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191.
Sodium poly(styrenesulfonate)(polySSNa)-grafted polymer nanoparticles were synthesized by core-cross-linking of block copolymer micelles and subsequent chemical transformation. Block copolymers, poly(p-((1-methyl)silacyclobutyl)styrene-block-poly(neopentyl p-styrenesulfonate)s, polySBS-b-polySSPen, were synthesized by nitroxy-mediated living radical polymerization. The block copolymers formed micelles (Rh=15-23 nm, where Rh represents the hydrodynamic radius) with a polySBS core and polySSPen shell in acetone. The micelle core was cross-linked by ring-opening polymerization of silacyclobutyl groups in polySBS. Hydrolysis of the neopentyl groups provided polySSNa-grafted nanoparticles. The Rh of the particles before the hydrolysis ranged from 12 to 21 nm in acetone, while they varied to the range from 50 to 110 nm in water after the hydrolysis. 相似文献
192.
István Szilágyi Krisztina Imrik Dariusz Sarzisky Sándor Dóbé Tibor Bérces 《Reaction Kinetics and Catalysis Letters》2002,77(2):341-345
The title reactions have been studied at room temperature by applying the discharge flow method coupled with laser induced fluorescence detection of methoxy radicals and resonance fluorescence detection of bromine atoms. The following rate constants were determined: CH3O + Br Õ products (1) k
1 (298 K) = (3.4 ± 0.4 (1)) × 1013 cm3 mol-1 s-1, CH3O + Br2 Õ products (2) k
2 (298 K) £ 5 × 108 cm3 mol-1 s-1. 相似文献
193.
利用波长为266nm的激光光解CHBr3产生CH自由基,其与NO反应作为NCO自由基的来源.在298K,总压2660Pa的条件下,采用激光诱导荧光的方法,研究了NCO自由基与SO2、CS2的反应.得到了NCO自由基与SO2、CS2双分子反应速率常数分别为(1.8±0.3)×10-11和(3.1±0.4)×10-12cm3·molecule-1·s-1.对这两个反应在B3LYP/6-31 G(d)的水平上进行理论研究的结果表明,NCO自由基与SO2、CS2的反应是加成反应,其机理是NCO自由基中的N原子攻击反应物的中心原子,得到加成产物. 相似文献
194.
Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD3OD/(D6)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents. 相似文献
195.
规整链球型含C_(60)聚(丙烯酸β-羟乙酯)的合成及其在水中的自组装 总被引:2,自引:0,他引:2
C60 由于其独特的物理化学性质 ,在生命科学中引起了人们的广泛兴趣 .例如 :水溶性C60 的羧酸衍生物 ,羟基取代C60 ,C60 的氨基酸水溶性衍生的合成已有报道[1~ 3] ,并被用来研究C60 的生物化学及医学活性 .Tokuyama[4 ] 等合成了酶功能化C60及与核酸连接的C60 ,研究并证明了它的细胞毒性及G 选择DNA切割能力等生化活性 .Friedman[5]等合成了水溶性C60 的羧酸衍生物 ,研究了它对HIV 1艾滋病毒的抑制作用 ,此外 ,关于不同C60含量的C60 蛋白质衍生物的合成及性质的研究也有报道[6] .C60 是一个直径为 0 71… 相似文献
196.
~~Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative@赵红卫$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@江致勤$Department of Chemistry, Tongji Unviersity!Shanghai 200092,China
@窦大营$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@吴铁一$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@王文锋$Shanghai… 相似文献
197.
CVD法不同条件下制备的多壁碳纳米管的Fenton氧化改性 总被引:2,自引:0,他引:2
碳纳米管经焙烧和稀硝酸纯化处理后,在相同的实验条件下,采用Fenton试剂产生的·OH分别对CVD法合成的两种制备条件不同的多壁碳纳米管进行氧化改性处理。红外光谱(FT IR)表明,改性后的两种碳管结构中都引入了羟基、羰基和羧基等含氧官能团。此外,由于制备条件不同,导致它们的石墨化程度、缺陷含量和抗氧化能力等性质也不同,因此CVD法制备条件能够对碳管Fenton氧化改性结果产生重要影响。机理分析表明,这些含氧官能团可以看作是具有强亲电性和强氧化性的·OH对碳管上缺陷位置和不饱和键进行攻击的结果。 相似文献
198.
S. Padmaja V. Ramakrishnan J. Rajaram J. C. Kuriacose 《Journal of Chemical Sciences》1988,100(4):297-303
The borate radical is produced by the flash photolysis of an aqueous alkaline solution of NaBO2 and K2S2O8. The absorption spectrum of the transient borate radical shows two maxima. The self decay of this radical is second order.
Rate constants for the reactions of this radical with some organic substrates have been determined. 相似文献
199.
Akiko Saito Mana Emoto Akira Tanaka Yuki Doi Kazuaki Shoji Yoshiyuki Mizushina Hiroshi Ikawa Hiromi Yoshida Nobuyasu Matsuura Noriyuki Nakajima 《Tetrahedron》2004,60(52):12043-12049
A simple method for the synthesis of procyanidin B3 substituted with a galloyl group at the 3 and 3″ position is described. Condensation of a benzylated catechin-3-O-gallate electrophile with a nucleophile, catechin and catechin-3-O-gallate, proceeded smoothly and stereoselectively to afford the corresponding dimer gallates, procyanidin B3-3-O-gallate and procyanidin B3-3,3″-di-O-gallate, in good yields. Further, their antioxidant activities on UV-induced lipid peroxide formation, DPPH radical scavenging activity and inhibitory activity of DNA polymerase were also investigated. Among three procyanidin B3 congeners (procyanidin B3, 3-O-gallate and 3,3″-di-O-gallate), the 3,3″-di-O-gallate derivative showed the strongest antioxidant and radical scavenging activity. Interestingly, the 3-O-gallate derivative was the strongest inhibitor of mammalian DNA polymerase with IC50 value of 0.26 μM, although it showed the weakest antioxidant and radical scavenging activity. It became apparent that the presence of a galloyl group at the C-3 position in the proanthocyanidin oligomer was very important for biological activity, however, the antioxidant activity of these compounds was not parallel to the DNA polymerase inhibitory activity. 相似文献
200.
Justicia J Rosales A Buñuel E Oller-López JL Valdivia M Haïdour A Oltra JE Barrero AF Cárdenas DJ Cuerva JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1778-1788
The titanocene-catalyzed cascade cyclization of epoxypolyenes, which are easily prepared from commercially available polyprenoids, has proven to be a useful procedure for the synthesis of C(10), C(15), C(20), and C(30) terpenoids, including monocyclic, bicyclic, and tricyclic natural products. Both theoretical and experimental evidence suggests that this cyclization takes place in a nonconcerted fashion via discrete carbon-centered radicals. Nevertheless, the termination step of the process seems to be subjected to a kind of water-dependent control, which is unusual in free-radical chemistry. The catalytic cycle is based on the use of the novel combination Me(3)SiCl/2,4,6-collidine to regenerate the titanocene catalyst. In practice this procedure has several advantages: it takes place at room temperature under mild conditions compatible with different functional groups, uses inexpensive reagents, and its end step can easily be controlled to give exocyclic double bonds by simply excluding water from the medium. 相似文献