Investigation into the Oxygen-Involved ... - ACS Publications

Subscriber access provided by TULANE UNIVERSITY

Article

Investigation into the Oxygen-Involved Electrochemiluminescence of Porphyrins and Its Regulation by Peripheral Substituents/Central Metals Guiqiang Pu, Zhaofan Yang, Yali Wu, Ze Wang, Yang Deng, Yunjing Gao, Zhen Zhang, and Xiaoquan Lu Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b05027 • Publication Date (Web): 14 Jan 2019 Downloaded from http://pubs.acs.org on January 19, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Analytical Chemistry

Investigation into the Oxygen-Involved Electrochemiluminescence of Porphyrins and Its Regulation by Peripheral Substituents/Central Metals Guiqiang Pu,a, b Zhaofan Yang,b Yali Wu,b Ze Wang,b Yang Deng,a YunJing Gao,b Zhen Zhang,a and Xiaoquan Lu* a, b a.

Tianjin Key Laboratory of Molecular Optoelectronic, Department of Chemistry, Tianjin University, Tianjin, 300072, P. R. China. b. Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China.

*E-mail: [email protected]; [email protected]. Tel.: +86 931 797 1276. Fax: +86 931 797 1276. ABSTRACT: We provide evidence of oxygen-involved electrochemiluminescence (ECL) of metal-free porphyrins and metalloporphyrins firstly. O2•− and OH•, that are oxygen intermediates, are indispensable for the formation of excited porphyrins, which has been proven by trapping free radical strategies. The wide differences regarding emission location and mechanism between metal-free porphyrins [including meso-tetra(4-methoxyphenyl)porphine (H2TMPP), meso-tetraphenylporphyrin (H2TPP) and meso-tetra(4-carboxyphenyl)porphine (H2TCPP)] and metalloporphyrins (MTPP) depend on whether protons are present in the center of the porphin ring. Besides, the oxygen-involved ECL of porphyrins can be controlled regularly by peripheral substituents with different polarities. Because of the stretched molecular structure and the decrease in electron density around the protons located at porphin ring; electron-withdrawing groups are more conducive to protons being attacked by O2•−, as well as the enhancement of porphyrins ECL. The ECL efficiency [ФECL, which is normalized with respect to Ru(bpy)3(PF6)2 (taking ФECL of Ru(bpy)3(PF6)2 = 1 )] is gradually improved from H2TMPP (ФECL = 0.16), H2TPP (ФECL = 2.20) to H2TCPP (ФECL = 3.83); and the ФECL = 4.21 of Zn(II)TPP is significantly higher than other MTPP [e.g. Co(II)TPP and Cu(II)TPP]. A deeper understanding regarding the improvement of porphyrins ECL efficiency and new application towards porphyrins-related devices can be achieved from this work.

Porphyrins (containing metal-free porphyrins and metalloporphyrins), which play irreplaceable role in organism such as photosynthesis and oxygen transport, are receiving constant attention because of their unique optoelectronic properties;1,2 and the delocalized π electrons endow them with outstanding performances in numerous domains.3-5 Recently, expanded porphyrins, reported by Stuyver et al., were excellent candidates for molecular switches in molecular electronic devices mainly attributed to high combination density, fast response and high energy efficiency.6 Zhang et al. reported that the conversion efficiency of solar cells could be significantly improved in the presence of zinc(II) 5,10,15,20tetraethynylporphyrin as a core and perylene diimide as end groups.7 Porphyrins and their derivatives have also been an important member in electrochemiluminescence (ECL) as typical luminophore.8-11 The ECL behavior of 5,10,15,20tetraphenylporphyrin (H2TPP) in methylene chloride was reported firstly by Bard under the condition of deoxygenation, which the radiation was derived from the collision between H2TPP radical anion (H2TPP•−) and H2TPP radical cation (H2TPP•+).8 Recently, our group, for the first time, proposed the cathode ECL phenomenon of the meso-tetra(4-

