碳氧、氮氧以及硫氧等活性氧化物的化學發(fā)光

1、碳氧、氮氧以及硫氧等活性氧化物的化學發(fā)光F*的能量 基態(tài)激發(fā)態(tài)F光A + BC*C化學反應能 光化學發(fā)光反應的特點氧化還原反應與發(fā)光現象的同時發(fā)生化學發(fā)光分析常用的緩沖溶液碳酸鹽緩沖溶液發(fā)光強度大體系穩(wěn)定 ？帶著疑問和好奇之心開始了超微弱化學發(fā)光的研究Flow-injection analysis with chemiluminescent determination of sulphite using Na2CO3-NaHCO3-Cu2+ systemJ.-M. Lin, T. Hobo, Anal. Chim. Acta, 1996, 323, 69-74.活性氧化合物化學發(fā)光研究與應用

2、活性氧 細胞破壞基因破壞疾病老化癌細胞的發(fā)生1O2 .OH .O2- H2O2HSO5-, HCO4-, ONOO-, 機體內活性氧的發(fā)生過程 O2.O22H+H2O2H+H2O.OHH+H2OC. Lu, J.-M. Lin, Trends Anal. Chem., 2006, 25(10), 985-995.Batch CL MethodSPMTNaHCO3H2O2HCO3與H2O2反應的化學發(fā)光現象H2O2 + HCO3- HCO4- H2O2M. Liu, X. Cheng, L. Zhao, J.-M. Lin, Luminescence, 2006, 21, 179-185.Kin

3、etic study of HCO4- In alcohol/water (1.76:1, v/v):HCO3+ H2O2 (solv) HCO4 + H2O (solv) (t=300 s)Keff = = 71, 25kobs = (2.4 )10-3 s-1HCO4- H2OH2O2 HCO3-D. E. Richardson, H. R. Yao, K. M. Frank, D. A. Bennett, J. Am. Chem. Soc. 122 (2000) 1729. 13C NMR 驗證HCO4的生成M. Liu, X. Cheng, L. Zhao, J.-M. Lin, Lu

4、minescence, 2006, 21, 179-185.在線生成HCO4Advantages:(1) Easily to prepare the fresh HCO4-(2) Stable and repeat(3) Mixing with different reagentsPumpH2O2HCO3HCO4 wasteM. Liu, L. Zhao, J.-M. Lin, J. Phys. Chem. A, 2006, 110, 7509-7514.熒光化合物的分析HCO3- + H2O2 HCO4- + H2O E（HCO4-/HCO3-）= 1.8V, vs. NHEHCO4-lig

5、htFluorescent organics J.-M. Lin, M. Liu, Spectrochim. Acta A, 2009, 72(1), 126-132.CL signals of different FOC in batch method Anthracene 110-3 MEosin Y 110-3 MFluorescein110-3 MRh6G 110-3 MUranine 110-3 M9-nitroanthracene110-3 M DCF 110-3 MRhB 110-3 M Calcein 110-3 M 流動注射發(fā)光體系Organic cosolventH2O2H

6、CO3PumpDRFOC WasteFlow cellMixing tube J.-M. Lin, M. Liu, Spectrochim. Acta A, 2009, 72(1), 126-132.碳酸鹽化學發(fā)光現象LightDCFH+H2O2 + HCO3- HOOCO2-H2OCO3-OH+O2-O21O2HCO3-HO2DCF*1）形成活性氧2）能量轉移3) 實際應用發(fā)光光譜max = 509 nm DCF* DCF + hIn 2.0 M hydrogen peroxide (ethanol:water, 1.76;1, v/v)-0.05 M bicarbonate-DCF (11

7、0-5 M) system.1O2的ESR光譜圖35203500348034603440cbaGTEMPTEMPO不同體系DPA和DPA-O2的質譜比較a. HCO4-c. H2O2/ClO-b. H2O2/MoO42-TMPO標記的OH 的ESR光譜a. Fentonb. HCO4-.O2-化學發(fā)光試劑對體系的影響HCO4-的能量轉移Eu 1s2 2s2p6 3s2p6d10 4s2p6d10f7 5s2p6 6s2 5d0-7f15d0-7f2Eu(II)/(III)S.-X. Liang, L. Zhao, B. Zhang, J.-M. Lin, J. Phys. Chem. A, 2

8、008, 112(4), 618-623.Energy harvestingEnergy transferLight emission Light converting device能量轉移受體 A number of chelating agents were investigated with Eu as the metal ion, but the strongest emission was observed for the Eu-2,6-pyridinedicarboxylic acid (DPA) complex. The Eu-DPA complex exhibited the

9、strongest luminescence, and it was selected as the candidate for further study.a, HCO4 system; b, HCO4-Eu(II)-EDTA system. Conditions: 2 mol/L H2O2 (ethanol:water=1.76:1), 0.05 mol/L HCO3, 0.01 mol/L Eu(II), 0.03 mol/L EDTA. 1O2的ESR譜圖Conditions: Receiver gain: 8.00e+04; Mod amplitude: 1G; Sweep widt

10、h: 100.00G; Microwave power: 3.17e+00mW.動力學曲線化學發(fā)光機理 H2O2 + HCO3 H2O + HCO4 HCO4 + Eu(II) CO3- + OH + Eu(III) H2O2 + CO3- HCO3 + HO2 HO2 H+ + O2- (pK=4.8) O2- + OH 1O2 + HO O2- + HO2 1O2 + HO2 HO2 + HO2 1O2 + H2O2 1O2 + Eu(III)(EDTA) 2O2 + Eu(III)(EDTA)* Eu(III)(EDTA)* Eu(III)*(EDTA) Eu(III)*(EDTA) E

