synthesis and thermal bromination of octahydropentalene was studied. The reaction afforded 1a,3a,4b,6b-tetrabromo-1,2,3,4,5,6-hexahydropentalene (14) with remarkable regio- and stereospecificity. The structure of the product was determined by 1H and 13C NMR data and single X-ray structural analysis. The treatment of octahydropentalene with tenfold bromine gave the octabromopentalene derivative. The formation mechanism of the products is discussed. 相似文献
4.
Duygu Avci Selim H. Kseflu Robert D. Thompson Lon J. Mathias 《Journal of polymer science. Part A, Polymer chemistry》1994,32(15):2937-2945
New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using acid chlorides (traditional solution reactions), sodium salts of acids (with phase transfer catalysis), and trifluoroacetic anhydride (trifluoroacetate). The interfacial process gave high yields of clean products under very mild conditions. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with 2,2′-azobis (isobutyronitrile) gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million [based on size-exclusion chromatography (SEC) comparison to polystyrene standards]. These high molecular weights were the result of autoacceleration in the bulk as shown by monitoring molecular weight with respect to conversion. Solution polymerization in benzene gave more typical polymer, e.g., the acetate derivative showed an SEC molecular weight of 52,000. Glass transition temperatures for the n-alkyl esters decreased from the formate (77°C) to the hexanoate (15°C); the stearate showed a side-chain melting point of 40°C but no Tg. Glass transitions were observed for the trifluoroacetate, benzoate, and adamantanoate polymers at 69, 130, and 214°C, respectively. Solution 13C-NMR showed evidence of tacticity information for the formate and acetate derivatives with appaent preference for syndiotactic polymer formation similar to that of methyl methacrylate. FTIR and solid-state 13C-NMR analysis gave spectra with functional group peaks and chemical shift values expected based on composition. The stearate monomer and polymer gave solid-state 13C chemical shifts of 34 and 33 ppm, respectively, for the central CH2 units consistent with monoclinic and orthorhombic crystal packing. © 1994 John Wiley & Sons, Inc. 相似文献
5.
The conditions of thermal decomposition of thep-aminosalicylates of Y, La and the lanthanides from Ce(III) to Lu have been studied. On heating, the hydrated complexes of La and the light lanthanides decompose to the oxides with the intermediate formation of Ln2[H2N·C6H3(O)COO]3. Only the complex of La decomposes to La2O3 through La2[H2N·C6H3(O)COO]3 and La2O2CO3. The anhydrous complexes of the heavy lanthanides decompose directly to the oxides, whereas the anhydrous complex of Y decomposes to Y2O3 via Y2[H2N·C6H3(O)COO]3 formation. During heating, the hydrated complexes lose crystallization water and decompose simultaneously, and the endothermic effect of dehydration is masked by the strong exothermic effect of burning of the organic ligand.
Zusammenfassung Es wurden die Bedingungen für die thermische Zersetzung derp-Aminosalicylate von Y, La und der Lanthanoide von Ce(III) bis Lu untersucht. Beim Erhitzen zersetzen sich die hydratierten Komplexe von La und der leichteren Lanthanoide unter Bildung des Zwischenproduktes Ln2[H2NC6H3(O)COO]3 in ihre Oxide. Nur der Komplex mit La zersetzt sich zu La2O3 über die Zwischenstufen La2[H2NC6H3(O)COO]3 und La2O2CO3. Die wasserfreien Komplexe der schweren Lanthanoide zersetzen sich direkt in die Oxide, wÄhrend sich der wasserfreie Komplex von Y über die Bildung von y2[H2NC6H3(O)COO]3 in y2O3 zersetzt. Beim Erhitzen verlieren die hydratierten Komplexe ihr Kristallwasser und zersetzen sich gleichzeitig, der endotherme Effekt der Dehydratation wird durch den starken exothermen Effekt der Verbrennung der organischen Liganden überdeckt.相似文献
6.
Hubbuch J Linden T Knieps E Ljunglöf A Thömmes J Kula MR 《Journal of chromatography. A》2003,1021(1-2):93-104
An experimental study on the interplay of sorbent structure and fluid phase conditions (pH) has been carried out examining adsorption and transport of bovine serum albumin (BSA) and a monoclonal antibody (IgG 2a) on SP Sepharose Fast Flow and SP Sepharose XL. SP Sepharose Fast Flow is characterised by a relatively open pore network, while SP Sepharose XL is a composite structure with ligand-carrying dextran chains filling the pore space. Both adsorbents have similar ionic capacity. Protein transport and adsorption profiles were evaluated using confocal laser scanning microscopy. Under all investigated conditions, BSA uptake could be adequately explained by a pore diffusion mechanism. The adsorption profiles obtained for IgG 2a, however, indicated that changes in fluid phase conditions as well as a change in the solid phase structure could result in a more complex uptake mechanism as compared to pore diffusion alone. This mechanism results in a fast transport of proteins into the adsorbent, followed by an overshoot of protein in the center of the sorbent and a setback towards a homogeneous adsorption profile. 相似文献
7.