carboxyphenyl)porphine (H2TCPP)/K2S2O8.12,13 We have also constructed a novel biomimetic luminescence technology defined as interfacial electron-induced ECL (IEIECL), the pathways of charge transfer at the interface are probed conveniently using the ECL of H2TPP.14 However, the roles of oxygen intermediates (e. g. O2•−, 1O2, OH•) in the ECL process of porphyrins are still ambiguous; the impact of peripheral substitutes and central metals on the ECL of porphyrins has not been probed meticulously yet. More comprehensive understanding to oxygen-involved ECL of porphyrins is urgently desired. ECL involves the production of excited state species and ultimately light from the reaction of electrogenerated oxidants and reductants.15,16 It is the perfect product produced by the combination of chemiluminescence and electrochemistry.17-18 Conventional ECL sensors with co-reactant pathways and ECL luminescent device with annihilation mechanism have been approved in the past two decades.19-24 However, the emergence of ECL as a functional characterization technique, like UV-vis and Raman spectra, is even more exciting. For instance, Wang et al. successfully distinguished the active roles of point defects in semiconductor Cd−In−S nanoclusters by

ACS Paragon Plus Environment

Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 10

Scheme 1. Oxygen-involved ECL of metal-free porphyrins and metalloporphyrins, along with the structures of investigated porphyrins.

ECL technology.25 Xu et al. also employed ECL microscopy to image the electrocatalysis of a novel bimetallic gold−platinum Janus nanoparticle.26 Furthermore, the effect of peripheral substitutes on luminophore can be distinguished using ECL.2729 Hence more meticulous and unique perspective information can be presented for materials with the help of ECL. In the present work, we describe the oxygen-involved ECL of various porphyrins for the first time (shown in Scheme 1). The participation of oxygen contributes to a remarkable improvement in ECL strength and stability through a new approach, which is completely different from the annihilation mechanism of the collision between cation and anion radical of porphyrins.8 Hydroxyl radicals (OH•) and superoxide anion radicals (O2•-), the intermediates of O2, are indispensable for the anode ECL of metal-free porphyrins and cathode ECL of metalloporphyrins, respectively; and it has been confirmed by trapping free radical strategies. The location and mechanism of ECL radiation are completely transformed after the porphyrin centre is occupied by metal ions; the intrinsic interaction was subsequently investigated. In addition, peripheral substituents with different polarities can directly regulate the ECL behavior of porphyrins on account of the molecular spatial structure and electron density distribution. The ECL spectrum was measured finally to illustrate the correctness of the mechanisms. This study shows that the protons located at porphin ring, molecular spatial structure, and the distribution of delocalized π electrons have a regular impact on the oxygeninvolved ECL of porphyrins.

EXPERIMENTAL SECTION Reagents. Meso-tetra(4-methoxyphenyl)porphine (H2TMPP), meso-tetraphenylporphyrin (H2TPP), mesotetra(4-carboxyphenyl)porphine (H2TCPP), zinc(II) mesotetraphenylporphyrin [Zn(II)TPP] were synthesized according to the literature; and 1H NMR (500 MHz) characterization of the as-synthesized porphyrins can be found in Supporting Information.8 Copper(II) mesotetraphenylporphine [Cu(II)TPP, 99%], cobalt(II) mesotetraphenylporphine [Co(II)TPP, 99%], iron(III) mesotetraphenylporphine chloride [Fe(III)TPP, 99%] and tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate [Ru(bpy)3(PF6)2, +99.8%] were obtained from Aladdin Industrial Corporation (Shanghai, China). Tetra-nbutylammonium hexafluorophosphate [(TBA)PF6, 99%] obtained from Aladdin Industrial Corporation (Shanghai,

China) was recrystallized three times from absolute ethanol and dried for 48 hours under vacuum at 60 °C. Anhydrous 1, 2, -dichloromethane (DCM, +99.9%, H2OIH2TPP>IH2TMPP) further illustrates the correctness of the aforementioned mechanism. The ECL efficiency (ФECL, which is the standard for judging the performance of luminophore) of the porphyrins can be obtained by means of the following formula.47-49 ФECL = Ф0ECL (IQf0/I0Qf)

(9)

