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Determination of protonation constants of some fluorinated polyamines by means of 13C NMR data processed by the new computer program HypNMR2000. Protonation sequence in polyamines

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Abstract.

The pK a values of 6-fluoro-4,8-diazadodecane-1,12-diamine (6-fluorospermine) (1), 6,6-difluoro-4,8-diazadodecane-1,12-diamine (6,6-difluorospermine) (2), 6-fluoro-4-azaoctane-1,8-diamine (6-fluorospermidine) (3) and 6,6-difluoro-4-azaoctane-1,8-diamine (6,6-difluorospermidine) (4) in D2O solution have been determined at 40 °C from 13C NMR chemical shifts data using the new computer program HypNMR2000. The enthalpies of protonation of compounds 1–4 and the parent amines spermine (5) and spermidine (6) have been determined from microcalorimetric titration data. The values of ΔH° were used to derive basicity constants relative to 25 °C. The NMR data have been analysed by two different methods to obtain information on the protonation sequence in the polyamines 1–5. The protonation sequence for spermine is related to its biological activity.

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Abbreviations

PKC :

Protein kinase C

PS :

Phosphatidylserine

VB :

Microsoft Visual Basic

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Acknowledgements.

The Italian Ministry for Education, University and Research, MIUR, and the Italian National Council for Research, CNR, are gratefully acknowledged for funding. The authors are grateful to Centro Interdipartimentale Grandi Strumenti dell'Università di Modena, for allowing the use of the AMX-400 WB Bruker spectrometer. We thank Dr Francesca Benevelli, formerly at the Centro Grandi Strumenti dell'Università di Pavia, for technical assistance with the NMR measurements.

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Authors and Affiliations

  1. Dipartimento di Scienze Biomediche, Università degli Studi di Modena, via Campi 287, 41100 , Modena, Italy

    Chiara Frassineti

  2. Department of Chemistry, The University of Leeds, LS2 9JT, Leeds, England

    Peter Gans

  3. Dipartimento di Chimica, Università degli Studi di Firenze, via della Lastruccia 3, 50019, Sesto Fiorentino, Italy

    Lucia Alderighi, Antonio Sabatini & Alberto Vacca

  4. SPIN, via Tamagno 3, 42048, Rubiera (Reggio Emilia), Italy

    Stefano Ghelli

Authors
  1. Chiara Frassineti
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  2. Lucia Alderighi
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  3. Peter Gans
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  4. Antonio Sabatini
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  5. Alberto Vacca
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  6. Stefano Ghelli
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Corresponding author

Correspondence to Alberto Vacca.

Additional information

Presented at the Spanish-Italian Congress on the Thermodynamics of Metal Complexes, Santiago de Compostela, Spain, June 2–6, 2002

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Frassineti, C., Alderighi, L., Gans, P. et al. Determination of protonation constants of some fluorinated polyamines by means of 13C NMR data processed by the new computer program HypNMR2000. Protonation sequence in polyamines. Anal Bioanal Chem 376, 1041–1052 (2003). https://doi.org/10.1007/s00216-003-2020-0

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  • DOI: https://doi.org/10.1007/s00216-003-2020-0

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