有机激发三重态参与的光化学反应研究进展

doi:10.16085/j.issn.1000-6613.2019-1754

摘要/Abstract

摘要：

光化学反应包括直接光解和间接氧化反应，其中间接氧化反应主要通过活性氧化性物种（reactive oxygen species, ROS）包括单线态氧（¹O₂）、过氧自由基（ $O 2 -$ ）和羟基自由基（·OH）等进行。近年来，有机激发三重态（³C^*）作为一种特殊的氧化剂参与光化学反应引起了广泛关注。本文主要综述了有机三重态光敏剂的形成和光化学反应机制、³C^*参与的环境光化学反应、³C^*自由基寿命、反应速率及稳态浓度测定和激发三重态的应用5个方面，并对未来有机分子激发三重态的研究方向进行了展望，指出³C^*是很多挥发性有机化合物（VOCs）或半/中等挥发性有机化合物（S/IVOCs）在大气中重要的汇，自然水体中溶解性有机质（dissolved organic matter，DOM）的激发三重态（³DOM^*）是污染物降解的主要氧化剂。今后应扩大³C^*与有机物反应的研究范畴，测定不同体系中³C^*的稳态浓度、产生速率（量子产率）等，为污染物治理提供理论依据。

关键词: 光化学反应, 活性氧化性物种, 光敏剂, 激发三重态, 形成机制

Abstract:

Photochemical reactions include direct photolysis and indirect oxidation, in which the indirect oxidation is mainly triggered by reactive oxygen species (ROS), including singlet oxygen (¹O₂), superoxide ( $O 2 -$ ) and hydroxyl radical (·OH). In recent years, organic triplet excited state (generally refer to as ³C^*), as a special oxidant, has attracted extensive attention in photochemical reactions. In this paper, the formation and photochemical reaction mechanism of organic triplet photosensitizers, the environmental photochemical reactions in which ³C^* participates, the lifetime of ³C^*, the determination of reaction rate and steady concentration, as well as the application of triplet excited states were reviewed. Meanwhile, the research direction of triplet excited states of organic molecules in the future is prospected. It was pointed out that ³C^* was an important sink of VOC_S and semi-/intermediate VOCs (S/IVOCs)_{in the atmosphere. The triplet states of dissolved organic matter (³DOM^*) in natural water was the main oxidant for pollutant degradation. In the future, the research scope of the reaction of ³C^* with organic matter and the determination of steady concentration and production rate (quantum yield) of ³C^* in different systems should be extended in order to provide theoretical basis for pollutant treatment.}

Key words: photochemical reaction, reactive oxygen species, photosensitizer, triple excited states, formation mechanism

中图分类号:

X513

陈彦彤, 李旭东, 陶冶, 黄红缨, 叶招莲, 盖鑫磊. 有机激发三重态参与的光化学反应研究进展[J]. 化工进展, 2020, 39(8): 3344-3353.

Yantong CHEN, Xudong LI, Ye TAO, Hongying HUANG, Zhaolian YE, Xinlei GE. A review on photochemical reaction via organic triplet excited state[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3344-3353.

