Platinization: a novel technique to anchor photosystem I reaction centres onto a metal surface at biological temperature and pH

Abstract Photosystem I (PSI) reaction centre core antenna complexes containing about 40 chlorophylls per P700 (PSI-40) are 6 nm biological photovoltaic device. PSI particles carry positively-charged domain(s) and can therefore interact electrostatically with a negatively-charged surface. PSI particles were platinized by reduction of [PtCl 6 ] −2 at neutral pH and 20°C. The presence of metallic platinum on PSI particles was observed directly by scanning tunnelling microscopy (STM). The platinized PSI particles were larger than control PSIs (without platinization), due to the presence of metallic platinum. The electric properties of PSI and metallic platinum were characterized by STM tunnelling conductance (I–V) measurements. Diodic response was obtained in platinized PSI. Metallic platinum formed during the reduction of [PtCl 6 ] 2− caused bonding between PSI particles and a gold metal surface. Using the technique of chemical platinization, PSI particles can be “welded” onto gold plates under biologically compatible conditions, resulting in a 2-dimensional spatial array of PSI particles anchored on the metal surface. Metallic platinum is not only a good conductor but also an active catalyst. This platinization “welding” technique is potentially important for both bioelectronics and biometallocatalysis.

[1]  T. Thundat,et al.  Scanning tunneling microscopy of DNA: The chemical modification of gold surfaces for immobilization of DNA , 1992 .

[2]  H. Berg Immobilized Cells and Enzymes: A Practical Approach. : J. Woodward (Editor). IRL Press, Oxford, 1985, 177 pp., £13.00. , 1986 .

[3]  T. G. Owens,et al.  Chemical platinization and its effect on excitation transfer dynamics and P700 photooxidation kinetics in isolated photosystem I. , 1995, Biophysical journal.

[4]  B. Kê,et al.  Difference spectra and extinction coefficients of P 700 . , 1972, Biochimica et biophysica acta.

[5]  A. Rutherford,et al.  The effect of ambient redox potential on the transient electron spin echo signals observed in chloroplasts and photosynthetic algae , 1982 .

[6]  John F. Kennedy,et al.  Immobilised Enzymes and Cells , 1990 .

[7]  Y. Kuk,et al.  Scanning tunneling spectroscopy of metal surfaces , 1990 .

[8]  R. Collins,et al.  Photosynthetic water splitting: in situ photoprecipitation of metallocatalysts for photoevolution of hydrogen and oxygen , 1994 .

[9]  E. Greenbaum,et al.  Molecular electronics of a single photosystem I reaction center: studies with scanning tunneling microscopy and spectroscopy. , 1995, Proceedings of the National Academy of Sciences of the United States of America.

[10]  C. Betzel,et al.  Three-dimensional structure of system I of photosynthesis at 6 Å resolution , 1993, Nature.

[11]  T. Thundat,et al.  Immobilization of DNA for scanning probe microscopy. , 1992, Proceedings of the National Academy of Sciences of the United States of America.

[12]  D. Hall,et al.  [8] Higher plant chloroplasts and grana: General preparative procedures (excluding high carbon dioxide fixation ability chloroplasts) , 1980 .

[13]  T. G. Owens,et al.  Antenna size dependence of fluorescence decay in the core antenna of photosystem I: estimates of charge separation and energy transfer rates. , 1987, Proceedings of the National Academy of Sciences of the United States of America.

[14]  E. Greenbaum Kinetic studies of interfacial photocurrents in platinized chloroplasts , 1992 .

[15]  T. G. Owens,et al.  Quenching of chlorophyll excited states in photosystem I by quinones: Stern-Volmer analysis of fluorescence and photochemical yield , 1992 .

[16]  E. Greenbaum Platinized Chloroplasts: A Novel Photocatalytic Material , 1985, Science.

[17]  A. P. Fein,et al.  Tunneling spectroscopy of the Si(111)2 × 1 surface , 1987 .

[18]  E. Greenbaum Vectorial photocurrents and photoconductivity in metalized chloroplasts , 1990 .

[19]  G. F. Humphrey,et al.  New spectrophotometric equations for determining chlorophylls a, b, c1 and c2 in higher plants, algae and natural phytoplankton , 1975 .

[20]  E. Greenbaum Photobioelectronic studies with thylakoid membranes , 1989 .

[21]  D. Hall,et al.  Photoelectrochemical responses of photosystem II particles immobilized on dye-derivatized TiO2 films , 1990 .

[22]  G. Fleming,et al.  Simulations of the temperature dependence of energy transfer in the PSI core antenna. , 1992, Biophysical journal.

[23]  J. Golbeck Structure, function and organization of the Photosystem I reaction center complex. , 1987, Biochimica et biophysica acta.

[24]  J. Markwell,et al.  Effect of detergents on the reliability of a chemical assay for P-700. , 1980, Biochimica et biophysica acta.

[25]  J. Norris,et al.  An electron spin echo phase shift observed in photosynthetic algae: Possible evidence for dynamic radical pair interactions , 1980 .

[26]  A. Holzwarth,et al.  Energy transfer and charge separation kinetics in photosystem I: Part 1: Picosecond transient absorption and fluorescence study of cyanobacterial photosystem I particles. , 1993, Biophysical journal.

[27]  V. Shuvalov,et al.  COUPLING OF PHOTOINDUCED CHARGE SEPARATION IN REACTION CENTERS OF PHOTOSYNTHETIC BACTERIA WITH ELECTRON-TRANSFER TO A CHEMICALLY MODIFIED ELECTRODE , 1989 .