Formation of hydroxymethyl-furfural and hydroxymethylfuroic acid in foods

M. Murkovic

Graz University of Technology

Institute of BiochemistryFunctional Food Group

EUROPEAN

COMMISSION

FOOD QUALITY AND SAFETY

Food and Chemical Toxicology 46 (2008) 3697–3702

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

Furane

2-Methyl-3-oxo-THF

Furfural

Furfurylalkohol

5-Methylfurfural

2-Furanmethanol-acetate

Furane derivatives in roasted foods

Roasting temperature: 220 °C

Erich Leitner, TU Graz

Perez-Locas, Yaylayan, 2008

Proposed mechanism of thermal generation of glucose,

levoglucosan, and fructofuranosyl cation,

showing percent contribution of glucose and fructose

moieties to HMF formation at 350 °C and 65 °C

Formation of HMF from C3 units

O

OH

OH

OH

OH

OH O

OH

OIsomerization

-H2O

glycerol-aldehyde methyl-glyoxal

glycerol-aldehyde

methyl-glyoxal

HMF

O

OH

OH

O

OH

OO

OHO+-2 H2O

Cämmerer et al., 2009

OH

O

CH2

OHH

OHH

CH2

OH

OH

O

H

OHH

CH2

OH

H

OOH O

O

O

CH2

OH

OH

OH

O

CH2

CH2

CH2

OH

O

NOH O

R

N

R

O

CH2

OHdidesoxy-triketo

RNH2HMF-Formation

Acid catalyzed formation of HMF

O

OH

OHOHOH

OH

OOH O

Fructose

H+/-3H2O

HMF

HMF with different acids, 254 nm

0

2

4

6

8

10

12

14

0 1 2 3 4 5

Time (h)

Co

nce

ntr

atio

n (

ug

/ml)

NaH2PO4

Citric acid

Without

Fumaric acid

Tartaric acid

Maleic acid

Acetic acid

Oxalic acid

Model system: 0.1 M amino acid + carbohydrate

Chromatogram of HMFRP, 280 nm

Retention time (min)

0 1 2 3 4 5 6

UV

-Abs

orpt

ion

Dryed fruit

Standard

Coffee

Formation of HMF in apple juice(90 °C)

Heating time (min)

0 50 100 150 200

HM

F (

µg/

mL)

14

16

18

20

22

24

26

28

Foods with a high content of HMF (1)

HMF

(mg/kg)

n HMF

(mg/kg)

n

Apricot 30, 780 2 Date 1000 1

Pear 100 1 Fig 1 1

Peach 40 1 Pineapple 280 1

Plum 1600, 2200 2 Apple 80 1

Plum jam 1100, 1200 2 Fruit bread 450 1

Coffee (roasted, ground) 300 - 1900 22

Foods with a high content of HMF (2)

HMF (mg/L) n

Sherry 2 – 320 3

Port 40 – 60 5

Balsamico 190 – 3400 9

White wine 0.3 - 4 35

Formation of HMF in Madeira-wine

Storage time (years)

0 2 4 6 8 10 12 14 16

HM

F in

win

e (µ

g/m

L)

0

100

200

300

400

500

600

700

sweet half-sweet dry extra-dry

Formation kinetics of HMF and HMFA in arabica and robusta coffee

Roasting time [min]

0 2 4 6 8 10

HM

F a

nd

HM

FA

[µ

g/g

]

0

50

100

150

200

900

HMFA in arabica HMF in robustaHMFA in robustaHMF in arabica

arabicamodel-arabica

robustamodel-robusta

HM

F a

nd H

MF

A [M

ol%

]

0,0

0,5

1,0

1,5

2,0

2,5

3,0

HMFAHMF

Formation of HMF and HMFA in coffee and the model system

Proposed mechanism of HMFA formation in model systems

CH

CH

CH2

O

HO

HO

CH3

C

COHO

O

CH2

CH

HCCH

C O

COHO

HO

HO

OHO

O

OHaldol-condensation(-H2O)

ketalisation(-H2O)

Formation of HMF and HMFA during roasting of coffee

Roasting time [min]

0 2 4 6 8 10

HM

F [µ

g/g

]

0

100

200

300

400

500

600

700H

MF

A [µ

g/g

]

0

20

40

60

80

100

120

140

160

180

200

HMFHMFA

Industrial roastinglo

w me

dium

hig

h

Formation of HMF and HMFA in model systems

HM

F a

nd H

MF

[mm

ol/m

ol]

0

10

20

30

40 HMF HMFA

met

hylg

lyox

algl

ycer

alde

hyde

glyc

eral

dehy

de +

pyr

uvat

e

met

hylg

lyox

alpy

ruva

te

pyru

vate

met

hylg

lyox

al

glyc

eral

dehy

de

equimolar mixtures pure substances

Co-workers

• Kristina Bagdonaite

• Draxl Sigrid

• Derler Karin

• Maria Bornik

• Pichler Nicole

• Daniela Jöbstl

• Alam Zeb

• H. Günther – Kraft Foods Bremen