参考文献

1	CHEN Y F, GE X L, CHEN H, et al. Seasonal light absorption properties of water-soluble brown carbon in atmospheric ?ne particles in Nanjing, China[J]. Atmospheric Environment, 2018, 187: 230-240.
2	郭松, 胡敏, 尚冬杰, 等. 基于外场观测的大气二次有机气溶胶研究[J]. 化学学报, 2014, 72(2): 145-157.
2	GUO S, HU M, SHANG D J, et al. Research on secondary organic aerosols basing on field measurement[J]. Acta Chimica Sinica, 2014, 72(2): 145-157.
3	YU L, SMITH J D, LASKIN A, et al. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical[J]. Atmospheric Chemistry and Physics, 2014, 14(24): 13801-13816.
4	GE X L, ZHANG Q, SUN Y L, et al. Effect of aqueous-phase processing on aerosol chemistry and size distributions in Fresno, California, during wintertime[J]. Environmental Chemistry, 2012, 9(3): 221-235.
5	祁骞, 周学华, 王文兴. 二次有机气溶胶的水相形成研究[J]. 化学进展, 2014, 26(2/3): 458-466.
5	QI Q, ZHOU X H, WANG W X. Study on the formation of the aqueous phase of the secondary organic aerosols[J]. Progress in Chemistry, 2014, 26(2/3): 458-466.
6	MCNEILL V F. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols[J]. Environmental Science & Technology, 2015, 49(3): 1237-1244.
7	叶招莲, 瞿珍秀, 马帅帅, 等. 气溶胶水相反应生成二次有机气溶胶研究进展[J]. 环境科学, 2018, 39(8): 491-501.
7	YE Z L, QU Z X, MA S S, et al. Progress in the formation of secondary organic aerosols by the reaction of aerosol water[J]. Environmental Science, 2018, 39(8): 491-501.
8	庄雨, 陈彦彤, 李旭东, 等. 四乙基愈创木酚液相·OH氧化SOA产率及特征分析:初始浓度的影响[J]. 环境科学, 2020, 41(1): 147-155.
8	ZHUANG Y, CHEN Y T, LI X D, et al. Secondary organic aerosol mass yield and characteristics from 4-ethylguaiacol aqueous ·OH oxidation: effects of initial concentration[J]. Environmental Science, 2020, 41(1): 147-155.
9	YE Z L, ZHUANG Y, CHEN Y T, et al. Aqueous-phase oxidation of three phenolic compounds by hydroxyl radical: insight into secondary organic aerosol formation yields, mechanisms, products and optical properties[J]. Atmospheric Environment, 2020, 223: 117240-117252.
10	FELBER T, SCHAEFER T, HERRMANN H. OH-Initiated oxidation of imidazoles in tropospheric aqueous-phase chemistry[J]. Physical Chemistry A, 2019, 123: 1505-1513.
11	MOONSHINE M, RUDICH Y, KATSMAN S, et al. Atmospheric HULIS enhance pollutant degradation by promoting the dark Fenton reaction[J]. Geophysical Research Letters, 2008, 35(20): L20807.
12	LU J C, GE X L, LIU Y, et al. Significant secondary organic aerosol production from aqueous-phase processing of two intermediate volatility organic compounds[J]. Atmospheric Environment, 2019, 211: 63-68.
13	ANASTASIO C, MCGREGOR K G. Chemistry of fog waters in California's central valley: 1. In situ photoformation of hydroxyl radical and singlet molecular oxygen[J]. Atmospheric Environment, 2001, 35(6): 1079-1089.
14	VIONE D, MAURINO V, MINERO C, et al. Photochemical reactions in the tropospheric aqueous phase and on particulate matter[J]. Chemical Society Reviews, 2006, 35(5): 441-453.
15	YE Z L, QU Z X, MA S S, et al. A comprehensive investigation of aqueous-phase photochemical oxidation of 4-ethylphenol[J]. Science of the Total Environment, 2019, 685: 976-985.
16	ARNOLD W A. One electron oxidation potential as a predictor of rate constants of N-containing compounds with carbonate radical and triplet excited state organic matter[J]. Environmental Science Processes and Impacts, 2014, 16: 832-838.
