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Chemistry and Physics of Vanillin

Chaim Frenkel, Professor


Department of Plant Biology and Pathology
Rutgers-the State University of New Jersey
New Brunswick, NJ 08901-8520
(732) 932-9711 x 365
(732) 932-9441
fax
<frenkel@aesop.rutgers.edu>

Cross section of vanilla bean showing a dark central cavity


(seeds) surrounded by vanillin forming cells.

O
C

O
H

OCH3
O
H

Hydrophobicity
of the aromatic ring

OCH3

OCH3
O
H

Hydrogen bonds
(intra and intermolecular)

O
H

Reactivity
of a carbonyl group
(Maillard Reaction)

Molecular features of vanillin, including hydrophobicity, efficacy


for forming hydrogen bonds and reactive carbonyl group, which
could influence the fate of vanillin during various handling stages.

- stacking of aromatic rings. This phenomenon, stemming


from the hydrophobicity of aromatic compounds contributes
to the tendency of vanillin to form aggregates.

Inter and Intra Hydrogen Bonds in Crystalline Vanillin*

O
C

CH3

CH3
O

O
O

H
O
C

CH3
O
O
H

* Adapted from: Aihara A (1973) A study of hydrogen bonds in Vanillin I.


Denki Tsaushin Daigaku 24:71-75

20O C
100

40O C

50O C

Percent Vanillin

80

60

60O C

40

20

80O C
0
0

10

20

30

40

50

Days

Rate of disappearance of dry vanillin held at atmospheric


pressure and at different temperatures.

0O C, 20O C

100

40O C

40O C

Percent Vanillin

80
50O C
60

60O C

40

20
60O C

80O C
0
0

10

12

14

Time (days)

Rate of disappearance of dry vanillin held at 0.1 atmospheric


pressure and at different temperatures.

100

Percent Vanillin

80

60

40

1.0 atmospheric pressure

20

0.1 atmospheric pressure


0
20

30

40

50

60

70

80

Temperature (OC)

Disappearance of vanillin held at 1.0 or 0.1 atmospheric pressure.


Vanillin was held for 18 and 4 days at 1.0 or 0.1 atmospheric pressure,
respectively. The data shows that vanillin disappearance is greatly
accelerated above 40o C.

vanillin

methanol

290

10

M vanillin

280

270

260

ml Methanol after 24 hours

250

10

20

30

40

50

60

Temperature ( O C)

Vanillin content solubilized in 100% methanol


and held for 24 hours at different temperatures.
The data shows that while methanol is volatilized
vanillin remains in solution.

water
vanillin

10

8
270
6
230
4

ml Water

Vanillin Content (M)

310

190
2
150

10

20

30

40

50

60

70

80

Temperature (OC)

Vanillin content solubilized in water and held for


48 hours at different temperatures. The data shows
That disappearance of vanillin is correlated to the
rate of water disappearance.

vanillin

340

10

M Vanillin

320

310
4

300

10

20

30

40

50

60

70

Remaining Volume of Liquid (40% methanol)

methanol (40%)

Temperature (OC)

Vanillin content solubilized in 40% methanol-water


solution and held for 2 days at different temperatures.
The data shows that presence of water caused some
disappearance of vanillin.

O
C

H
CH3
O

O
H

HEAT

C H

CH3
O
O

O
H

WATER

CH3

O
C

O
CH3
O

CH3

O
H

O
O
H

A hypothetical scheme indicating that hydration of vanillin,


due to vanillin-water hydrogen bonding, leads to the
volatilization of vanillin-water complex.

11

KOH
NaOH

10
9
8

pH

7
6
5
4
3

1000

2000

3000

4000

5000

6000

mole KOH or NaOH

Titration curve of vanillin in water.


The data shows that native vanillin is acidic and,
moreover, exhibits a substantial buffering capacity.

10

8
2.6
6
2.2

ml Water

Vanillin Content ( mole)

3.0

4
1.8

water

vanillin pH 8.0
vanillin pH 6.5

1.4

10

20

30

40

50

60

70

80

Temperature (OC)

Vanillin content in water, adjusted to pH 6.5 or 8.0 and held


for 48 hours at different temperatures. Disappearance of vanillin
is function of solubility (greater at pH 8.0 that 6.5, above 40o C).

3.4

3.0

6
2.6

ml Water

Vanillin Content ( mole)

10

4
water
vanillin pH 2.0
vanillin pH 3.0

2.2

10

20

30

40

50

60

70

Temperature (OC)

Vanillin content in water, adjusted to pH 3.0 or 2.0 and held


for 48 hours at different temperatures. Disappearance of vanillin
is function of solubility (greater at pH 3.0 that 2.0, above 30o C).
Lower levels of vanillin at pH 3.0, below 30o C, reflect precipitation
of the compound in the aggregate state.

A schematic view of water structure showing a tight intermolecular arrangement created by hydrogen bonding of
neighboring water molecules.

Solute cavity in water showing disengagement of water


structure to accommodate a guest molecule (middle) *
* Martnez JM, Pappalardo RR., Marcos ES, Mennucci B,

Tomasi J (2002) Analysis of the Opposite Solvent Effects Caused


by Different Solute Cavities on the Metal-Water Distance of Monoatomic Cation Hydrates. J Phys Chem B 106:1118-1123

Maillard Reaction
Inhibitors

Promoters

Cl Br I

ClO4 SCN

Li+ Na+

K+ Rb+ Cs+ NH4+

Water Structure
Makers
(Kosmotropes)

Water Structure Breakers


(Chaotropes)

Some ions, which enhance or diminish the structure of water.


Water structure-breaking ions are presumed to enhance the
solubility and, thereby, the chemical reactivity of vanillin.

Schiff's base formation

C=O + H2NR

HO

Carbinolamine

H
C=O + H2NR

HO

H
C

Carbinolamine

Aldose

R + HOH

HO C H

HO C H

HO C H

+ HOH

H C OH

H C OH

H C OH

Schiff's base

H
C

Schiff's base

Amadori Rearrangement

H
C

H
C

HC OH

H
N

C OH

HO C H

H
HC

HO C H

HO C H

Schiff's base

1-amino-2-keto sugar

Sciff's base Hydrolysis


C

RNH 3

HOH + H

In acid medium Schiff's base will undergo hydrolysis

A generalized scheme of Maillard Reaction showing Schiff base


formation followed by Amadori Rearrangement, leading to further
degradation including formation of brown color.

CsCl

OD 420 nm

0.5

0.4

0.3

0.2

LiCl

0.1

20

40

60

80

100

Concentration of CsCl or LiCl (mM)

Rate of Maillard reaction occurring between vanillin and


lysine in presence of varying concentrations of water structurebreaking ions (CsCl) or water structure-maker ion (LiCl).
Solutions containing 5 mM vanillin and lysine adjusted to pH 6.5, held at

65o C for 2 days. Brown pigment formation estimated by spectroscopy.

Visualization of Maillard reaction for vanillin and lysine occurring


in absence or presence of varying concentrations of water structurebreaking ions (CsCl) or water structure-maker ion (LiCl).

Summary
Conditions, which increase the water solubility of vanillin
(alkalinity or chaotropic agents) enhance water co-volatility
and chemical reactivity of the compound.

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