Design, synthesis and photophysical properties of C60-modified proteins

Hiroto Murakami, Rika Matsumoto, Yuko Okusa, Takamasa Sagara, Mamoru Fujitsuka, Osamu Ito, Naotoshi Nakashima

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Fullerene-porphyrin conjugates coordinated with Fe and Zn ions (1·Fe and 1·Zn) were designed and synthesized. Compounds 1·Fe and 1·Zn were reconstituted into apomyoglobin successfully to produce C60-modified myoglobins, 1·Fe-Mb and 1·Zn-Mb, respectively. The axial-ligand exchange reaction revealed that 1·Fe-Mb maintains the intrinsic properties of native Mb, except for the autooxidation rate constant, suggesting similar microenvironment of the porphyrin moieties in the proteins. Cyclic voltammogram (CV) of a graphite electrode modified with a film of 1·Fe-Mb-didodecyldimethylammonium bromide (DDAB) showed two reversible redox couples with E0 = -206 and -1048 mV which are attributable to Fe2+/3+ and the reduction of the porphyrin ring, respectively. Differential pulse voltammogram of an electrode modified with a 1·Fe-Mb-tridodecylmethylammonium bromide (TDAB) film in water containing 0.5 M tetraethylammonium chloride and 10 mM 2,2′,2″-nitrilotriethanol showed three cathodic peaks at E1/2.1 = -372, E1/2.2 = -555, and E1/2.3 = -1028 mV which are attributable to Fe2+/3+, C600/1-, and the reduction of the porphyrin ring, respectively. The electrodes modified with 1·Fe-Mb and 1·Zn-Mb gave anodic photocurrent coupled with on-off light irradiation. The action spectrum of photocurrent for a 1·Zn-Mb-DDAB film was in accord with the UV-vis absorption spectrum of 1·Zn-Mb. Transient absorption spectra of 1·Zn in benzonitrile and 1·Zn-Mb in a 50 mM phosphate buffer at 100 ns after the ns-laser light pulse irradiation at 532 nm showed three absorption maxima at 700, 830, and 1000 nm which are assignable to the triplet excited state of C60 (3C60*), the triplet excited state of the zinc porphyrin (3Znp*), and C60 radical anion (C60.-), respectively. Existence of the apparent C60.- indicates the generation of charge-separation state, ZnP.+-C60.-. The rate constants for the generation of the charge separation states in 1·Zn and 1·Zn-Mb calculated from the fluorescence data were 8.2 × 108 s-1 and 6.4 × 108 s-1, respectively, and the corresponding quantum yields were 0.62 and 0.59.

Original languageEnglish
Pages (from-to)2026-2033
Number of pages8
JournalJournal of Materials Chemistry
Volume12
Issue number7
DOIs
Publication statusPublished - Jan 1 2002

Fingerprint

Porphyrins
Proteins
Photocurrents
Excited states
Absorption spectra
Rate constants
Irradiation
Fullerenes
Graphite electrodes
Electrodes
Tetraethylammonium
Myoglobin
Quantum yield
Bromides
Anions
Laser pulses
Buffers
Fluorescence
Phosphates
Ions

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Chemistry

Cite this

Murakami, H., Matsumoto, R., Okusa, Y., Sagara, T., Fujitsuka, M., Ito, O., & Nakashima, N. (2002). Design, synthesis and photophysical properties of C60-modified proteins. Journal of Materials Chemistry, 12(7), 2026-2033. https://doi.org/10.1039/b201145j

Design, synthesis and photophysical properties of C60-modified proteins. / Murakami, Hiroto; Matsumoto, Rika; Okusa, Yuko; Sagara, Takamasa; Fujitsuka, Mamoru; Ito, Osamu; Nakashima, Naotoshi.

In: Journal of Materials Chemistry, Vol. 12, No. 7, 01.01.2002, p. 2026-2033.