Ф0

Where the value of the ECL of the 1.00 mM standard Ru(bpy)3(PF6)2 is artificially defined as 1.00. Values of Qf0 and Qf are the amount of transferred electrons in the process of ECL reaction toward Ru(bpy)3(PF6)2 and porphyrins, respectively. I0 and I represent the ECL intensity of Ru(bpy)3(PF6)2 under the deoxygenated conditions and porphyrins under the ambient conditions, respectively. Subsequently, the ФECL of the three metal-free porphyrins were all obtained, which gradually increased from H2TMPP (ФECL = 0.16), H2TPP (ФECL = 2.20) to H2TCP (ФECL = 3.83) (shown in table S2). The above results further demonstrate that electron-withdrawing groups substitution is more conducive to the enhancement of oxygen-involved ECL of porphyrins.

Figure 6. Oxygen-involved ECL spectrum of the H2TMPP(red trace), H2TPP(black trace), H2TCPP(green trace) and Zn(II)TPP(blue trace) in DCM:DMF (v:v = 3:1) under the ambient conditions. The concentrations of all porphyrins are 0.50 mM. The inset shows the ECL spectrum of H2TMPP.

Oxygen-involved ECL of metalloporphyrins. The introduction of various metal ions into the porphyrin ring permits a series of physiological functions to porphyrins, such as chlorophyll with magnesium ions and heme with iron ions.33, 50 Meaningful difference exists in optical and electrochemical properties of metalloporphyrins compared to its protoporphyrin. However, changes in oxygen-involved ECL of porphyrins after the addition of metal ions have hardly been explored. Hence in the

Page 6 of 10

current work, Zn(II)TPP was chosen to illustrate the above puzzle. As shown by the blue trace in Figure 7a, O2 was first reduced at -0.85 V vs Fc+/Fc when scanning toward the negative direction, followed by the production of ZnTPP•− derived from ZnTPP (at -1.46 V vs Fc+/Fc). Simultaneously, intense ECL (~7400.a.u.) was produced (red trace in Figure 7a), which is a completely different result compared to anode ECL of H2TPP. More efficient affinity of Zn(II)TPP to O2 leads to a stronger ECL signal compared metal-free porphyrins. The ФECL of Zn(II)TPP, ФECL=4.21, is also superior to other porphyrins. It is worth noting that a new ECL radiation peak (at 700 nm) is generated in addition to the radiant peak of Zn(II)TPP located at 603 and 652 nm (blue trace in Figure 6). This indicates that another substance is also excited during the scanning process. Stable and continuous ECL always existed under the condition of applying constant voltage (at -1.80 V vs Fc+/Fc) shown in Figure 7b, which indicates that the oxygen-involved ECL of Zn(II)TPP is a completely steady state. The anode ECL of Zn(II)TPP cannot appear when the scan is in the positive direction, and the optimizations for scanning potential and stability testing are also explored in Supporting Information and are shown in Figure S9 and Figure S10. Obviously, the pathway to produce excited Zn(II)TPP [Zn(II)TPP*] is altered due to the addition of zinc ion.

Figure 7. (a) Oxygen-involved ECL (red trace) and CV (blue trace) of the 0.50 mM Zn(II)TPP in DCM:DMF (v:v = 3:1) under the ambient conditions; R(O2), R(D), R(D•−) represent the reduction potential of O2, Zn(II)TPP and Zn(II)TPP•−, respectively; scan rate: 0.10 V·s-1. (b) Oxygen-involved ECL of the 0.50 mM Zn(II)TPP under the condition of applying constant voltage (-1.80 V). (c) Spatial molecular structure of H2TPP and Zn(II)TPP.

Figure 8. Oxygen-involved ECL (a) and absorption spectra (b) from 0.50 mM Zn(II)TPP (red trace), 0.50 mM Zn(II)TPP+0.05 mM TEOA (blue trace), 0.50 mM Zn(II)TPP+0.05 mM Quinone (green trace) and 0.50 mM deoxygenated Zn(II)TPP (black


Page 7 of 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


trace). Inset: Fluorescent photos of 0.50 mM Zn(II)TPP (I), 0.50 mM Zn(II)TPP+0.05 mM TEOA (II), 0.50 mM Zn(II)TPP +0.05 mM Quinone (III) and 0.50 mM deoxygenated Zn(II)TPP (IV) (left); as well as enlargement of 530-630 nm region (right).