17	SMITH J D, SIO V, YU L, et al. Secondary organic aerosol production from aqueous reactions of atmospheric phenols with an organic triplet excited state[J]. Environmental Science & Technology, 2014, 48(2): 1049-1057.
18	SMITH J D, KINNEY H, ANASTASIO C. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol[J]. Physical Chemistry Chemical Physics, 2015, 17(15): 10227-10237.
19	KAUR R, HUDSON B M, DRAPER J, et al. Aqueous reactions of organic triplet excited states with atmospheric alkenes[J]. Atmospheric Chemistry and Physics, 2019, 19: 5021-5032.
20	KAUR R, ANASTASIO C. First measurements of organic triplet excited states in atmospheric waters [J]. Environmental Science & Technology, 2018, 52(9): 5218-5226.
21	KAUR R, LABINS J R, HELBOCK S S, et al. Photooxidants from brown carbon and other chromophores in illuminated particle extracts[J]. Atmospheric Chemistry and Physics, 2019, 19(9): 6579-6594.
22	CHEN H, GE X L, YE Z L. Aqueous-phase secondary organic aerosol formation via reactions with organic triplet excited states-a short review[J]. Current Pollution Reports, 2018, 4(1): 8-12.
23	WANG X K, GEMAYEI R, HAYECK N, et al. Atmospheric photosensitization: a new pathway for sulfate formation[J]. Environmental Science and Technology, 2020, 54(6): 3114-3120.
24	ZHOU Z C, CHEN B N, QU X L, et al. Dissolved black carbon as an efficient sensitizer in the photochemical transformation of 17β-estradiol in aqueous solution[J]. Environmental Science and Technology, 2018, 52: 10391-10399.
25	PORTER G, WINDSOR M W. The triplet state in fluid media[C]//Proceedings of the Royal Society A: Mathematical Physical and Engineering Sciences, 1958, 245(1241): 238-258.
26	方雪慧, 黄蓉, 路娟娟, 等. 水相中苯酚光催化降解的全额光子效率[J]. 环境科学研究, 2016, 29(1): 99-106.
26	FANG X H, HUANG R, LU J J, et al. Full photon efficiency of photocatalytic degradation of phenol in aqueous phase[J]. Environmental Scientific Research, 2016, 29(1): 99-106.
27	伍晚花, 郭颂, 赵建章. 三重态-三重态湮灭上转换的研究进展[J]. 中国科学: 化学, 2012, 42(10): 1381-1398.
27	WU W H, GUO S, ZHAO J Z. Progress in the transformation of the triplet-triplet annihilation[J]. Chinese Science: Chemistry, 2012, 42(10): 1381-1398.
28	SINGH-RACHFORD T N, CASTELLANO F N. Low power visible-to-UV up conversion[J]. The Journal of Physical Chemistry A, 2009, 113(20): 5912-5917.
29	CHEN H C, HUNG C Y, WANG K H, et al. White-light emission from an upconverted emission with an organic triplet sensitizer[J]. Chemical Communications, 2009, 27: 4064-4066.
30	MCCABE A J, ARNOLD W A. Reactivity of triplet excited states of dissolved natural organic matter in stormflow from mixed-use watersheds[J]. Environmental Science & Technology, 2017, 51(17): 9718-9728.
31	JI H F, SHEN L. Triplet excited state characters and photosensitization mechanisms of α-terthienyl: a theoretical study[J]. Journal of Photochemistry and Photobiology B: Biology, 2009, 94(1): 51-53.
32	ANASTASIO C, FAUST B C, RAO C J. Aromatic carbonyl compounds as aqueous-phase photochemical sources of hydrogen peroxide in acidic sulfate aerosols, fogs, and clouds. 1. Non-phenolic methoxybenzaldehydes and methoxyacetophenones with reductants (phenols)[J]. Environmental Science & Technology,1997, 31(1): 218-232.
33	ALEGR??A A E, FERRER A, SANTIAGO G, et al. Photochemistry of water-soluble quinones. Production of the hydroxyl radical, singlet oxygen and the superoxide ion[J]. Journal of Photochemistry and Photobiology A: Chemistry, 1999, 127(1/2/3): 57-65.
