Porphyrins functionalize graphene

Excellent recent reviews on graphene-based electrochemical sensors [113] and on analytical devices in biomolecules detection and cancer diagnostics [114] appeared recently, where the superior electrochemical sensing performances of graphene-based electrodes toward the detection of various biomolecules and chemicals have been demonstrated. Also in this field, porphyrin-functionalized graphene hybrids resulted in interesting analytical applications, as will be discussed next. 

Another interesting report presents the one-pot preparation of a ternary hybrid nanomaterial composed of a porphyrin-functionalized graphene, tin oxide, and gold nanoparticles [134]. This composite was applied to the simultaneous determination of epinephrine and uric acid. First, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin was linked to GO sheets dispersed in aqueous solution, then HAuCLt was added, followed by SnCl2. The latter ensured reduction to graphene and Au nanoparticles while forming Sn02. Reduction of GO was completed with hydrazine in alkaline medium. 

Malic E, Appel H, Hofmann OT, Rubio A. Energy transfer in porphyrin-functionalized graphene. Phys Status Solidi B 2014 251 2495-8. 

WangR-X, Fan J-J, FanY-J,ZhongJ-P, Wang L, Sun S-G, ShenX-C. Platinum nanoparticles on porphyrin functionalized graphene nanosheets as superior catalyst for methanol electrooxidation. Nanoscale 2014 6 14999-5007. 

Guo CX, Lei Y, Li CM. Porphyrin functionalized graphene for sensitive electrochemical detection of ultratrace explosives. Electroanalysis 2011 23 885-93. 

Wu Y, Luo S, Chen L. Manganese porphyrin functionalized graphene and its application on dimethoate electrochemical sensor. Adv Mater Res 2014 850-851 152—5. 

Wu L, Wang J, Feng L, Ren J, Wei W, Qu X. Label-free ultrasensitive detection of human telomerase activity using porphyrin-functionalized graphene and electrochemiluminescence technique. Adv Mater 2012 24 2447-52. 

Lv M, Mei T, Zhang C, Wang X. Selective and sensitive electrochemical detection of dopamine based on water-soluble porphyrin functionalized graphene nanocomposites. RSC Adv 2014 4 9261-70. 

Su S, Wang J, Wei J, Martinez-Zaguilan R, Qiu J, Wang S. Efficient photothermal therapy of brain cancer through porphyrin functionalized graphene oxide. New J Chem 2015 39 5743-5749. 

Zhang H, Han Y, Guo Y, Dong C (2012) Porphyrin functionalized graphene nanosheets-based electrochemical aptascnsor for label-free ATP detection. J Mater Chem 22 23900-23905... 

CHART 14.1 Structures of porphyrins most commonly used to functionalize graphene, GO, and RGO and one phthalocyanine. 

Electropolymerized films of Co(III) tetrakis(4-hydroxyphenyl)porphyrin, doped with ionic liquid (CoPbr-IL/G) functionalized graphene gave O2 electroreduction [90]. l-Butyl-3-melhylimidazolium tetrafluoroborate was used as IL. It is noteworthy that the performance of CoPor-IL/G resulted better than that of cobalt porphyrin alone, in terms of potential required and amount of undesired H2O2. 

Zinc 5,10,15,20-tetrakis(4-pyridyl)porphyrin was used to functionalize graphene quantum dots [108]. The nanocomposite was efficient in photocatalyz-ing degradation of methylene blue upon visible-light irradiation. Moreover, the nanomaterial could be recovered and reused with no variance of degradation rate. Therefore, it can be used as visible light-driven photocatalyst to decompose organic pollutants soluble in water. 

Kaplan A, Soifer L, Eliyahu D, Korin E, Bettelheim A. Electrocatalytic activity towards oxygen reduction of electropolymerized cobalt porphyrin doped with ionic-liquid-functionalized graphene. J Electrochem Soc 2015 162 H481-5. 

You J-M, Han HS, Lee HK, Cho S, Jeon S. Enhanced electrocatalytic activity of oxygen reduction by cobalt-porphyrin functionalized with graphene oxide in an alkaline solution. Int J Hydrogen Ener 2014 39 4803-11. 

Tripkovic V, Vanin M, Karamad M, Bjorketun ME, Jacobsen KW, Thygesen KS, Rossmeisl J. Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene. J Phys Chem C 2013 117 9187-95. 

Karimnezhad K, Moghimi A. Separation of Cr(III) from by functionalized graphene oxide with covalently linked porphyrin (GO-H2NP) adsorbed on surfactant coated Cjg. Orient J Chem 2014 30 187-94. 

Shi P, Ye N. Investigation of the adsorption mechanism and preconcentration of sulfonamides using a porphyrin-functionalized Fej04-graphene oxide nanocomposite. Talanta 2015 143 219-25. 

Since functionalization of the graphene with a porphyrin was reported for the first time [166], photovoltaic properties of this type constructs have intensively been studied. Photovoltaic properties of an assembly of the covalently linked free-base me o-tetraphenyl porphyrin with graphene oxide were evaluated [167]. The IPCE spectrum of this conjugate resembled the UV-vis absorbance spectrum of the porphyrin used reaching merely 1.5 % at the Soret band wavelength. 

Hu Y, Xue Z, He H et al (2013) Photoelectrochemical sensing for hydroquinone based on porphyrin-functionalized Au nanoparticles on graphene. Biosens Bioelectron 47 45 9... 

Xu, Y., et al., A graphene hybrid material covalently functionalized with porphyrin Synthesis and optical limiting property. Advanced Materials, 2009. 21(12) p. 1275-1279. 

In vie w of the peculiar photo- aud optoelectronic properties of self-assembled architectures of porphyrins [64] and of porphyrin-based porous sheets [65], it is easy to understaud why many efforts have been devoted toward functionalization of graphene and graphene-oxide with these macrocycle. 

Noncovalent functionalizations were obtained synthesizing porphyrinoids in the presence of sulfonated graphene, which acted as solid acid carbocatalyst [74]. The obtained porphyrinoids gave supramolecular interactions with pristine graphene. Alternatively, GO intercalated into self-assanbled porphyrins J-aggregates [75]. 

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