Trapping free radical strategies were also used to explore intermediate produced by O2 reduction and the cathode ECL mechanism of Zn(II)TPP. As shown in Figure 8, The ECL of Zn(II)TPP could not be quenched by the addition of TEOA (blue trace); but it almost disappeared after adding Quinone (green trace) or deoxygenated treatment (black trace). Furthermore, the Zn(II)TPP is not denatured by the radical trappers because of the constancy of the UV-vis spectra and the FL characteristics before and after injecting radical trappers. This indicates that only O2•− exists in the process of Zn(II)TPP* production. Therefore, it can be concluded that the oxygen-involved ECL mechanism of Zn(II)TPP is as shown in eqs 10 - 16. Cathode scanning: O2 + e = O2•−

Ec = -0.85 V vs Fc+/Fc

Zn(II)TPP + e = Zn(II)TPP•− +

Zn(II)TPP•−

e=

Zn(II)TPP2−

Ec = -1.46 V vs

Fc+/Fc

Ec = -1.72 V vs

Fc+/Fc

Zn(II)TPP + Zn(II)TPP2− = Zn(II)TPP•−

(10) (11) (12) (13)

Zn(II)TPP•− + O2•− = Zn(II)TPP* + O22− or = Zn(II)TPP2− + 1O2* 1O

2*

=

3O

2

(14)

+ hv (λ = 700 nm)

(15)

Zn(II)TPP* = Zn(II)TPP + hv (λ = 603 and 652 nm)

(16)

Unlike H2TPP, there is no proton in the porphin ring of Zn(II)TPP, and the generated O2•− cannot be further converted into H2O. Hence Zn(II)TPP* and excited singlet oxygen molecules (1O2*), derived from the interaction of Zn(II)TPP•− with cumulated O2•−, are directly produced in the cathode region and releases overlaped cathode ECL. In addition, because the occupying of zinc ion has a negligible effect on the spatial framework and electron density distribution (Figure 7c and Figure 5), the internal causes of different oxygen-involved ECL between metalloporphyrins and metal-free porphyrins is whether protons are present in the center of the porphin ring.

shown in Figure 9 and Figure S11, although they have similar absorption spectra, fluorescence spectrum, electrochemical behavior and ECL mechanism (Eqs 10 - 16) compared to Zn(II)TPP, there are significant differences regarding ECL radiation intensity. Moreover, no ECL signal is detected and its reduction process is irreversible for Fe(III)TPP(Figure S12). It can be confirmed that there is a large difference in the oxygen-involved ECL intensity for different metalloporphyrin even if their ECL mechanism are the same. The possible reason is that different metalloporphyrins have different affinity for O2•−. which is being studied more deeply in our group.

CONCLUSION In summary, we have described the oxygen-involved ECL behavior of metal-free porphyrins and metalloporphyrins firstly; the intensity of this new ECL is about one hundred times compared to reported annihilation pathway. We have explored the role of various intermediates derived from O2 in the process of excited-state porphyrin production through trapping free radical strategies. For metal-free porphyrins, the anode ECL radiation comes from the interaction between OH• and porphyrins radical anions. But for metalloporphyrins, O2•− reacts directly with porphyrins radical anions, leading to overlaped cathode ECL. The above differences mainly depend on whether protons are present in the center of the porphin ring. Besides, the oxygen-involved ECL of porphyrins can be controlled regularly by peripheral substituents with different polarities. The difficulty of attacking protons located at porphin ring by O2•− determines the strength of ECL, which can be considered from the molecular space structure and electron density distribution. A deeper understanding regarding the improvement of porphyrins ECL efficiency can be achieved from this work, and this research will open new possibilities towards porphyrin-related sensors and lightemitting devices.

