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11.
自由基浓度测定方法的再验证及其在煤化学中应用 《燃料化学学报》2019,47(11):1281-1287
对前人建立的标准曲线法测煤中自由基浓度进行优化,以DPPH标准样品和基准样品的二次积分面积比值为新参数,结果显示新参数标准曲线法的实测值与理论值相对误差都在5%以内;重复性、复现性实验的相对标准偏差都小于3%。将新参数标准曲线法用于分析不同煤化程度煤和新疆黑山煤(HS)沥青质的自由基浓度,发现随着煤化程度增加,其煤中自由基浓度逐渐增大,从低阶褐煤的8.531×10~(17)/g上升到高阶无烟煤3.37899×10~(19)/g;而在HS煤液化过程中,随着加氢液化温度的升高,其沥青质自由基浓度逐渐下降,从290℃的1.5793×10~(18)/g降到450℃的7.410×10~(17)/g,沥青质自由基浓度变化趋势与其产率变化趋势相一致。 相似文献
12.
Nursel Erey 《代数通讯》2018,46(9):4007-4020
We show that if G is a gap-free and diamond-free graph, then I(G)s has a linear minimal free resolution for every s≥2. 相似文献
13.
Duygu İNCİ 《应用有机金属化学》2020,34(12):e6016
NOO-type tridentate Schiff base, N-salicylidene-2-aminobenzoic acid, (H2L), and its ternary Cu (II) complex containing H2L Schiff base and 4,7-dimethyl-1,10-phenanthroline (4,7-dmphen), [Cu(4,7-dmphen)(H2L)]27H2O, have been synthesized and characterized by CHN analysis, ESI-MS, FTIR, and single-crystal X-ray diffraction techniques. The interaction of alone H2L Schiff base ligand and ternary Cu (II) complex with biomacramolecules {calf thymus DNA (CT-DNA) and bovine serum albumin (BSA)} has been investigated by electronic absorption and fluorescence spectroscopy. The experimental results indicate that H2L Schiff base ligand and ternary Cu (II) complex bind to CT-DNA by means of a moderate intercalation mode. Furthermore, the fluorescence quenching mechanism between H2L Schiff base ligand and ternary Cu (II) complex with BSA possesses a static quenching process. Radical scavenging activity of H2L Schiff base ligand and ternary Cu (II) complex was measured in terms of EC50, using the DPPH and H2O2 methods. Biomacromolecule interactions and scavenging activity studies revealed that ternary Cu (II) complex yielded better results than H2L Schiff base ligand alone. 相似文献
14.
Hydrodynamic cavitation (HC) and Fe(II) are advanced oxidation processes, in which pentachlorophenol (PCP) is treated by the redox method of activating persulfate (PS). The kinetics and mechanism of the HC and Fe(II) activation of PS were examined in aqueous solution using an electron spin resonance (ESR) spin trapping technique and radical trapping with pure compounds. The optimum ratio of Fe(II)/PS was 1:2, and the hydroxyl radical (HO) and sulfate radical (SO4−) generation rate were 5.56 mM h−1 and 8.62 μM h−1, respectively. The generation rate and Rct of HO and SO4− at pH 3 and 50 °C in the Fe(II)/PS/HC system are 7584.6 μM h−1, 0.013 and 24.02 μM h−1, 3.95, respectively. The number of radicals was reduced as the pH increased, and it increased with increasing temperature. The PCP reaction rate constants was 4.39 × 10−2 min−1 at pH 3 and 50 °C. The activation energy was 10.68 kJ mol−1. In addition, the mechanism of PCP treatment in the Fe(II)/PS/HC system was a redox reaction, and the HO−/SO4− contribution was 81.1 and 18.9%, respectively. In this study, we first examined PCP oxidation through HO and SO4− quantification using only the Fe(II)/PS/HC process. Furthermore, the results provide the foundation for activation of PS by HC and Fe(II), but also provide a data basis for similar organic treatments other than PCP. 相似文献
15.
目的 观察丹酚酸A 对H2O2所致大鼠脑微血管内皮细胞(RCMECs)氧化损伤的保护作用,并探讨其可能的作用机
制。方法 分离并培养大鼠脑微血管内皮细胞,用H2 O2 损伤的方法建立氧自由基损伤模型。采用丹酚酸A 进行干预后,分别测定细胞培养液中乳酸脱氢酶(LDH)活性、血栓素B2(TXB2)水平、6- 酮基前列腺素1α(6-keto-PGF1α)的含量,以及细胞内和培养液中脂质过氧化产物丙二醛(MDA)含量和超氧化物歧化酶(SOD)的活性。结果 H2O2致RCMECs 氧化损伤后,细胞LDH 释放水平、TXB2和MDA 的含量均明显增加,同时6-keto-PGF1α 含量和SOD 活性显著下降;而丹酚酸A 预处理后能呈浓度依赖性的降低RCMECs 氧化损伤后LDH 水平、TXB2含量和细胞内外的MDA 含量,提高受损细胞6-keto-PGF1α 的表达和细胞内外SOD 活性。结论 丹酚酸A 对H2O2所致RCMECs 氧化损伤具有保护作用,其机制可能与其抗氧化作用有关。 相似文献
16.