11、u(III)(EDTA) + h (= 620 nm)HCO4-納米金增強發(fā)光J.-M. Lin, M. Liu, J. Phys. Chem. B, 2008, 112(26), 7850-7855.61 nm50 nm33 nm22 nm16 nm14 nm反應前50 nm反應后50 nm不同粒徑的金納米化學發(fā)光信號H2O2 + HCO3 H2O + HCO4HOOCOO CO3+OHH2O2 + CO3 HCO3- + HO2HO2 H+ + O2HO2 + O2 1O2 + HO2-1O2 + Eosin Y Eosin Y* + O2Eosin Y* Eosin Y + h金納米表面

12、原子有較高的活性，有助于自由基的產生和電子轉移過程的發(fā)生。機理研究4NaBH4+ 2Se +7H2O 2 NaHSe + Na2B4O7 +14H2 (1)CdCl2+ NaHSe +NaOH CdSe + 2NaCl + H2O (2) Cd2+ + Na2S CdS + 2Na+ (3) Molar ratio Cd2+ / MAA / HSe-Quantum yield x = st(Mx/Mst) (x/st)2CdSe/CdS QDsCL ReactionsH. Chen, R. Li, L. Lin, G. Guo, J.-M. Lin, Talanta, 2010, 81, 16

13、88-1696.發(fā)光機理研究發(fā)光機理研究H. Chen, J.-M. Lin, et al., J. Phys. Chem. A, 2010, 114 (37), 1004910058 NO + .O2- ONOO- (K=6.7109 Lmol-ls-l) 過氧化亞硝基1998年諾貝爾生理學或醫(yī)學獎 Robert F. Furchgott Louis J. IgnarroFerid Murad 發(fā)現氧化氮是心血管系統的一種信號分子H2O2HOONOHNO2OH-LightO21 min510-11 AOONO-+Micellar1O2ONOO-的化學發(fā)光反應機理ONOO-化學發(fā)光研究Cata

14、l. Today, 2004, 90, 343-347.NO3-+NO O2- ONOO- CO2ONOOCO2-35%.NO2 + .CO3- 65%NO3-+CO2ArHArNO2H+ONOOH0.9s-1RHROH.NO2 .OH.NO2 +.OH分解分子重排 70%30%硝化氧化H2O2 + HNO2 HOONO HNO3 OH-NO + O2 - ONOO-ONOO- NO- + 1O2 1O2 + Uranine Uranine*Uranine* Uranine + hn ONOO-Micelle1O2+light增強化學發(fā)光機理研究與應用 利用ONOO-體系分析天然水中的亞硝酸根

15、 利用ONOO-體系分析血清中的總膽紅素Anal. Chim. Acta, 2002, 474: 107-114.Talanta, 2004, 63: 333-337.碳點增強化學發(fā)光Z. Lin, W. Xue, H. Chen, J.-M. Lin, Anal. Chem., 2011, in press.亞硝酸鹽測定Z. Lin, W. Xue, H. Chen, J.-M. Lin, Anal. Chem., 2011, in press.硫氧化合物化學發(fā)光W. Xue, Z. Lin, H. Chen, C. Lu, J.-M. Lin, J. Phys. Chem. C, 2011

16、, in press Middle seawaterSurfase seawaterBottom seawaterPhenol standard 1Humic acid standard 0Luminol Humic acid standard 1KMnO4Phenol standard 0Acid Ce(IV)WaterElectromagnetic valve V2V1V3V4V5V6V7V8V9V10V11Peristaltic pumpElectromagnetic valve controlA/D ConvertMicroprocessor Pre-amplifier HVWaste

17、 liquidPeristaltic pump control化學發(fā)光體系的儀器化林金明，程祥磊，趙利霞，用于水體樣品中污染物在線監(jiān)/檢測的化學發(fā)光檢測儀，中國發(fā)明專利，Automatic Instrument for the Analysis of Trace Phenol and Humic Acid in Marine海洋863課題成果活性氧化合物的化學發(fā)光研究與應用HO2-.O2-.OHONOO-HCO4-O2-ClO4-BrO3-IO4-H2O2HSO51O2過去十年的的研究最近五年的研究化學元素周期表固態(tài)液態(tài)氣態(tài)人造元素1H2He3Li4Be5B6C7N8O9F10Ne11Na12

18、Mg13Al14Si15P16S17Cl18Ar55Cs56Ba57La72Hf73Ta74W75Re76Os77Ir78Pt79Au80Hg81Ti82Pb83Bi84Po85At86Rn87Fr88Ra89Ac104Rf105Ha106Sg107Bh108Hs109Mt110Uun 111 Uuu112Uub113Uut114UuqLanthanons鑭系元素58Ce59Pr60Nd61Pr62Sm53Eu64Gd65Tb66Dy67Ho68Er69Tm70Yb71LuActinons錒系元素90Th91Pa92U93Np94Pu95Am96Cm97Bk98Cf99 Es100Fm101Md102No103Lr19K 20Ca21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn 31Ga 32Ge 33As 34Se35Br36Kr37Rb38Sr39Y40Zr41Nb42Mo43Tc44Ru45R