碳氧、氮氧以及硫氧等活性氧化物的化学发光

1、碳氧、氮氧以及硫氧等活性氧化物的化学发光F*的能量 基态激发态F光A + BC*C化学反应能 光化学发光反应的特点氧化还原反应与发光现象的同时发生化学发光分析常用的缓冲溶液碳酸盐缓冲溶液发光强度大体系稳定 ？带着疑问和好奇之心开始了超微弱化学发光的研究Flow-injection analysis with chemiluminescent determination of sulphite using Na2CO3-NaHCO3-Cu2+ systemJ.-M. Lin, T. Hobo, Anal. Chim. Acta, 1996, 323, 69-74.活性氧化合物化学发光研究与应用

2、活性氧 细胞破坏基因破坏疾病老化癌细胞的发生1O2 .OH .O2- H2O2HSO5-, HCO4-, ONOO-, 机体内活性氧的发生过程 O2.O22H+H2O2H+H2O.OHH+H2OC. Lu, J.-M. Lin, Trends Anal. Chem., 2006, 25(10), 985-995.Batch CL MethodSPMTNaHCO3H2O2HCO3与H2O2反应的化学发光现象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 验证HCO4的生成M. Liu, X. Cheng, L. Zhao, J.-M. Lin, Lu

4、minescence, 2006, 21, 179-185.在线生成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.荧光化合物的分析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 流动注射发光体系Organic cosolventH2O2H

6、CO3PumpDRFOC WasteFlow cellMixing tube J.-M. Lin, M. Liu, Spectrochim. Acta A, 2009, 72(1), 126-132.碳酸盐化学发光现象LightDCFH+H2O2 + HCO3- HOOCO2-H2OCO3-OH+O2-O21O2HCO3-HO2DCF*1）形成活性氧2）能量转移3) 实际应用发光光谱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光谱图35203500348034603440cbaGTEMPTEMPO不同体系DPA和DPA-O2的质谱比较a. HCO4-c. H2O2/ClO-b. H2O2/MoO42-TMPO标记的OH 的ESR光谱a. Fentonb. HCO4-.O2-化学发光试剂对体系的影响HCO4-的能量转移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能量转移受体 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谱图Conditions: Receiver gain: 8.00e+04; Mod amplitude: 1G; Sweep widt

10、h: 100.00G; Microwave power: 3.17e+00mW.动力学曲线化学发光机理 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-纳米金增强发光J.-M. Lin, M. Liu, J. Phys. Chem. B, 2008, 112(26), 7850-7855.61 nm50 nm33 nm22 nm16 nm14 nm反应前50 nm反应后50 nm不同粒径的金纳米化学发光信号H2O2 + HCO3 H2O + HCO4HOOCOO CO3+OHH2O2 + CO3 HCO3- + HO2HO2 H+ + O2HO2 + O2 1O2 + HO2-1O2 + Eosin Y Eosin Y* + O2Eosin Y* Eosin Y + h金纳米表面

12、原子有较高的活性，有助于自由基的产生和电子转移过程的发生。机理研究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.发光机理研究发光机理研究H. Chen, J.-M. Lin, et al., J. Phys. Chem. A, 2010, 114 (37), 1004910058 NO + .O2- ONOO- (K=6.7109 Lmol-ls-l) 过氧化亚硝基1998年诺贝尔生理学或医学奖 Robert F. Furchgott Louis J. IgnarroFerid Murad 发现氧化氮是心血管系统的一种信号分子H2O2HOONOHNO2OH-LightO21 min510-11 AOONO-+Micellar1O2ONOO-的化学发光反应机理ONOO-化学发光研究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增强化学发光机理研究与应用 利用ONOO-体系分析天然水中的亚硝酸根

15、 利用ONOO-体系分析血清中的总胆红素Anal. Chim. Acta, 2002, 474: 107-114.Talanta, 2004, 63: 333-337.碳点增强化学发光Z. Lin, W. Xue, H. Chen, J.-M. Lin, Anal. Chem., 2011, in press.亚硝酸盐测定Z. Lin, W. Xue, H. Chen, J.-M. Lin, Anal. Chem., 2011, in press.硫氧化合物化学发光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化学发光体系的仪器化林金明，程祥磊，赵利霞，用于水体样品中污染物在线监/检测的化学发光检测仪，中国发明专利，Automatic Instrument for the Analysis of Trace Phenol and Humic Acid in Marine海洋863课题成果活性氧化合物的化学发光研究与应用HO2-.O2-.OHONOO-HCO4-O2-ClO4-BrO3-IO4-H2O2HSO51O2过去十年的的研究最近五年的研究化学元素周期表固态液态气态人造元素1H2He3Li4Be5B6C7N8O9F10Ne11Na12

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