Research output: Contribution to journalArticle

Murakami, H, Matsumoto, R, Okusa, Y, Sagara, T, Fujitsuka, M, Ito, O & Nakashima, N 2002, 'Design, synthesis and photophysical properties of C60-modified proteins', Journal of Materials Chemistry, vol. 12, no. 7, pp. 2026-2033. https://doi.org/10.1039/b201145j
Murakami H, Matsumoto R, Okusa Y, Sagara T, Fujitsuka M, Ito O et al. Design, synthesis and photophysical properties of C60-modified proteins. Journal of Materials Chemistry. 2002 Jan 1;12(7):2026-2033. https://doi.org/10.1039/b201145j
Murakami, Hiroto ; Matsumoto, Rika ; Okusa, Yuko ; Sagara, Takamasa ; Fujitsuka, Mamoru ; Ito, Osamu ; Nakashima, Naotoshi. / Design, synthesis and photophysical properties of C60-modified proteins. In: Journal of Materials Chemistry. 2002 ; Vol. 12, No. 7. pp. 2026-2033.
@article{c2e9ab77582349548666e2f1e61dc821,
title = "Design, synthesis and photophysical properties of C60-modified proteins",
abstract = "Fullerene-porphyrin conjugates coordinated with Fe and Zn ions (1·Fe and 1·Zn) were designed and synthesized. Compounds 1·Fe and 1·Zn were reconstituted into apomyoglobin successfully to produce C60-modified myoglobins, 1·Fe-Mb and 1·Zn-Mb, respectively. The axial-ligand exchange reaction revealed that 1·Fe-Mb maintains the intrinsic properties of native Mb, except for the autooxidation rate constant, suggesting similar microenvironment of the porphyrin moieties in the proteins. Cyclic voltammogram (CV) of a graphite electrode modified with a film of 1·Fe-Mb-didodecyldimethylammonium bromide (DDAB) showed two reversible redox couples with E0 = -206 and -1048 mV which are attributable to Fe2+/3+ and the reduction of the porphyrin ring, respectively. Differential pulse voltammogram of an electrode modified with a 1·Fe-Mb-tridodecylmethylammonium bromide (TDAB) film in water containing 0.5 M tetraethylammonium chloride and 10 mM 2,2′,2″-nitrilotriethanol showed three cathodic peaks at E1/2.1 = -372, E1/2.2 = -555, and E1/2.3 = -1028 mV which are attributable to Fe2+/3+, C600/1-, and the reduction of the porphyrin ring, respectively. The electrodes modified with 1·Fe-Mb and 1·Zn-Mb gave anodic photocurrent coupled with on-off light irradiation. The action spectrum of photocurrent for a 1·Zn-Mb-DDAB film was in accord with the UV-vis absorption spectrum of 1·Zn-Mb. Transient absorption spectra of 1·Zn in benzonitrile and 1·Zn-Mb in a 50 mM phosphate buffer at 100 ns after the ns-laser light pulse irradiation at 532 nm showed three absorption maxima at 700, 830, and 1000 nm which are assignable to the triplet excited state of C60 (3C60*), the triplet excited state of the zinc porphyrin (3Znp*), and C60 radical anion (C60.-), respectively. Existence of the apparent C60.- indicates the generation of charge-separation state, ZnP.+-C60.-. The rate constants for the generation of the charge separation states in 1·Zn and 1·Zn-Mb calculated from the fluorescence data were 8.2 × 108 s-1 and 6.4 × 108 s-1, respectively, and the corresponding quantum yields were 0.62 and 0.59.",
author = "Hiroto Murakami and Rika Matsumoto and Yuko Okusa and Takamasa Sagara and Mamoru Fujitsuka and Osamu Ito and Naotoshi Nakashima",
year = "2002",
month = "1",
day = "1",
doi = "10.1039/b201145j",
language = "English",
volume = "12",
pages = "2026--2033",
journal = "Journal of Materials Chemistry",
issn = "0959-9428",
publisher = "Royal Society of Chemistry",
number = "7",