34	FEILBERG A, NIELSEN T. Effect of aerosol chemical composition on the photodegradation of nitro-polycyclic aromatic hydrocarbons[J]. Environmental Science & Technology, 2000, 34(5): 789-797.
35	ZHANG D N, YAN S W, SONG W H. Photochemically induced formation of reactive oxygen species (ROS) from effluent organic matter[J]. Environmental Science & Technology, 2014, 48(21): 12645-12653.
36	DALRYMPLE R M, CARFAGNO A K, SHARPLESS C M. Correlations between dissolved organic matter optical properties and quantum yields of singlet oxygen and hydrogen peroxide[J]. Environmental Science & Technology, 2010, 44(15): 5824-5829.
37	ERICKSON P R, WALPEN N, GUERARD J J, et al. Controlling factors in the rates of oxidation of anilines and phenols by triplet methylene blue in aqueous solution[J]. The Journal of Physical Chemistry A, 2015, 119 (13): 3233-3243.
38	VECCHIO R DEI, BIOUGH N V. On the origin of the optical properties of humic substances[J]. Environmental Science & Technology, 2004, 38(14): 3885-3891.
39	CANONICA S, JANS U, STEMMLER K, et al. Transformation kinetics of phenols in water: photosensitization by dissolved natural organic material and aromatic ketones[J]. Environmental Science & Technology, 1995, 29(7): 1822-1831.
40	LIU Y, LU J C, CHEN Y F, et al. Aqueous-phase production of secondary organic aerosols from oxidation of dibenzothiophene (DBT)[J]. Atmosphere, 2020, 11: 151-164.
41	CANONICA S, HELLRUNG B, WIRZ J. Oxidation of phenols by triplet aromatic ketones in aqueous solution[J]. The Journal of Physical Chemistry A, 2000, 104(6): 1226-1232.
42	YE Z L, LI Q, MA S S, et al. Summertime day-night differences of PM_2.5 components (Inorganic ions, OC, EC, WSOC, WSON, HULIS, and PAHs) in Changzhou, China[J]. Atmosphere, 2017, 8(10): 189.
43	顾远, 李清, 黄雯倩, 等. 常州市冬季PM_2.5中类腐殖质昼夜特征分析[J]. 环境科学, 2019, 40(3): 1091-1100.
43	GU Y, LI Q, HUANG W Q, et al. Analysis of diurnal characteristics of humus in winter PM_2.5 in Changzhou city[J]. Environmental Science, 2019, 40(3): 1091-1100.
44	TSUI W G, MCNEILL V F. Modeling secondary organic aerosol production from photosensitized humic-like substances (HULIS)[J]. Environmental Science & Technology Letters, 2018, 5(5): 255-259.
45	MONGE M E, ROSEN?RN T, FAVEZ O, et al. Alternative pathway for atmospheric particles growth[J]. Proceedings of the National Academy of Sciences, 2012, 109(18): 6840-6844.
46	ZEPP R G, SCHLOTZHAUER P F, SINK R M. Photosensitized transformations involving electronic energy transfer in natural waters: role of humic substances[J]. Environmental Science & Technology, 1985, 19(1): 74-81.
47	HALLADJA S, HALLE A TER, AGUER J P, et al. Inhibition of humic substances mediated photooxygenation of furfuryl alcohol by 2,4,6-trimethylphenol. Evidence for reactivity of the phenol with humic triplet excited states[J]. Environmental Science & Technology, 2007, 41(17): 6066-73.
48	WERNER J J, MCNEILL K, ARNOLD W A. Environmental photodegradation of mefenamic acid[J]. Chemosphere, 2005, 58(10): 1339-1346.
49	RENARD P, REED HARRIS A E, RAPF R J, et al. Aqueous phase oligomerization of methyl vinyl ketone by atmospheric radical reactions[J]. The Journal of Physical Chemistry C, 2014, 118(50): 29421-29430.
50	GUZMáN M I, COLUSSI A J, HOFFMANN M R. Photoinduced oligomerization of aqueous pyruvic acid[J]. The Journal of Physical Chemistry A, 2006, 110(10): 3619-3626.
