Micellar effect on quinquivalent vanadium ion oxidation of D-glucose in aqueous acid media: A kinetic study

Article abstract of DOI:10.1002/kin.20314

Vanadium(V) oxidation of D-glucose shows first-order dependence on D-glucose, vanadium(V), H⁺, and HSO₄^-. These observations remain unaltered in the presence of externally added surfactants. The effect of the cationic surfactant (i.e., N-cetylpyridinium chloride [CPC]), anionic surfactant (i.e., sodium dodecyl sulfate [SDS]), and neutral surfactant (i.e., Trion X-100 [TX-100]) has been studied. CPC inhibits the reactions, whereas SDS and TX-100 accelerate the reaction to different extents. Observed effects have been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants.

Full text of DOI:10.1002/kin.20314

Micellar Effect on
Quinquivalent Vanadium
Ion Oxidation of D-Glucose
in Aqueous Acid Media:
A Kinetic Study
1
2
1
BIDYUT SAHA, SUCHARITA SARKAR, KIRAN M. CHOWDHURY
1
Department of Chemistry, The University of Burdwan, Burdwan 713 104, West Bengal, India
Burdwan Medical College, Burdwan 713 104, West Bengal, India
2
Received 22 February 2007; revised 27 July 2007; accepted 5 December 2007
DOI 10.1002/kin.20314
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Vanadium(V) oxidation of D-glucose shows first-order dependence on D-glucose,
+
−
vanadium(V), H , and HSO . These observations remain unaltered in the presence of externally
4
added surfactants. The effect of the cationic surfactant (i.e., N-cetylpyridinium chloride [CPC]),
anionic surfactant (i.e., sodium dodecyl sulfate [SDS]), and neutral surfactant (i.e., Trion X-100
[TX-100]) has been studied. CPC inhibits the reactions, whereas SDS and TX-100 accelerate
the reaction to different extents. Observed effects have been explained by considering the
hydrophobic and electrostatic interaction between the surfactants and reactants. ꢀC 2008 Wiley
Periodicals, Inc. Int J Chem Kinet 40: 282–286, 2008
INTRODUCTION
levels [1–6] in a variety of animal models of both type
I and type II diabetes.
Demand for an understanding of the vanadium(V)
and vanadium(IV) reaction mechanisms is increasing
day by day and is mainly based on the following four
reasons.
Vanadium compounds acting in an insulin-mimetic
fashion both in vitro and in vivo is well established
The study of the mechanism of oxidation of organic
compounds by vanadium(V) [7] has applications in the
behavior of vanadium oxide catalysts and is of value
in problems concerning the possible action of transient
ions of chromium and manganese on certain oxidation
reactions by both chromic acid and potassium perman-
ganate [8].
[1–6]. Both inorganic and organic vanadium com-
pounds have been shown to lower plasma glucose
Carbohydrates are biologically important sub-
stances whose microbiological and physiological
activities largely depend on their redox behavior.
Oxidations of carbohydrates by different oxidizing
agents are of special importance due to their biological
relevance [9–13].
Correspondence to: Bidyut Saha; e-mail: b saha31@rediffmail.
com.
Contract grant sponsor: Burdwan University, Burdwan, West
Bengal, India.
ꢀ
c 2008 Wiley Periodicals, Inc.

