Isomerization of cholecalciferol through energy transfer as a protective mechanism against flavin-sensitized photooxidation

Regina S Sccurachio; Willy G. Santos; Eduardo S.P. do Nascimento; Leif Horsfelt Skibsted; Daniel R Cardoso

doi:10.1021/jf505958c

Isomerization of cholecalciferol through energy transfer as a protective mechanism against flavin-sensitized photooxidation

Regina S Sccurachio, Willy G. Santos, Eduardo S.P. do Nascimento, Leif Horsfelt Skibsted, Daniel R Cardoso

Food Chemistry

3 Citations (Scopus)

Abstract

Cholecalciferol, vitamin D₃, was found to isomerize to 5,6-trans-vitamin-D₃ with a quantum yield of 0.15 ± 0.01 in air-saturated 7/3 tert-butyl alcohol/water (v/v) at 25 °C, increasing to 0.32 ± 0.02 in the absence of oxygen, through quenching of triplet excited state flavin mononucleotide, FMN, rather than becoming oxidized. The quenching was found by laser flash photolysis to have a rate constant of 1.4 × 10⁸ L mol^-1 s^-1 in 7/3 tert-butyl alcohol/water (v/v) at 25 °C, assigned to energy transfer from ³FMN∗ to form a reactive vit.D₃ diradical. vit.D₃ forms a 1/1 precomplex with FMN by hydrophobic stacking with ΔH° = -36 ± 7 kJ mol^-1 and ΔS° = -4 ± 3 J mol^-1 K^-1, as shown by single photon counting fluorescence spectroscopy and steady-state fluorescence spectroscopy. Both ground-state precomplex formation and excited-state energy transfer seem important for vit.D₃ protection against flavin-sensitized photooxidation of nutrients in food and biological systems.

Original language	English
Journal	Journal of Agricultural and Food Chemistry
Volume	63
Issue number	18
Pages (from-to)	4629-4637
Number of pages	9
ISSN	0021-8561
DOIs	https://doi.org/10.1021/jf505958c
Publication status	Published - 13 May 2015

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Isomerization of cholecalciferol through energy transfer as a protective mechanism against flavin-sensitized photooxidation. / Sccurachio, Regina S; Santos, Willy G.; do Nascimento, Eduardo S.P. et al.
In: Journal of Agricultural and Food Chemistry, Vol. 63, No. 18, 13.05.2015, p. 4629-4637.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Isomerization of cholecalciferol through energy transfer as a protective mechanism against flavin-sensitized photooxidation",

abstract = "Cholecalciferol, vitamin D3, was found to isomerize to 5,6-trans-vitamin-D3 with a quantum yield of 0.15 ± 0.01 in air-saturated 7/3 tert-butyl alcohol/water (v/v) at 25 °C, increasing to 0.32 ± 0.02 in the absence of oxygen, through quenching of triplet excited state flavin mononucleotide, FMN, rather than becoming oxidized. The quenching was found by laser flash photolysis to have a rate constant of 1.4 × 108 L mol-1 s-1 in 7/3 tert-butyl alcohol/water (v/v) at 25 °C, assigned to energy transfer from 3FMN∗ to form a reactive vit.D3 diradical. vit.D3 forms a 1/1 precomplex with FMN by hydrophobic stacking with ΔH° = -36 ± 7 kJ mol-1 and ΔS° = -4 ± 3 J mol-1 K-1, as shown by single photon counting fluorescence spectroscopy and steady-state fluorescence spectroscopy. Both ground-state precomplex formation and excited-state energy transfer seem important for vit.D3 protection against flavin-sensitized photooxidation of nutrients in food and biological systems.",

author = "Sccurachio, {Regina S} and Santos, {Willy G.} and {do Nascimento}, {Eduardo S.P.} and Skibsted, {Leif Horsfelt} and Cardoso, {Daniel R}",

year = "2015",

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doi = "10.1021/jf505958c",

language = "English",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Isomerization of cholecalciferol through energy transfer as a protective mechanism against flavin-sensitized photooxidation

AU - Sccurachio, Regina S

AU - Santos, Willy G.

AU - do Nascimento, Eduardo S.P.

AU - Skibsted, Leif Horsfelt

AU - Cardoso, Daniel R

PY - 2015/5/13

Y1 - 2015/5/13

N2 - Cholecalciferol, vitamin D3, was found to isomerize to 5,6-trans-vitamin-D3 with a quantum yield of 0.15 ± 0.01 in air-saturated 7/3 tert-butyl alcohol/water (v/v) at 25 °C, increasing to 0.32 ± 0.02 in the absence of oxygen, through quenching of triplet excited state flavin mononucleotide, FMN, rather than becoming oxidized. The quenching was found by laser flash photolysis to have a rate constant of 1.4 × 108 L mol-1 s-1 in 7/3 tert-butyl alcohol/water (v/v) at 25 °C, assigned to energy transfer from 3FMN∗ to form a reactive vit.D3 diradical. vit.D3 forms a 1/1 precomplex with FMN by hydrophobic stacking with ΔH° = -36 ± 7 kJ mol-1 and ΔS° = -4 ± 3 J mol-1 K-1, as shown by single photon counting fluorescence spectroscopy and steady-state fluorescence spectroscopy. Both ground-state precomplex formation and excited-state energy transfer seem important for vit.D3 protection against flavin-sensitized photooxidation of nutrients in food and biological systems.

AB - Cholecalciferol, vitamin D3, was found to isomerize to 5,6-trans-vitamin-D3 with a quantum yield of 0.15 ± 0.01 in air-saturated 7/3 tert-butyl alcohol/water (v/v) at 25 °C, increasing to 0.32 ± 0.02 in the absence of oxygen, through quenching of triplet excited state flavin mononucleotide, FMN, rather than becoming oxidized. The quenching was found by laser flash photolysis to have a rate constant of 1.4 × 108 L mol-1 s-1 in 7/3 tert-butyl alcohol/water (v/v) at 25 °C, assigned to energy transfer from 3FMN∗ to form a reactive vit.D3 diradical. vit.D3 forms a 1/1 precomplex with FMN by hydrophobic stacking with ΔH° = -36 ± 7 kJ mol-1 and ΔS° = -4 ± 3 J mol-1 K-1, as shown by single photon counting fluorescence spectroscopy and steady-state fluorescence spectroscopy. Both ground-state precomplex formation and excited-state energy transfer seem important for vit.D3 protection against flavin-sensitized photooxidation of nutrients in food and biological systems.

U2 - 10.1021/jf505958c

DO - 10.1021/jf505958c

M3 - Journal article

C2 - 25891983

SN - 0021-8561

VL - 63

SP - 4629

EP - 4637

JO - Journal of Agricultural and Food Chemistry

JF - Journal of Agricultural and Food Chemistry

IS - 18

ER -

Isomerization of cholecalciferol through energy transfer as a protective mechanism against flavin-sensitized photooxidation

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