51	EUGENE A J, XIA S S, GUZMAN M I. Aqueous photochemistry of glyoxylic acid[J]. The Journal of Physical Chemistry A, 2016, 120(21): 3817-3826.
52	RICHARDS-HENDERSON N K, PHAM A T, KIRK B B, et al. Secondary organic aerosol from aqueous reactions of green leaf volatiles with organic triplet excited states and singlet molecular oxygen[J]. Environmental Science & Technology, 2015, 49(1): 268-276.
53	GRGI? I, NIETO-GLIGOROVSKI L I, Net S, et al. Light induced multiphase chemistry of gas-phase ozone on aqueous pyruvic and oxalic acids[J]. Physical Chemistry Chemical Physics, 2010, 12(3): 698-707.
54	ROSSIGNOL S, AREGAHEGN K Z, TINEL L, et al. Glyoxal induced atmospheric photosensitized chemistry leading to organic aerosol growth[J]. Environmental Science & Technology, 2014, 48(6): 3218-3227.
55	AREGAHEGN K Z, NOZIèRE B, GEORGE C. Organic aerosol formation photo-enhanced by the formation of secondary photosensitizers in aerosols[J]. Faraday Discussions, 2013, 165: 123-134.
56	MONGE M E, D' ANNA B, MAZRI L, et al. Light changes the atmospheric reactivity of soot[J]. Proceedings of the National Academy of Sciences of the United States of America, 2010, 107(15): 6605-6609.
57	REMUCAL C K. The role of indirect photochemical degradation in the environmental fate of pesticides: a review[J]. Environmental Science: Processes & Impacts, 2014, 16: 628-653.
58	BAXTER R M, CAREY J H. Evidence for photochemical generation of superoxide ion in humic waters[J]. Nature, 1983, 306(5943): 575-576.
59	CHEN Z Y, ANASTASIO C. Concentrations of a triplet excited state are enhanced in illuminated ice[J]. Environmental Science: Processes & Impacts, 2017, 19(1): 12-21.
60	GRANNAS A M, JONES A E, DIBB J, et al. An overview of snow photochemistry: evidence, mechanisms and impacts[J]. Atmospheric Chemistry and Physics, 2007, 7(2): 4329-4373.
61	SHARPLESS C M. Lifetimes of triplet dissolved natural organic matter (DOM) and the effect of NaBH₄ reduction on singlet oxygen quantum yields: implications for DOM photophysics[J]. Environmental Science and Technology, 2012, 46(8): 4466-4473.
62	PFLUG N C, SCHMITT M, MCNEILL K. Development of N?cyclopropylanilines to probe the oxidative properties of triplet-state photosensitizers[J]. Environmental Science and Technology, 2019, 53: 4813-4822.
63	FISCHER A M, KLIGER D S, WINTERLE J S, et al. Direct observation of phototransients in natural waters[J]. Chemosphere, 1985, 14(9): 1299-1306.
64	WENK J, EUSTIS S N, MCNEILL K, et al. Quenching of excited triplet states by dissolved natural organic matter[J]. Environmental Science & Technology, 2013, 47(22): 12802-12810.
65	FRLMMEL F H, BAUER H, PUTZLEN J, et al. Laser flash photolysis of dissolved aquatic humic material and the sensitized production of singlet oxygen[J]. Environmental Science and Technology, 1987, 21(6): 541-545.
66	CHAIKOVSKAYA O N, LEVIN P P, SUL'TIMOVA N B, et al. Triplet states of humic acids studied by laser flash photolysis using different excitation wavelengths[J]. Russian Chemical Bulletin, 2004, 53(2): 313-317.
67	ROSARIO-ORTIZ F L, CANONICA S. Probe compounds to assess the photochemical activity of dissolved organic matter[J]. Environmental Science and Technology, 2016, 50(23): 12532-12547.