ASSOCIATED CONTENT Supporting Information

NMR characterization of as-synthesized various porphyrins; additional CV curves; and ECL response curves. The Supporting Information is available free of charge on the ACS Publications website.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]; [email protected]. Tel.: +86 931 797 1276. Fax: +86 931 797 1276. Figure 9. (a) Oxygen-involved ECL (dark cyan trace) and CV (black trace) of the 0.50 mM Co(II)TPP in DCM:DMF (v:v = 3:1) under the ambient conditions. (b) Oxygen-involved ECL (magenta trace) and CV (black trace) of the 0.50 mM Cu(II)TPP in DCM:DMF (v:v = 3:1) under the conditions of ambient conditions. R(O2), R(E), R(E•−), R(F) and R(F•−) represent the reduction potential of O2, Co(II)TPP, Co(II)TPP•−, Cu(II)TPP and Cu(II)TPP•−, respectively; scan rate: 0.10 V·s-1.

Co(II)TPP and Cu(II)TPP were subsequently explored in order to confirm the correctness of the above conclusions. As

ORCID Xiaoquan Lu: 0000-0003-2375-668X

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by National Natural Science Foundation of China (Grant Nos. 21575115, 21327005, 21705117, 21427808); the Program for Chang Jiang Scholars and Innovative Research Team, Ministry of Education, China (Grant No. IRT-16R61) and the Program of Gansu



Provincial Higher Education Research Project (Grant No. 2017-D-01). Furthermore, we extend our thanks to Professor Guizheng Zou at Shandong University for his support.

REFERENCES (1) Ethirajan, M.; Chen, Y.; Joshi, P.; Pandey, R. K. The role of porphyrin chemistry in tumor imaging and photodynamic therapy. Chem. Soc. Rev. 2011, 40, 340−362. (2) Galván-Miranda, E. K.; Castro-Cruz, H. M.; Arias-Orea, J. A.; Iurlo, M.; Valenti, G.; Marcaccio, M.; Macıás-Ruvalcaba, N. A. Synthesis, photophysical, electrochemical and electrochemiluminescence properties of A2B2 zinc porphyrins: the effect of π-extended conjugation. Phys. Chem. Chem. Phys. 2016, 18, 15025−15038. (3) Hartnett, P. E.; Mauck, C. M.; Harris, M. A.; Young, R. M.; Wu, Y.; Marks T. J.; Wasielewski, M. R. Influence of anion delocalization on electron transfer in a covalent porphyrin donor– perylenediimide dimer acceptor system. J. Am. Chem. Soc. 2017, 139, 749−756. (4) Li, L.; Diau, E. W.G. Porphyrin-sensitized solar cells. Chem. Soc. Rev. 2013, 42, 291−304. (5) Wu, H.; Fan, S.; Jin, X.; Zhang, H.; Chen, H.; Dai Z.; Zou, X. Construction of a zinc