MICELLAR EFFECT ON QUINQUIVALENT VANADIUM ION OXIDATION OF D-GLUCOSE
283
+
Vanadium(V) enhances proliferation of progenitor
cells in the adult rat subventricular zone after focal
cerebral ischemia [14].
performed keeping [H ] constant ([H SO ] + [HClO ]
2
4
4
+
= [H ]). The formation of free radical during the reac-
tion was confirmed by the induced polymerization of
acrylonitrile, whereas neither vanadium(V) nor sugar
solution alone induced polymerization.
The kinetics of vanadium(V) oxidation of differ-
ent monosaccharides in sulfuric, perchloric, and hy-
drochloric acid solutions have been studied by a large
number of researchers [15–19]. But they did not carry
out their work in micellar media, which has appeared
as a powerful probe to support the reaction mecha-
nism [20–31] for different transition metal ions; it also
behaves as a cellular membrane.
RESULTS AND DISCUSSION
Under the kinetic conditions (i.e., [S]T ꢁ [V(V)]T,
where [S]T and [V(V)]T are total substrate and vana-
dium(V) concentration, respectively), qualitative iden-
tification of the reaction products was carried out
by using paper chromatography [33–35]. Lactone of
gluconic acid [36] was confirmed as the oxidation
product. Paper chromatography was effected by using
butan-1-ol–acetic-acid–water (4:1:5) as eluent. Paper
chromatographs were visualized by two kinds of de-
veloping reagents: a three-stage dip of silver nitrate,
sodium hydroxide, and sodium thiosulfate [37] and
p-anisidine, a specific reagent for aldose detection.
The rate shows first-order dependence on the sub-
GENERAL EXPERIMENTAL PROCEDURE
Solutions were prepared in double-distilled water.
◦
The conductivity of this water at 25 C and at atmo-
−1
spheric pressure is 0.0550 µS cm . Stock solution of
D-glucose (SRL, Mumbai, India) was freshly prepared
and was stored in a refrigerator. Ammonium metavana-
date (SRL), SDS (SRL), CPC (SRL), TX-100 (SRL),
and all other chemicals used were of AR/GR grade.
Ammonium metavanadate was dissolved in the sulfuric
acid solution. The acid concentration of the stock vana-
dium(V) solution was taken as the difference between
the amount initially added and the amount consumed
by the reaction
−
+
strate concentration, HSO4 and H ions concentra-
tion (cf., Figs. 1–3). Earlier studies [7,38,39] have
indicated that the form of the active vanadium(V)
species depends on acid types and their concentration
range. It has been established by the earlier workers
+
+
+
[
7,38,39] that in aqueous sulfuric acid media (≤4.5 mol
NH4VO3 + 2H → NH + VO + H2O
4
2
−3
dm ) the kinetically active species of vanadium(V) is
+
[
V(OH)3HSO4] and the equilibrium leading to this
active species is given by [7, 38–41]
Solutions of the oxidant and reaction mixtures, con-
taining the known quantities of the substrates (S) (i.e.,
D-glucose; under the conditions [S]T ꢁ [V(V)]T), acid,
and other necessary chemicals, were separately ther-
+
+
−
4
+
VO + H3O + HSO ꢁꢀ [V(OH)3HSO4]
2
◦
mostated (± 0.1 C). The reaction was initiated by mix-
ing the requisite amount of the oxidant with the reac-
tion mixture. The concentration of the unreacted vana-
dium(V) at different time intervals was determined
titrimetrically by using the standard Mohr’s solution
in the presence of barium diphenylamine sulfonate as
the redox indicator [32]. The pseudo-first-order rate
constants (kobs) were calculated as usual. Under the
experimental conditions, the possibility of decompo-
sition of the surfactants by vanadium(V) was investi-
gated, and the rate of decomposition in this way was
found to be kinetically negligible. The pseudo-first-
order rate constants (kobs) were reproducible within
the experimental error limit. The error limit is 1%–3%,
showing that the experimental technique is a sound one.
The reaction mixtures have an excess of D-glucose to
ensure that there is no appreciable reduction in vana-
dium(V) by the product if oxidizable, and it also main-
Figure 1 Dependence of kobs on [D-glucose]T for the
◦
vanadium(V) oxidation of D-glucose at 35 C. [V(V)]T =
−
3
−3
−3
2
[
[
1
.5 × 10
mol dm , [H2SO4] = 1.8 mol dm . A:
−3
−3
−3
CPC]T = 4.0 × 10 mol dm , [SDS]T = 0 mol dm
,
−
3
TX-100]T = 0 mol dm ; B: [CPC]T = [SDS]T = [TX-
−3
−3
00]T = 0 mol dm ; C: [CPC]T = 0 mol dm , [SDS]T = 0
−3
−2
−2
−3
mol dm , [TX-100]T = 4 × 10 mol dm ; D: [SDS]T = 4
+
tains the pseudo-first-order conditions. H variation
−3
−3
×
10 mol dm , [SDS]T = [CPC]T = 0 mol dm ; where
−
was performed keeping [HSO ] constant ([H2SO4]
[CPC] , [SDS] , and [TX-100] are total CPC, SDS, and
4
T
T
T
−
−
4
+
[NaHSO4] = [HSO ]), and HSO variation was
TX-100 concentrations, respectively.
4
International Journal of Chemical Kinetics DOI 10.1002/kin

