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排序方式: 共有1036条查询结果,搜索用时 15 毫秒
1.
Tomasz Pdzinski Katarzyna Grzyb Konrad Skotnicki Piotr Filipiak Krzysztof Bobrowski Chryssostomos Chatgilialoglu Bronislaw Marciniak 《International journal of molecular sciences》2021,22(9)
Within the reactive oxygen species (ROS) generated by cellular metabolisms, hydroxyl radicals (HO•) play an important role, being the most aggressive towards biomolecules. The reactions of HO• with methionine residues (Met) in peptides and proteins have been intensively studied, but some fundamental aspects remain unsolved. In the present study we examined the biomimetic model made of Ac-Met-OMe, as the simplest model peptide backbone, and of HO• generated by ionizing radiation in aqueous solutions under anoxic conditions. We performed the identification and quantification of transient species by pulse radiolysis and of final products by LC-MS and high-resolution MS/MS after γ-radiolysis. By parallel photochemical experiments, using 3-carboxybenzophenone (CB) triplet with the model peptide, we compared the outcomes in terms of short-lived intermediates and stable product identification. The result is a detailed mechanistic scheme of Met oxidation by HO•, and by CB triplets allowed for assigning transient species to the pathways of products formation. 相似文献
2.
Yuanyuan Chen Jian Peng Tian Sheng Ruixuan Qin Shuqi Dai Zaifa Shi Zichao Tang Laisen Wang Qinghua Zhang Bin Han Liping Sun Jun Xu Jian Weng 《Advanced functional materials》2021,31(42):2104246
Radicals are closely related to human life and health and have been widely used in biology, chemistry, functional materials, etc. However, the high reactivity, disorder, and short half-lives limit their wide applications. Therefore, it remains a great challenge to prepare stable and ordered radicals. Herein, radicals are prepared with protective umbrellas (diethylmethyleneamine, DEMA) that are integrated on the surface of 2D layered materials to isolate water and oxygen and enhance the stability of radicals. Taking 2D black phosphorus (BP) as an example: triethylamine reacts with dichloromethane to form quaternary ammonium salts with further Hoffmann elimination to produce DEMA radicals that could react with one electron of a lone pair electrons in P on the surface of BP to produce P radicals, which shows a prolonged half-life of 21 days at room temperature. First-principle calculations and electron paramagnetic resonance fitting confirm that the steric hindrance constructed by dense DEMA passivation layer acts as a protective umbrella and the 2D coupling of P radicals and other P atoms in 2D BP plane to enhance the stability and strong superexchange interaction of P radicals. Furthermore, it is a general strategy to produce stable radicals integrated on the 2D plane. 相似文献
3.
Shensong Wang Zheng Wu Jie Chen Jiangping Ma Jingshi Ying Shouchen Cui Shigang Yu Yongming Hu Jinhe Zhao Yanmin Jia 《Ceramics International》2019,45(9):11703-11708
In this work, the hydrothermally-synthesized sodium niobate nanowires were used to decompose Rhodamine B dye solution through the piezo-catalytic effect. With the sodium niobate catalyst, a high piezo-catalytic degradation ratio of ~80% was achieved under the excitation of vibration for the Rhodamine B dye solution (~5?mg/l). These active species in the catalytic process, hydroxyl radicals and superoxide radicals with the strong oxidation ability, were also observed, which confirmed the key role of piezoelectric effect for piezo-catalysis. The piezo-catalysis of sodium niobate nanowires provides a high-efficiency and reusable tool in application in depredating the dye wastewater. 相似文献
4.
The interface of nitroxide radicals with cucurbit[n]urils (CB[n]) is covered in this review. Either used as spin probes, spin labels, or stoppers for paramagnetic rotaxanes, nitroxides offer new opportunities to investigate CB[n] and their inclusion complexes, especially thanks to EPR spectroscopy. On the other hand, CB[n] also offer interesting opportunities to modulate nitroxide properties such as protection or structuring. The multiple back and forth between the two well-established areas where nitroxides bring information about CB[n], and CB[n] modulate nitroxide properties, have enabled to shed some light at this new interesting interface. 相似文献
5.
6.
Fei Xu Xiangli Shi Qingzhu Zhang Wenxing Wang 《International journal of molecular sciences》2015,16(8):18714-18731
The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. 相似文献
7.