68	KAUR R, ANASTASIO C. Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters[J]. Atmospheric Environment., 2017, 164: 387-397.
69	GREBEL J E, PIGNATELLO J J, MITCH W A. Sorbic acid as a quantitative probe for the formation, scavenging and steady-state concentrations of the triplet-excited state of organic compounds[J]. Water Research, 2011, 45(19): 6535-6544.
70	ALBINET A, MINERO C, VIONE D. Photochemical generation of reactive species upon irradiation of rainwater: negligible photoactivity of dissolved organic matter[J]. Science of the Total Environment, 2010, 408 (16): 3367-3373.
71	SAVCHENKOVA A S, SEMENIKHIN A S, CHECHET I V. Mechanism and rate constants of the CH₂+CH₂CO reactions in triplet and singlet states: a theoretical study[J]. Journal of Computational Chemistry, 2019, 40: 387-399.
72	LI Y J, WEI X X, CHEN J W, et al. Photodegradation mechanism of sulfonamides with excited triplet state dissolved organic matter: a case of sulfadiazine with 4-carboxybenzophenone as a proxy[J]. Journal of Hazardous Materials, 2015, 290: 9-15.
73	LI Y J, CHEN J W, QIAO X L. Insights into photolytic mechanism of sulfapyridine induced by triplet-excited dissolved organic matter[J]. Chemosphere, 2016, 147: 305-310.
74	ZENG T, ARNOLD W A. Pesticide photolysis in prairie potholes: probing photosensitized processes[J]. Environmental Science & Technology, 2013, 47(13): 6735-6745.
75	KELLY M M, ARNOLD W A. Direct and indirect photolysis of the phytoestrogens genistein and daidzein[J]. Environmental Science & Technology, 2012, 46(10): 5396-5403.
76	WENK J, GUNTEN U VON, CANONICA S. Effect of dissolved organic matter on the transformation of contaminants induced by excited triplet states and the hydroxyl radical[J]. Environmental Science & Technology, 2011, 45(4): 1334-1340.
77	ROSADO-LAUSELL S L, WANG H T, GUTIéRREZ L, et al. Roles of singlet oxygen and triplet excited state of dissolved organic matter formed by different organic matters in bacteriophage MS2 inactivation[J]. Water Research, 2013, 47(14): 4869-4879.
78	CUI S S, YIN D Y, CHEN Y Q, et al. In vivo targeted deep-tissue photodynamic therapy based on near-infrared light triggered upconversion nanoconstruct[J]. American Chemical Society, 2013, 7(1): 676-688.
79	ZHENG G, CHEN J, STEFFLOVA K, et al. Photodynamic molecular beacon as an activatable photosensitizer based on protease-controlled singlet oxygen quenching and activation[J]. Proceedings of the National Academy of Sciences, 2007, 104(21): 8989-8994.
80	PHILLIPS D. Light relief: photochemistry and medicine[J]. Photochemical & Photobiological Sciences, 2010, 9(12): 1589-1596.
81	SCH?ERLING M. The art of fluorescence imaging with chemical sensors[J]. Angewandte Chemie International Edition, 2012, 51(15): 3532-3554.
82	CIRIMINNA R, PAGLIARO M. Organofluoro-silica xerogels as high-performance optical oxygen sensors[J]. The Analyst, 2009, 134(8): 1531-1535.
83	O'CONNOR A E, GALLAGHER W M, BYRNE A T. Porphyrin and nonporphyrin photosensitizers in oncology: preclinical and clinical advances in photodynamic therapy[J]. Photochemistry and Photobiology, 2009, 85(5): 1053-1074.
84	WU W H, WU W T, JI S M, et al. Tuning the emission properties of cyclometalated platinum (Ⅱ) complexes by intramolecular electron-sink/arylethynylated ligands and its application for enhanced luminescent oxygen sensing[J]. Journal of Materials Chemistry, 2010, 20(43): 9775-9786.