porphyrin–fullerene-derivative based nonenzymatic electrochemical sensor for sensitive sensing of hydrogen peroxide and nitrite. Anal. Chem. 2014, 86, 6285−6290. (6) Stuyver, T.; Perrin, M.; Geerlings, P.; Proft, F. De.; Alonso, M. Conductance switching in expanded porphyrins through aromaticity and topology changes. J. Am. Chem. Soc. 2018, 140, 1313−1326. (7) Zhang, A.; Li, C.; Yang, F.; Zhang, J.; Wang, Z.; Wei Z.; Li, W. An electron acceptor with porphyrin and perylene bisimides for efficient non-fullerene solar cells. Angew. Chem., Int. Ed. 2017, 56, 2694−2698. (8) Tokel, N. E.; Keszthelyi, C. P.; Bard, A. J. Electrogenerated Chemiluminescence. X. α, β, γ, δ-Tetraphenylporphin Chemiluminescence. J. Am. Chem. Soc. 1972, 94, 4871−4877. (9) Deng, S.; Zhang, T.; Ji, X.; Wan, Y.; Xin, P.; Shan, D.; Zhang, X. Detection of zinc finger protein (EGR1) based on electrogenerated chemiluminescence from singlet oxygen produced in a nanoclay-supported porphyrin environment. Anal. Chem. 2015, 87, 9155−9162. (10) Deng, S.; Lei, J.; Huang, Y.; Cheng, Y.; Ju, H. Electrochemiluminescent quenching of quantum dots for ultrasensitive immunoassay through oxygen reduction catalyzed by nitrogen-doped graphene-supported hemin. Anal. Chem. 2013, 85, 5390−5396. (11) Yao, C.; Song, H.; Wan, Y.; Ma, K.; Zheng, C.; Cui, H.; Xin, P.; Ji, X.; Deng, S. Electro-photodynamic visualization of singlet oxygen induced by zinc porphyrin modified microchip in aqueous media. ACS Appl. Mater. Interfaces. 2016, 8, 34833−34843. (12) Luo, D.; Huang, B.; Wang, L.; Idris, A. M.; Wang, S.; Lu, X. Cathodic electrochemiluminescence of meso-tetra(4carboxyphenyl) porphyrin/potassium peroxydisulfate system in aqueous media. Electrochimica Acta. 2015, 151, 42−49. (13) Li, L.; Ning, X.; Qian, Y.; Pu, G.; Wang, Y.; Zhang, X.; Wang, H.; Chen, J.; Shan, D.; Lu, X. Porphyrin nanosphere– graphene oxide composite for ehanced electrochemiluminescence and sensitive detection of Fe3+ in human serum. Sensors and Actuators B. 2018, 257, 331−339. (14) Pu, G.; Zhang, D.; Mao, X.; Zhang, Z.; Wang, H.; Ning, X.; Lu, X. Biomimetic interfacial electron-induced electrochemiluminesence. Anal. Chem. 2018, 90, 5272−5279. (15) Miao, W. Electrogenerated chemiluminescence and its biorelated applications. Chem. Rev. 2008, 108, 2506−2553. (16) Li, L.; Chen, Y., Zhu, J. Recent advances in electrochemiluminescence analysis. Anal. Chem. 2017, 89, 358−371.