Zhigang Xue Zhen Wang Dan He Xingping Zhou Xiaolin Xie 《Journal of polymer science. Part A, Polymer chemistry》2016,54(5):611-620
Cationic emulsions of triblock copolymer particles comprising a poly(n‐butyl acrylate) (PnBA) central block and polystyrene (PS) outer blocks were synthesized by activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Difunctional ATRP initiator, ethylene bis(2‐bromoisobutyrate) (EBBiB), was used as initiator to synthesize the ABA type poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) (PS‐PnBA‐PS) triblock copolymer. The effects of ligand and cationic surfactant on polymerizations were also discussed. Gel permeation chromatography (GPC) was used to characterize the molecular weight (Mn) and molecular weight distribution (MWD) of the resultant triblock copolymers. Particle size and particle size distribution of resulted latexes were characterized by dynamic light scattering (DLS). The resultant latexes showed good colloidal stability with average particle size around 100–300 nm in diameter. Glass transition temperature (Tg) of copolymers was studied by differential scanning calorimetry (DSC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 611–620 相似文献
17.
Domino Radical Addition/Oxidation Sequence with Photocatalysis: One‐Pot Synthesis of Polysubstituted Furans from α‐Chloro‐Alkyl Ketones and Styrenes 下载免费PDF全文
Shuang Wang Wen‐Liang Jia Lin Wang Prof. Dr. Qiang Liu Prof. Dr. Li‐Zhu Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13794-13798
A new domino reaction has been developed that allows the combination of styrenes and α‐alkyl ketone radicals to afford a wide array of polysubstituted furans in good to excellent yields under mild and simple reaction conditions. The key to success of this novel protocol is the use of photocatalyst fac‐Ir(ppy)3 and oxidant K2S2O8. Mechanistic studies by a radical scavenger and photoluminescence quenching suggest that a radical addition/oxidation pathway is operable. 相似文献
18.
Romain Bénéteau Anne Boussonnière Jean‐Christophe Rouaud Prof. Dr. Jacques Lebreton Dr. Jérôme Graton Prof. Dr. Denis Jacquemin Dr. Muriel Sebban Prof. Dr. Hassan Oulyadi Ghanem Hamdoun Dr. Amber N. Hancock Prof. Dr. Carl H. Schiesser Dr. Fabrice Dénès 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4809-4824
α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences. 相似文献
19.
Naphthalic anhydride derivatives: Structural effects on their initiating abilities in radical and/or cationic photopolymerizations under visible light 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Bernadette Graff Fabrice Morlet‐Savary Jean Pierre Fouassier Didier Gigmes Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(24):2860-2866
Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1‐ANH8) have been prepared and combined with an iodonium salt (and optionally N‐vinylcarbazole) or an amine (and optionally 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (~ 12 mW cm?2), laser diode at 405 nm (~1.5 mW cm?2) or blue LED centered at 455 nm (80 mW cm?2). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well‐known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin‐trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2860–2866 相似文献
20.
Novel hyperbranched polymers synthesized via A3 + B(B′) approach by radical addition‐coupling polymerization 下载免费PDF全文
In this study, a novel application of radical addition‐coupling polymerization (RACP) for synthesis of hyperbranched polymers is reported. By Cu/PMDETA‐mediated RACP of 2‐methyl‐2‐nitrosopropane with trimethylolpropane tris(2‐bromopropionate) or a bromo‐ended 3‐arm PS macromonomer, two types of hyperbranched polymers with high degree of polymerization are synthesized under mild conditions, respectively. The chemical structures of the hyperbranched polymers are carefully characterized. By selective degradations of the ester groups and weak bonds of NO? C in the polymers, high degree of alternative connection of the two monomers in the synthesized polymers have been identified. Based on the experimental results, mechanism of formation of the hyperbranched polymer is proposed, which includes formation of carbon radicals from the tribromo monomer through single electron transfer, its capture by 2‐methyl‐2‐nitrosopropane that results in nitroxide radical, and cross‐coupling reaction of the nitroxide radical with other carbon radicals. Hyperbranched polymer can be formed in a step‐growth mode after multiple steps of such reactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 904–913 相似文献