The conditions of decomposition of Y, La and lanthanide (from Ce(III) to Lu) salicylates have been studied. On heating, the hydrated salicylates of Y and lanthanides from Nd to Lu lose crystallization water in one step to yield the anhydrous salts. The anhydrous complexes of Y, La, Ce(III), Pr, Nd, Sm, Eu(III), Gd and Tb subsequently decompose in several steps to the oxides Ln2O3, CeO2, Pr6O11 and Tb4O7. The anhydrous complexes of the remaining lanthanides decompose directly to the oxides Ln2O3.
Zusammenfassung Die Zersetzungsreaktionsbedingungen von Y-, La- und Lanthanid-(Ce(III) bis Lu) salizylaten wurden untersucht. Beim Erhitzen geben hydrierte Salizylate von Y und der Lanthanide Nd bis Lu Kristallwasser in einem Schritt ab und bilden wasserfreie Salze. Die wasserfreien Komplexe von Y, La, Ce(III), Pr, Nd, Sm, Eu(III), Gd und Tb zersetzen sich in mehreren Schritten und bilden die Oxide Ln2O3, CeO2, Pr6O11 und Tb4O7. Die wasserfreien Komplexe der übrigen Lanthaniden zerfallen direkt in Ln2O3 Oxide.
, . , . , , , , , , , , Ln2O3, CeO2, Pr6O11 47. Ln2O3.相似文献
8.
Radosław Bonikowski Józef Kula Anna Bujacz Anna Wajs-Bonikowska Małgorzata Zakłos-Szyda Stanisław Wysocki 《Tetrahedron: Asymmetry》2012,23(14):1038-1045
Ten enantiomerically pure hydroindene-derived compounds obtained by the transformation of (+)-carotol, the main constituent of carrot seed essential oil, were examined for their ability to inhibit the growth of myeloid leukaemia (HL-60) cancer cell lines. All compounds showed significant activity, which was comparable to the most active volatile organic compounds, such as trans–trans-farnesol, citral and nerolidol. Based on the bioactivity and molecular modelling, a 3D QSAR pharmacophore model was generated. 相似文献
9.
Burcin Akgun Duygu Avci 《Journal of polymer science. Part A, Polymer chemistry》2012,50(23):4854-4863
Two new bismethacrylamide ( 1 , 2 ) and two new methacrylamide ( 3 , 4 ) dental monomers were synthesized. In each group, one monomer contains a bisphosphonate group, the other a bisphosphonic acid group. Monomer 1 and 3 were synthesized by amidation of 2‐(2‐chlorocarbonyl‐allyloxymethyl)‐acryloylchloride and methacryloyl chloride with tetraethyl aminomethyl‐bis(phosphonate) and converted to the bisphosphonic acid monomers 2 and 4 by hydrolysis with trimethylsilyl bromide. Monomer 1 (m.p.: 71–72 °C), monomer 3 ( 33–34 °C), and monomer 4 (no m.p.) were obtained as white solids and monomer 2 a viscous liquid, soluble in water. Homopolymerization of 1 gave crosslinked polymers, indicating its low cyclization tendency. The photopolymerization studies indicated that its copolymerizability with 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloyloxy propyloxy) phenyl] propane and 2‐hydroxyethyl methacrylate (HEMA) without changing their rates and conversions significantly means that it could be used as a biocompatible crosslinker. Although monomer 2 showed low polymerizability, because of its good performance in terms of solubility, hydrolytic stability, hydroxyapatite interaction, acidity, and copolymerizability with HEMA, it shows potential to be used in self‐etching dental adhesives. The thermal polymerization of 3 resulted in soluble polymers and evaluation of monomer 4 in terms of solubility, acidity, and copolymerizability with HEMA indicated its potential as an adhesive monomer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
10.
Bünyamin Ak Duygu Elma Nermin Meriç Cezmi Kayan Uğur Işık Murat Aydemir Feyyaz Durap Akın Baysal 《Tetrahedron: Asymmetry》2013,24(20):1257-1264
A new and versatile class of unsymmetrical ferrocenyl-phosphinite ligands possessing a stereogenic center has been prepared from commercially available, inexpensive aminoacids such as, d-, l-phenylglycine and d-, l-phenylalanine, through a concise synthetic procedure. These ligands are not very sensitive to air and moisture, and display good enantioselectivities in the ruthenium-catalyzed asymmetric transfer hydrogenation of acetophenone derivatives, in which up to 91% ee was obtained. A comparison of the catalytic properties of amino alcohols and other analogues based on a ferrocenyl backbone is also discussed briefly. The structures of these ligands and their corresponding complexes have been elucidated by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis. 相似文献