It was observed that hydrazine could enhance the chemiluminescence （CL） intensity of tris-（1,10 phenanthroline）ruthenium（Ⅱ） （Ru（ phen）3^2＋ ）- Cerium（ Ⅳ ） ice（ Ⅳ ）） system, based on which, a novel CL...It was observed that hydrazine could enhance the chemiluminescence （CL） intensity of tris-（1,10 phenanthroline）ruthenium（Ⅱ） （Ru（ phen）3^2＋ ）- Cerium（ Ⅳ ） ice（ Ⅳ ）） system, based on which, a novel CL system, Ru（phen）3^2＋ Hydrazine-Ce（Ⅳ）, was established. This CL system was investigated and employed to detect hydrazine. Under the optimum experimental conditions, the linear range and detection limit of the proposed method are 2.0× 10^-6-2.0×10^-3g·L^-1 and 1. 8×10^-6g·L^-1, respectively. For 1. 5 × 10^-5, 1.5×10^-4 and 1.2×10^-3 g·L^-1 hydrazine, the relative standard deviation （RSD） is 2.9%, 2.2% and 3. 1%, respectively （n= 11）. The proposed method has been used to detect the content of hydrazine in the synthetic samples with satisfactory results.展开更多
The ubiquitous distribution of halogenated aromatic compounds（XAr） coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced ox...The ubiquitous distribution of halogenated aromatic compounds（XAr） coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes（AOPs） have been considered as an＂environmentally-friendly＂ technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals（UOH） by halogenated quinones and H_2O_2, we found, unexpectedly, that an unprecedented UOH-dependent two-step intrinsic chemiluminescene（CL） can be produced by H_2O_2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all UOH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure–activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that UOH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive,simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants.展开更多
基金Supported by Alexander von Humboldt Founda-tion,the National Natural Science Foundation of China (20575046) National Key Basic Research and Development Program (973 Pro-gram,2002CB211800) .
文摘It was observed that hydrazine could enhance the chemiluminescence （CL） intensity of tris-（1,10 phenanthroline）ruthenium（Ⅱ） （Ru（ phen）3^2＋ ）- Cerium（ Ⅳ ） ice（ Ⅳ ）） system, based on which, a novel CL system, Ru（phen）3^2＋ Hydrazine-Ce（Ⅳ）, was established. This CL system was investigated and employed to detect hydrazine. Under the optimum experimental conditions, the linear range and detection limit of the proposed method are 2.0× 10^-6-2.0×10^-3g·L^-1 and 1. 8×10^-6g·L^-1, respectively. For 1. 5 × 10^-5, 1.5×10^-4 and 1.2×10^-3 g·L^-1 hydrazine, the relative standard deviation （RSD） is 2.9%, 2.2% and 3. 1%, respectively （n= 11）. The proposed method has been used to detect the content of hydrazine in the synthetic samples with satisfactory results.
基金supported by the Strategic Priority Research Program of CAS(No.XDB01020300)NSF China Grants(Nos.21577149,21477139,21237005 and 21321004)NIH Grants(Nos.ES11497,RR01008 and ES00210)
文摘The ubiquitous distribution of halogenated aromatic compounds（XAr） coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes（AOPs） have been considered as an＂environmentally-friendly＂ technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals（UOH） by halogenated quinones and H_2O_2, we found, unexpectedly, that an unprecedented UOH-dependent two-step intrinsic chemiluminescene（CL） can be produced by H_2O_2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all UOH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure–activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that UOH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive,simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants.
