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Fabrication of anodic photocurrent generation systems by use of 6-O-dihydrophytylcellulose as a matrix or a scaffold of porphyrins

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Abstract

Langmuir-Blodgett (LB) films containing porphyrin molecules were fabricated by use of 6-O-dihydrophytylcellulose (DHPC) toward anodic photocurrent generation systems. To suppress the porphyrin aggregation, two different approaches were applied: (1) mixing a low-molecular-weight porphyrin having a diterpenoid carbon skeleton (DPor) with DHPC as a matrix (matrix fabrication) and (2) bonding porphyrin molecules to the hydroxyl groups of DHPC covalently, converting into 6-O-dihydrophytyl-2,3-di-O-[p-(10,15,20-triphenyl-5-porphyrinyl)-benzoyl]cellulose as a scaffold (scaffold fabrication). The structure and film properties of the monolayers and the LB films were investigated by the surface pressure (π)–area (A) isotherm measurements, atomic force microscopy, UV–Vis spectroscopy, and absorption dichroism measurements. The porphyrin aggregation in the LB film could be well suppressed only by the scaffold fabrication, leading to the improvement of the photocurrent quantum yields. The efficient photocurrent performance can be demonstrated by the isolation and the parallel orientation of porphyrin moieties due to the cellulose rigid scaffold.

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References

  • Aoki A, Abe Y, Miyashita T (1999) Effective photoinduced electron transfer in hetero-deposited redox polymer LB films. Langmuir 15:1463–1469

    Article  CAS  Google Scholar 

  • Brabec CJ, Sariciftci NS, Hummelen JC (2001) Plastic solar cells. Adv Funct Mater 11:15–26

    Article  CAS  Google Scholar 

  • Choudhury B, Weedon AC, Bolton JR (1998) Effects of molecular organization on photophysical behavior. 2. Photoelectrochemical and photocurrent quantum yield studies of the Langmuir-Blodgett monolayers of some surfactant porphyrins. Langmuir 14:6199–6206

    Article  CAS  Google Scholar 

  • Elemans JAAW, Hameren R, Nolte RJM, Rowan AE (2006) Molecular materials by self-assembly of porphyrins, phthalocyanines, and perylenes. Adv Mater 18:1251–1266

    Article  CAS  Google Scholar 

  • Fujihira M, Yamada H (1988) Molecular photodiodes consisting of unidirectionally oriented amphathic acceptor-sensitizer-donor triads. Thin Solid Films 160:125–132

    Article  CAS  Google Scholar 

  • Ifuku S, Tsujii Y, Kamitakahara H, Takano T, Nakatsubo F (2005) Preparation and characterization of redox cellulose Langmuir-Blodgett films containing a ferrocene derivative. J Polym Sci A Polym Chem 43:5023–5031

    Article  CAS  Google Scholar 

  • Imahori H, Fukuzumi S (2004) Porphyrin- and fullerene-based molecular photovoltaic devices. Adv Funct Mater 14:525–536

    Article  CAS  Google Scholar 

  • Ishiwatari M, Yamada K, Ishiwatari R (2000) Pyrolytic formation of C19 isoprenoid hydrocarbons from dihydrophytol: in relation to the genesis of pristane in petroleum. Chem Lett 2000:206–207

    Article  Google Scholar 

  • Itoh T, Yano K, Inada Y, Fukushima Y (2002) Photostabilized chrolophyll a in mesoporous silica: absorption properties and photoreduction activity of chlorophyll a. J Am Chem Soc 124:13437–13441

    Article  CAS  Google Scholar 

  • Kadish KM, Morrison MM (1976) Solvent and substituent effects on the redox reactions of para-substituted tetraphenylporphyrin. J Am Chem Soc 98:3326–3328

    Article  CAS  Google Scholar 

  • Kondo T, Uosaki K (2007) Self-assembled monolayers (SAMs) with photo-functionalities. J Photochem Photobiol C 8:1–17

    Article  CAS  Google Scholar 

  • Konishi T, Ikeda A, Asai M, Hatano T, Shinkai S, Fujitsuka M, Ito O, Tsuchiya Y, Kikuchi J-I (2003) Improvement of quantum yields for photoinduced energy/electron transfer by isolation of self-aggregative zinc tetraphenyl porphyrin-pendant polymer using cyclodextrin inclusion in aqueous solution. J Phys Chem B 107:11261–11266

    Article  CAS  Google Scholar 

  • Konishi T, Ikeda A, Shinkai S (2005) Supramolecular design of photocurrent-generating devices using fullerenes aimed at modelling artificial photosynthesis. Tetrahedron 61:4881–4899

    Article  CAS  Google Scholar 

  • Li C, Imae T (2003) Protoporphyin IX zinc(II) organization at the air/water interface and its Langmuir-Blodgett films. Langmuir 19:779–784