2
84
SAHA, SARKAR, AND CHOWDHURY
+
Figure 3 Dependence of kobs on [H ] for the vana-
◦
−
dium(V) oxidation of D-glucose at 25 C. [V(V)]T = 2.5 ×
Figure 2 Dependence of kobs on [HSO ] for the vana-
4
−3
−3
−3
−3
mol dm ,
◦
10
mol dm , [D-glucose]T = 60 × 10
dium(V) oxidation of D-glucose at 25 C. [V(V)]T = 2.5 ×
−3
−3
−3
−3
−3
,
[NaHSO4] + [H2SO4] = 4.5 mol dm
.
10
mol dm , [D-glucose]T = 60 × 10
mol dm
−3
[
HClO4] + [H2SO4] = 4.0 mol dm
.
range:
+
+
−
4
+
In the same way, the results obtained in higher acid
VO + 2H + 2HSO ꢁꢀ [V(OH)2(HSO4)2]
2
−3
concentration range (>4.5 mol dm ), the following
equilibria can be considered to be operative [42]
for the formation of the active species in this
The result can be explained by considering the pro-
posed mechanism (Scheme 1)
Scheme 1 Vanadium (V) oxidation of D-glucose
International Journal of Chemical Kinetics DOI 10.1002/kin

MICELLAR EFFECT ON QUINQUIVALENT VANADIUM ION OXIDATION OF D-GLUCOSE
285
◦
Table I Some Representative Pseudo-First-Order Rate Constants (kobs) at 40 C for Vanadium(V) Oxidation of
D-Glucose under Different Conditions
3
3
2
2
4
1
(
0 [D-Glucose]T
10 [CPC]T
10 [SDS]T
10 [TX-100]T
10 kobs
−1
−
3
−3
−3
−3
mol dm
)
(mol dm
)
(mol dm
)
(mol dm
)
(s
)
60
60
60
60
60
60
60
60
60
60
90
90
90
90
90
00
00
00
00
00
00
00
00
00
00
02
04
06
08
10
02
04
06
08
10
00
00
00
00
00
00
00
00
00
00
00
00
00
00
00
02
04
06
08
10
00
00
00
00
00
7.5 ± 0.2
8.7 ± 0.2
10.0 ± 0.3
11.2 ± 0.4
12.5 ± 0.4
7.0 ± 0.2
8.0 ± 0.3
9.0 ± 0.2
10.0 ± 0.3
11.0 ± 0.4
10.0 ± 0.2
8.2 ± 0.2
6.7 ± 0.15
5.8 ± 0.2
5.0 ± 0.15
1
03[V(V)]
T
= 3.0 mol dm−3 and [H
2
SO
4
] = 2.0 mol dm−3, where [V(V)]
T
is the total V(V) concentration.
+
−
Rate = k3K1K2[S]T[H ][OX][HSO ]
[20]. SDS being an anionic surfactant, owing to the
electrostatic attraction between the positively charged
4
+
−
4
=
k3K1K2[S]T[H ][OX]T[HSO ]/1
+
[
V(OH)3HSO4] species and negatively charged mi-
+
−
+
+
K1[H ][HSO ]
cellar head group, the active oxidant [V(OH)3HSO4]
easily attaches to the Stern layer of micelle. The re-
action takes place in both the micellar and aqueous
media. The observed rate acceleration is due to the fa-
vored reaction in the micellar phase, where both the
active oxidant and the substrate are preferably accu-
mulated. In the case of TX-100, the active oxidant also
attaches to the Stern layer of micelle, but the amount is
less compared to SDS because TX-100 is a neutral sur-
factant, so no electrostatic attraction takes place. CPC
is a cationic surfactant and consequently due to the
4
+
−
4
=
k3K1K2[S]T[H ][OX]T[HSO ]
+
−
(
where K1[H ][HSO ] ꢂ 1)
4
The pseudo-first-order rate constants (kobs) in the pres-
ence of various concentrations of different types of
surfactants, SDS (sodium dodecyl sulfate, a representa-
tive anionic surfactant), CPC (N-cetylpyridinium chlo-
ride, a representative cationic surfactant), and TX-100
Trion X-100, a neutral surfactant), are presented in
Table I.
The data reveal that SDS and TX-100 accelerate the
rate, whereas CPC decreases the rate. Rate acceleration
is higher in the case of SDS than TX-100. This can be
explained by Scheme 2.
The substrate is partitioned in the Stern layer of
the micellar phase. Partitioning of the D-glucose in
the Stern layer has been noticed by earlier workers
(
electrostatic repulsion between the positively charged
+
[
V(OH)3HSO4] species and positively charged micel-
+
lar head group, the active oxidant ([V(OH)3HSO4] )
does not attaches to the Stern layer of micelle through
the substrate. The reaction takes place only in aqueous
media, which is depleted in the substrate concentration.
We thank Burdwan University, Burdwan, West Bengal, India,
for laboratory support and Prof. Asim K. Das, Visva-Bharati
University, for his helpful discussion.
BIBLIOGRAPHY
1. Orvig, C.; Thompson, K. H.; Battell, M.; McNeill, J. H.
Met Ions Biol Syst 1959, 31, 575–594.
Scheme 2 Partitioning of the reactive species between the
aqueous and micellar phases
2. Boden, G.; Chen, X.; Ruiz, J.; Van Rossum, G. D.; Turco,
S. Metabolism 1996, 45, 1130–1135.
International Journal of Chemical Kinetics DOI 10.1002/kin

