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Synthesis of heme substituted with fluoro and perfluoroalkyl groups, and application of fluorine nuclear to NMR-probe

Research Project

Project/Area Number 16550153
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemistry related to living body
Research InstitutionNagaoka National College of Technology

Principal Investigator

SUZUKI Akihiro  Nagaoka National College of Technology, Materials Engineering, associate professor, 物質工学科, 助教授 (60179190)

Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2006: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordsfluorine / porphyrin / heme / hemoprotein / NMR / ヘムタンパク
Research Abstract

Site-specific fluoro-groups(-F, -CF_3) introduction to a enzymatic reaction, coenzyme and protein has been a unique method to elucidate function-structure relationship in biological systems. Aiming at incorporation into Myoglobin, several fluorinated hemes have been synthesized and their particular physicochemical properties have been characterized by electrochemical measurement and ^<19>F NMR.
The starting pyrrole β-difluoropyrrole was prepared by the improved method (ref. Henne, A.L. ; Zimmer, W.F. J.Am.Chem.Soc. 1951, 73, 1103-1104). Then, coupling reactions of β-difluoropyrrole and β-monofluoropyrrole gave rise to a new fluorinated dipyrromethene hydrobromide. Cyclization of fluorinated dipyrromethene hydrobromide and another dipyrromethene hydrobromide gave the site specific fluoroporphyrin in low yield (2,3,7-TFP:1.2%).
Symmetrical bis-trifluoromethylated porphyrin (2,8-DPF) was obtained by oxidative cyclization in moderate yield (14 %).The ^<19>F NMR spectrum of 2,8-DPF was observed a single signal at δ-103.77ppm downfield from trifluoroacetic acid (TFA) as an external reference.
2,8-DPF was incorporated into sperm whale apo-myoglobin. The pattern of absorption spectra of the met-, deoxy- and oxy-adduct-forms of reconstituted myoglobin with 2,8-DPF was similar to the native myoglobin. The pattern of spectral similarities among the reconstituted myoglobin with 2,8-DPF, mesohemin and native hemin indicate that the structure of these myoglobins are much the same.
Thus, the ring-fluorinated heme may be useful as a mimicking prosthetic heme in the reconstitutional studies of various heme enzymes.

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (4 results)

All 2007 2006

All Journal Article (4 results)

  • [Journal Article] Heme Orientational Disorder in Human Adult Hemoglobin Reconstituted with a Ring Fluorinated Heme and Its Functional Consequences2007

    • Author(s)
      Satoshi, Nagao
    • Journal Title

      Biochemical and Biophysical Research Communications 354

      Pages: 681-685

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Heme Orientational Disorder in Human Adult Hemoglobin Reconstituted with a Ring Fluorinated Heme and Its Functional Consequences2007

    • Author(s)
      Satoshi Nagao
    • Journal Title

      Biochemical and Biophysical Research Communications 354

      Pages: 681-685

    • Related Report
      2006 Annual Research Report
  • [Journal Article] ^<19>F NMR Study of b-type haemoproteins2006

    • Author(s)
      Yasuhiko, Yamamoto
    • Journal Title

      Modern Magnetic Resonance (G. A. Webb ed.)

      Pages: 1-8

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] ^<19>F NMR Study of b-type haemoproteins2006

    • Author(s)
      Yasuhiko, Yamamoto
    • Journal Title

      Modern Magnetic Resonance(G.A.Webb ed.)

      Pages: 1-8

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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