}

TY - JOUR

T1 - Design, synthesis and photophysical properties of C60-modified proteins

AU - Murakami, Hiroto

AU - Matsumoto, Rika

AU - Okusa, Yuko

AU - Sagara, Takamasa

AU - Fujitsuka, Mamoru

AU - Ito, Osamu

AU - Nakashima, Naotoshi

PY - 2002/1/1

Y1 - 2002/1/1

N2 - Fullerene-porphyrin conjugates coordinated with Fe and Zn ions (1·Fe and 1·Zn) were designed and synthesized. Compounds 1·Fe and 1·Zn were reconstituted into apomyoglobin successfully to produce C60-modified myoglobins, 1·Fe-Mb and 1·Zn-Mb, respectively. The axial-ligand exchange reaction revealed that 1·Fe-Mb maintains the intrinsic properties of native Mb, except for the autooxidation rate constant, suggesting similar microenvironment of the porphyrin moieties in the proteins. Cyclic voltammogram (CV) of a graphite electrode modified with a film of 1·Fe-Mb-didodecyldimethylammonium bromide (DDAB) showed two reversible redox couples with E0 = -206 and -1048 mV which are attributable to Fe2+/3+ and the reduction of the porphyrin ring, respectively. Differential pulse voltammogram of an electrode modified with a 1·Fe-Mb-tridodecylmethylammonium bromide (TDAB) film in water containing 0.5 M tetraethylammonium chloride and 10 mM 2,2′,2″-nitrilotriethanol showed three cathodic peaks at E1/2.1 = -372, E1/2.2 = -555, and E1/2.3 = -1028 mV which are attributable to Fe2+/3+, C600/1-, and the reduction of the porphyrin ring, respectively. The electrodes modified with 1·Fe-Mb and 1·Zn-Mb gave anodic photocurrent coupled with on-off light irradiation. The action spectrum of photocurrent for a 1·Zn-Mb-DDAB film was in accord with the UV-vis absorption spectrum of 1·Zn-Mb. Transient absorption spectra of 1·Zn in benzonitrile and 1·Zn-Mb in a 50 mM phosphate buffer at 100 ns after the ns-laser light pulse irradiation at 532 nm showed three absorption maxima at 700, 830, and 1000 nm which are assignable to the triplet excited state of C60 (3C60*), the triplet excited state of the zinc porphyrin (3Znp*), and C60 radical anion (C60.-), respectively. Existence of the apparent C60.- indicates the generation of charge-separation state, ZnP.+-C60.-. The rate constants for the generation of the charge separation states in 1·Zn and 1·Zn-Mb calculated from the fluorescence data were 8.2 × 108 s-1 and 6.4 × 108 s-1, respectively, and the corresponding quantum yields were 0.62 and 0.59.

AB - Fullerene-porphyrin conjugates coordinated with Fe and Zn ions (1·Fe and 1·Zn) were designed and synthesized. Compounds 1·Fe and 1·Zn were reconstituted into apomyoglobin successfully to produce C60-modified myoglobins, 1·Fe-Mb and 1·Zn-Mb, respectively. The axial-ligand exchange reaction revealed that 1·Fe-Mb maintains the intrinsic properties of native Mb, except for the autooxidation rate constant, suggesting similar microenvironment of the porphyrin moieties in the proteins. Cyclic voltammogram (CV) of a graphite electrode modified with a film of 1·Fe-Mb-didodecyldimethylammonium bromide (DDAB) showed two reversible redox couples with E0 = -206 and -1048 mV which are attributable to Fe2+/3+ and the reduction of the porphyrin ring, respectively. Differential pulse voltammogram of an electrode modified with a 1·Fe-Mb-tridodecylmethylammonium bromide (TDAB) film in water containing 0.5 M tetraethylammonium chloride and 10 mM 2,2′,2″-nitrilotriethanol showed three cathodic peaks at E1/2.1 = -372, E1/2.2 = -555, and E1/2.3 = -1028 mV which are attributable to Fe2+/3+, C600/1-, and the reduction of the porphyrin ring, respectively. The electrodes modified with 1·Fe-Mb and 1·Zn-Mb gave anodic photocurrent coupled with on-off light irradiation. The action spectrum of photocurrent for a 1·Zn-Mb-DDAB film was in accord with the UV-vis absorption spectrum of 1·Zn-Mb. Transient absorption spectra of 1·Zn in benzonitrile and 1·Zn-Mb in a 50 mM phosphate buffer at 100 ns after the ns-laser light pulse irradiation at 532 nm showed three absorption maxima at 700, 830, and 1000 nm which are assignable to the triplet excited state of C60 (3C60*), the triplet excited state of the zinc porphyrin (3Znp*), and C60 radical anion (C60.-), respectively. Existence of the apparent C60.- indicates the generation of charge-separation state, ZnP.+-C60.-. The rate constants for the generation of the charge separation states in 1·Zn and 1·Zn-Mb calculated from the fluorescence data were 8.2 × 108 s-1 and 6.4 × 108 s-1, respectively, and the corresponding quantum yields were 0.62 and 0.59.

UR - http://www.scopus.com/inward/record.url?scp=0036318488&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0036318488&partnerID=8YFLogxK

U2 - 10.1039/b201145j

DO - 10.1039/b201145j

M3 - Article

AN - SCOPUS:0036318488

VL - 12

SP - 2026

EP - 2033

JO - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

SN - 0959-9428

IS - 7

ER -