Synthesis of heme substituted with fluoro and perfluoroalkyl groups, and application of fluorine nuclear to NMR-probe
| Project/Area Number |
16550153
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemistry related to living body
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| Research Institution | Nagaoka National College of Technology |
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Principal Investigator |
SUZUKI Akihiro Nagaoka National College of Technology, Materials Engineering, associate professor, 物質工学科, 助教授 (60179190)
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| Project Period (FY) |
2004 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| 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)
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| Keywords | fluorine / porphyrin / heme / hemoprotein / NMR / ヘムタンパク |
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| 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.
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Report
(4 results)
Research Products
(4 results)