Page 8 of 10

(17) Valenti, G.; Rampazzo, E.; Bonacchi, S.; Petrizza, L.; Marcaccio, M.; Montalti, M.; Prodi L.; Paolucci, F. Variable doping induces mechanism swapping in electrogenerated chemiluminescence of Ru(bpy)32+ core–shell silica nanoparticles. J. Am. Chem. Soc. 2016, 138, 15935−15942. (18) Richter, M. M. Electrochemiluminescence (ecl). Chem. Rev. 2004, 104, 3003−3036. (19) Zhang, X.; Tan, X.; Zhang, B.; Miao, W.; Zou, G. Spectrumbased electrochemiluminescent immunoassay with ternary CdZnSe nanocrystals as labels. Anal. Chem. 2016, 88, 6947−6953. (20) Yang, X.; Yu, Y.; Peng, L.; Lei, Y.; Chai, Y.; Yuan R.; Zhuo, Y. Strong electrochemiluminescence from MOF accelerator enriched quantum dots for enhanced sensing of trace cTnl. Anal. Chem. 2018, 90, 3995−4002. (21) Kudruk, S.; Villani, E.; Polo, F.; Lamping, S.; Korsgen, M.; Arlinghaus, H. F.; Paolucci, F.; Ravoo, B. J.; Valenti, G.; Rizzo, F. Solid state electrochemiluminescence from homogeneous and patterned monolayers of bifunctional spirobifluorene. Chem. Commun. 2018, 54, 4999−5002. (22) Gao, W.; Muzyka, K.; Ma, X.; Lou B.; Xu, G. A singleelectrode electrochemical system for multiplex electrochemiluminescence analysis based on a resistance induced potential difference.Chem. Sci. 2018, 9, 3911−3916. (23) Carrara, S.; Aliprandi, A.; Hogan, C. F.; Cola, L. D. Aggregation-induced electrochemiluminescence of platinum(II) complexes. J. Am. Chem. Soc. 2017, 139, 14605−14610. (24) Li, H.; Voci, S.; Ravaine V.; Sojic, N. Tuning electrochemiluminescence in multistimuli responsive hydrogel films. J. Phys. Chem. Lett. 2018, 9, 340−345. (25) Wang, F.; Lin, J.; Zhao, T.; Hu, D.; Wu T.; Liu, Y. Intrinsic “vacancy point defect” induced electrochemiluminescence from coreless supertetrahedral chalcogenide nanocluster. J. Am. Chem. Soc. 2016, 138, 7718−7724. (26) Zhu, M.; Pan, J.; Wu, Z.; Gao, X.; Zhao, W.; Xia, X.; Xu J.; Chen, H. Electrogenerated chemiluminescence imaging of electrocatalysis at a single Au-Pt Janus nanoparticle. Angew. Chem., Int. Ed. 2018, 130, 4074−4078. (27) Qi, H.; Zhang, C.; Huang, Z.; Wang, L.; Wang W.; Bard, A. J. Electrochemistry and electrogenerated chemiluminescence of 1,3,5-tri(anthracen-10-yl)-benzene-centered starburst oligofluorenes. J. Am. Chem. Soc. 2016, 138, 1947−1954. (28) Rizzo, F.; Polo, F.; Bottaro, G.; Fantacci, S.; Antonello, S.; Armelao, L.; Quici, S.; Maran, F. From blue to green: fine-tuning of photoluminescence and electrochemiluminescence in bifunctional organic dyes. J. Am. Chem. Soc., 2017, 139, 2060−2069. (29) Xiang, G.; Wang, X.; Li, M. S. M.; Kevin, L. Wang, S.; Ding, Z. Probing excimers of Pt(II) compounds with phenyl-1,2,3triazolyl and pyridyl-1,2,4-triazolyl chelate ligands by means of electrochemiluminescence. ChemElectroChem. 2017, 4, 1757−1762. (30) Eugenia, F.; Ramona, T.; Dana, V.; Costisor, O. UV-VIS and fluorescence spectra of meso-tetraphenylporphyrin and mesotetrakis-(4-methoxyphenyl) porphyrin in THF and THF-water systems. The influence of pH. Rev. Chim. 2007, 58, 451−455. (31) Hameren, R.; Buul, A. V.; Castriciano, M.; Villari, V.; Micali, N.; Schoön, P.; Speller, S.; Scolaro, L. M.; Rowan, A.; Elemans, J. A. W.; Nolte, R. J. M. Supramolecular porphyrin polymers in solution and at the solid−liquid interface. Nano Lett. 2008, 8, 253−259. (32) Ema, T.; Senge, M.; Nelson, N. Y.; Ogoshi, H.; Smith, K. M. 5,10,15,20-Tetra-tert-butylporphyrin and its remarkable reactivity in the 5- and 15-positions. Angew. Chem., Int. Ed. 1994, 33, 1879−1881. (33) Mousawi, A.; Poriel, C.; Dumur, F.; Toufaily, J.; Hamieh, T.; Fouassier, J. P.; Lalevée, J. Zinc tetraphenylporphyrin as high performance visible light photoinitiator of cationic photosensitive