    Article  CAS  Google Scholar 

  • Matile S, Berova N, Nakanishi K, Fleischhauer J, Woody RW (1996) Structural studies by exciton coupled circular dichroism over a large distance: porphyrin derivatives of steroids, dimeric steroids, and brevetoxin B-. J Am Chem Soc 118:5198–5206

    Article  CAS  Google Scholar 

  • Miyashita T (1993) Recent studies on functional ultrathin polymer films prepared by the Langmuir-Blodgett technique. Prog Polym Sci 18:263–294

    Article  CAS  Google Scholar 

  • Ogi T, Ito S (2006) Migration and transfer of excitation energy in homogeneously dispersed porphyrin monolayers prepared from amphiphilic copolymers. Thin Solid Films 500:289–295

    Article  CAS  Google Scholar 

  • Petty MC (1996) Langmuir-Blodgett films: an introduction. The Press Syndicate of the University of Cambridge, New York

    Google Scholar 

  • Redl FX, Lutz M, Daub J (2001) Chemistry of porphyrin-appended cellulose strands with a helical structure: spectroscopy, electrochemistry, and in situ circular dichroism. Chem Eur J 7:5350–5358

    Article  CAS  Google Scholar 

  • Sakakibara K, Ifuku S, Tsujii Y, Kamitakahara H, Takano T, Nakatsubo F (2006) Langmuir-Blodgett films of a novel cellulose derivative with dihydrophytyl group: the ability to anchor β-carotene molecules. Biomacromolecules 7:1960–1967

    Article  CAS  Google Scholar 

  • Sakakibara K, Kamitakahara H, Takano T, Nakatsubo F (2007a) Redox-active cellulose Langmuir-Blodgett films containing β-carotene as a molecular wire. Biomacromolecules 8:1657–1664

    Article  CAS  Google Scholar 

  • Sakakibara K, Ogawa Y, Nakatsubo F (2007b) First cellulose Langmuir-Blodgett films towards photocurrent generation systems. Macromol Rapid Commun 28:1270–1275

    Article  CAS  Google Scholar 

  • Sereno L, Silber JJ, Otero L, Bohorquez MDV, Moore AL, Moore TA, Gust D (1996) Photoelectrochemistry of Langmuir-Blodgett films of carotenoid pigments on ITO electrodes. J Phys Chem 100:814–821

    Article  CAS  Google Scholar 

  • Taniguchi T, Fukasawa Y, Miyashita T (1999) Photoelectrochemical response of polymer Langmuir-Blodgett films containing tris(2,2’-bipyridine)ruthenium(II) complex. J Phys Chem B 103:1920–1924

    Article  CAS  Google Scholar 

  • Tomé JPC, Neves MGPMS, Tomé AC, Cavaleiro JAS, Mendonça AF, Pegado IN, Duarte R, Valdeira ML (2005) Synthesis of glycoporphyrin derivatives and their antiviral activity against herpes simplex virus types 1 and 2. Bioorg Med Chem 13:3878–3888

    Article  CAS  Google Scholar 

  • Yoneyama M, Sugi M, Saito M, Ikegame K, Kuroda S-i, Iizima S (1986) Photoelectric properties of copper phthalocyanine Langmuir-Blodgett film. Jpn J Appl Phys 25:961–965

    Article  CAS  Google Scholar 

  • Yu J-H, Li F-Y, Wang X-S, Huang Y, Zhang B-W, Huang C-H, Cao Y (2002) Chain-length dependence of photoelectric conversion from a porphyrin monolayer modified electrode. Opt Mater 21:467–473

    Article  Google Scholar 

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Acknowledgments

We are grateful to Prof. Tokuji Miyashita and Dr. Jun Matsui (Tohoku University) for useful suggestions for the photocurrent measurements. This investigation was supported by a Grant-in-Aid for Scientific Research (No. 17380107) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. K.S. acknowledges the Research Fellowships of the Japan Society for the Promotion of Science (JSPS) for Young Scientists.

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Authors and Affiliations

  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto, 606-8502, Japan

    Keita Sakakibara & Fumiaki Nakatsubo

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  1. Keita Sakakibara
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  2. Fumiaki Nakatsubo
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Correspondence to Fumiaki Nakatsubo.

Additional information

This paper was the subject of the Best Poster Award of the 235th edition of the ACS National Meeting, Cellulose and Renewable Materials.

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Sakakibara, K., Nakatsubo, F. Fabrication of anodic photocurrent generation systems by use of 6-O-dihydrophytylcellulose as a matrix or a scaffold of porphyrins. Cellulose 15, 825–835 (2008). https://doi.org/10.1007/s10570-008-9228-2

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  • DOI: https://doi.org/10.1007/s10570-008-9228-2

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