在先进飞行器发动机中,吸热碳氢燃料在进入燃烧室之前会发生热裂解反应,生成未反应燃料和小分子裂解产物的混合物(称为裂解态燃料)。本工作研究了在1300~1800 K、0.1~3.0 MPa和当量比为1.0的条件下,不同的裂解转化率、裂解压力、点火压力和自由基对正癸烷裂解着火特性的影响。通过采用一种精确的组合机理,从理论上计算了流动反应器中3.0和5.0 MPa下正癸烷裂解组分,与文献中的实验结果吻合较好。结果表明,正癸烷在3 MPa和5 MPa下裂解的出口转化率分别为46.2%和58.8%,裂解产物分布一致,但乙烯的含量随着压力的升高明显的降低,而烷烃含量随着压力的增大而增加。尽管自由基总体含量很低,但在3 MPa条件下裂解产物中的自由基浓度依然高于5 MPa条件下。对于点火延迟时间的计算结果则表明,裂解态正癸烷的点火延迟时间随着转化率的增大而延长,且在5 MPa下随着转化率的变化更明显。相同转化率下,5 MPa下的裂解态正癸烷的点火延迟时间比3 MPa下更短。此外,与无自由基的裂解正癸烷相比,裂解正癸烷中自由基的存在可以加速着火过程,转化率小于40%时,着火延迟时间缩短15%以上。 相似文献
8.
9.
The efficiency of Co(II)-, Mn(II)-, and Ti(IV)-doped carbon aerogels for the transformation of ozone into (*)OH radicals was investigated. The carbon aerogels had a markedly acid surface character (pH(PZC approximately equal) congruent with 3-4) with very high surface oxygen concentrations (O approximately equal with 20%). X-ray photoelectron spectroscopy (XPS) analyses of the samples showed the oxidation state of the metals was +2 for Co and Mn and +4 for Ti. The presence of Mn(II)-doped carbon aerogel enhanced ozone transformation into (*)OH radicals, whereas the presence of Co(II) and Ti(IV) carbon aerogels presented no activity in this process. Moreover, it was observed that an increase in the concentration of Mn in the surface of the aerogel increases its efficiency to transform ozone into (*)OH radicals, with an Rct value ([OH]/[O(3)]) of 5.36 x 10(-8) for the aerogel doped with 16% of surface Mn(II) compared to an R(ct) of 2.68 x 10(-9) for conventional ozonation. Regardless of the aerogel used, XPS analysis of the ozonated aerogel samples showed an increase in the concentration of surface oxygen when the exposure to ozone was longer. However, presence of oxidized metal species after ozone treatment was only detected in the case of the Mn-doped aerogel, (Mn(III) and Mn(IV)). CO(2) activation of carbon aerogel produced a marked increase in its efficiency to transform ozone into (*)OH radicals compared with non-activated sample. The efficiency of Mn activated carbon aerogel to transform ozone into (*)OH radicals was greater than that of Witco commercial activated carbon or H(2)O(2) in the ozonation of water from Lake Zurich (Zurich, Switzerland). 相似文献
10.
Efficiency of activated carbon to transform ozone into *OH radicals: influence of operational parameters 总被引:3,自引:0,他引:3
Based on previous findings (Jans, U., Hoigné, J., 1998. Ozone Sci. Eng. 20, 67-87), the activity of activated carbon for the transformation of ozone into *OH radicals including the influence of operational parameters (carbon dose, ozone dose, carbon-type and carbon treatment time) was quantified. The ozone decomposition constant (k(D)) was increased by the presence of activated carbon in the system and depending on the type of activated carbon added, the ratio of the concentrations of *OH radicals and ozone, the R(ct) value ([*OH]/[O3]), was increased by a factor 3-5. The results obtained show that the surface chemical and textural characteristics of the activated carbon determines its activity for the transformation of ozone into *OH radicals. The most efficient carbons in this process are those with high basicity and large surface area. The obtained results show that the interaction between ozone and pyrrol groups present on the surface of activated carbon increase the concentration of O2*- radicals in the system, enhancing ozone transformation into *OH radicals. The activity of activated carbon decreases for extended ozone exposures. This may indicate that activated carbon does not really act as a catalyst but rather as a conventional initiator or promoter for the ozone transformation into *OH radicals. Ozonation of Lake Zurich water ([O3] = 1 mg/L) in presence of activated carbon (0.5 g/L) lead to an increase in the k(D) and R(ct) value by a factor of 10 and 39, respectively, thereby favouring the removal of ozone-resistant contaminants. Moreover, the presence of activated carbon during ozonation of Lake Zurich water led to a 40% reduction in the content of dissolved organic carbon during the first 60 min of treatment. The adsorption of low concentrations of dissolved organic matter (DOM) on activated carbon surfaces did not modify its capacity to initiate/promote ozone transformation into *OH radicals. 相似文献