Page 9 of 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


resins for LED projector 3D printing applications. Macromolecules. 2017, 50, 746−753. (34) Ma, T.; Pan, Z.; Miao, L.; Chen, C.; Han, M.; Shang Z.; Chen, J. Porphyrin-based symmetric redox-flow batteries towards cold-climate energy storage. Angew. Chem., 2018, 130, 3212−3216. (35) Wilson, G.; Neri, B. Cyclic voltammetry of porphyrins and metalloporphyrins. Ann. N. Y. Acad. Sci. 1973, 206, 568−578. (36) Ezzayani, K.; Denden, Z.; Najmudin, S.; Bonifácio, C.; Saint-Aman, E.; Loiseau, F.; Nasri, H. Exploring the effects of axial pseudohalide ligands on the photophysical and cyclic voltammetry properties and molecular structures of MgII tetraphenyl/porphyrin complexes. Eur. J. Inorg. Chem. 2014, 31, 5348−5361. (37) Kumar, S. S.; Bard, A. J. Background emission of electrogenerated chemiluminescence during oxidation of tri-npropylamine from the dimeric 1Δg state of O2. Anal. Chem. 2013, 85, 292−295. (38) Zhao, J.; Guo, W.; Li, J.; Chu, H.; Tu, Y. Study of the electrochemically generated chemiluminescence of reactive oxygen species on indium tin oxide glass. Electrochimica Acta. 2012, 61, 118-123. (39) Liu, Y.; Yan, K.; Zhang, J. Graphitic carbon nitride sensitized with CdS quantum dots for visible-light-driven photoelectrochemical aptasensing of tetracycline. ACS Appl. Mater. Interfaces. 2015, 8, 28255−28264. (40) Hou, H.; Zhang, X.; Huang, D.; Ding, X.; Wang, S.; Yang, X.; Li, S.; Xiang, Y.; Chen, H. Conjugated microporous poly(benzothiadiazole)/TiO2 heterojunction for visible-lightdriven H2 production and pollutant removal. Appl. Catal. B Environ. 2017, 203, 563−571. (41) Yong, Z.; Ren, J.; Hu, H.; Li, P.; Ouyang, S.; Xu, H.; Wang, D. Synthesis, characterization, and photocatalytic activity of gC3N4/KTaO3 composites under visible light irradiation. J. Nanomater. 2015, 2015, 1−7. (42) Han, J.; Jiang, S.; Gao Y.; Sun, F. Intramolecular-initiating photopolymerization behavior of nanogels with the capability of reducing shrinkage. J. Mater. Chem. C. 2016, 4, 10675−10683. (43) Stylidi, M.; Kondarides, D.; Verykios, X. Visible lightinduced photocatalytic degradation of Acid Orange 7 in aqueous TiO2 suspensions. Appl. Catal. B Environ. 2004, 47, 189−201. (44) Baciocchi, E.; Giacco, T. D.; Elisei, F.; Gerini, M. F.; Guerra, M.; Lapi, A.; Liberali, P. Electron transfer and singlet oxygen mechanisms in the photooxygenation of dibutyl sulfide and thioanisole in MeCN sensitized by N-methylquinolinium tetrafluoborate and 9,10-dicyanoanthracene. The probable involvement of a thiadioxirane intermediate in electron transfer photooxygenations. J. Am. Chem. Soc. 2003, 125, 16444−16454. (45) Shu, J.; Han, Z.; Zheng, T.; Du, D.; Zou, G.; Cui, H. Potential-resolved multicolor electrochemiluminescence of N-(4aminobutyl)-N-ethylisoluminol/tetra(4-carboxyphenyl) porphyrin/TiO2 nanoluminophores. Anal. Chem. 2017, 89, 12636−12640. (46) Cai, W.; Zhang, G.; Lu, K.; Zeng, H.; Cosnier, S.; Zhang, X.; Shan, D. Enhanced electrochemiluminescence of onedimensional self-assembled porphyrin hexagonal nanoprisms. ACS Appl. Mater. Interfaces. 2017, 9, 20904−20912. (47) Wallace, W. L.; Bard, A. J. Electrogenerated chemiluminescence. 35. temperature dependence of the ECL efficiency of Ru(bpy)32+ in acetonitrile and evidence for very high excited state yields from electron transfer reactions. J. Phys. Chem. C. 1979, 83, 1350−1357. (48) Polo, F.; Rizzo, F.; Veiga-Gutierrez, M.; De Cola, L.; Quici, S. Efficient Greenish Blue Electrochemiluminescence from Fluorene and Spirobifluorene Derivatives. J. Am. Chem. Soc. 2012, 134, 15402−15409. (49) Zhao,Y.; Zhang, Q.; Chen, K.; Gao, H.; Qi, H.; Shi, X.; Han,Y.; Wei, J.; Zhang, C. Triphenothiazinyl triazacoronenes: dnor–acceptor molecular graphene exhibiting multiple fluorescence and

electrogenerated chemiluminescence emissions. J. Mater. Chem. C. 2017, 5, 4293−4301. (50) Devaramani, S.; Ma, X.; Zhang, S.; Shinger, M. I.; Qin, D.; Shan, D.; Lu, X. Photo-switchable and wavelength selective axial ligation of thiol-appended molecules to zinc tetraphenylporphyrin: spectral and charge transfer kinetics studies. J. Phys. Chem. C. 2017, 121, 9729−9738.



Page 10 of 10

Table of Contents


10

Investigation into the Oxygen-Involved ... - ACS Publications

Recommend Documents