2
86
SAHA, SARKAR, AND CHOWDHURY
3
. Goldfine, A. B.; Patti, M. E.; Zuberi, L.; Goldstein,
B. J.; Le Blance, R.; Landaker, E. J.; Jiang, Z. Y.;
Willsky, G. R.; Kahn, C. R. Metabolism 2000, 49, 400–
21. Saha, B.; Islam, M.; Das, A. K. Prog React Kinet Mech
2005, 30, 145–156.
22. Saha, B.; Islam, M.; Das, A. K. J Chem Res (S) 2005,
471–474.
410.
4
5
. Crans, D. C. J Inorg Biochem 2000, 80, 123–131.
. Wilsky, G. R.; Goldfine, A. B.; Kostyniak, P. J.; McNeill,
J. H.; Yang, L. Q.; Khan, H. R.; Crans, D. C. J Inorg
Biochem 2001, 85, 33–42.
23. Bayen, R.; Islam, M.; Saha, B.; Das, A. K. Carbohydr
Res 2005, 340, 2163–2170.
24. Islam, M.; Saha, B.; Das, A. K. J Mol Catal: A Chem
2005, 236, 260–266.
6
7
8
9
. Facchini, D. M.; Yuen, V. G.; Battel, M. L.; McNeill,
J. H.; Grynpas, M. D. Bone 2006, 38, 368–377.
. Waters, W. A.; Littler, J. S. J Chem Soc 1959, 3014–
25. Kabir-ud-Din; Ali, M. S.; Khan, Z. Indian J Chem A
2005, 44, 2462–2469.
26. Panda, J.; Panigrahi, G. P. J Indian Chem Soc 2002, 79,
58–61.
27. Swain, R.; Panigrahi, G. P. Indian J Chem A 2001, 40,
1191–1195.
28. Islam, M.; Saha, B.; Das, A. K. Int J Chem Kinet 2006,
38, 531–539.
3019.
. Turney, T. A. Oxidation Mechanism; Butterworths:
London, 1965; pp. 102–109.
. Sala, L. F.; Cirelli, A. F.; de Lederkren, R. M. J Chem
Soc, Perkin Trans 2 1977, 685–688.
1
1
1
1
0. Gupta, M.; Saha, S. K.; Banerjee, P. J. Chem. Soc.,
29. Saha, B.; Islam, M.; Das, A. K. Inorg React Mech 2006,
6, 141–149.
30. Islam, M.; Saha, B.; Das, A. K. J Mol Catal: A Chem
2007, 266, 21–30.
31. Saha, B.; Pal, K. K. Prog React Kinet Mech 2005, 30,
283–291.
32. Littler, J. S.; Waters, W. A. J Chem Soc 1959, 1299–
1305.
Perkin Trans 2 1988, 1781–1785.
1. Barek, J.; Berka, A.; Pokorna- Hladikova, A. Collect
Czech Chem Commun 1982, 47, 2466–2477.
2. Signorella, S.; Civllo, L.; Lafarga, R.; Sala, L. F. New J
Chem 1996, 20, 989–991.
3. Ribeiro, A. C. F.; Lobo, V. M. M.; Valente, A. J. M.;
Simoes, S. M. N.; Sobral, A. J. F. N.; Ramos, M. L.;
Burrows, H. D. Polyhedron 2006, 25, 3581–3587.
4. Matsumoto, J.; Morioka, M.; Hasegawa, Y.; Kawano, T.;
Yoshinaga, Y.; Maeda, T.; Yano, S.; Kai, Y.; Fukunaga,
K.; Kuratsu, J. J Pharmacol Exp Ther 2006, 318, 982–
33. Sengupta, K. K.; Basu, N. N. Carbohydr Res 1980, 80,
223–232.
1
34. Sala, L. F.; Signorella, S. R.; Rizzotto, M.; Frascaroli,
M. I.; Gandolfo, F. Can J Chem 1992, 70, 2046–2052.
35. Rizzotto, M.; Frascaroli, M. I.; Signorella, S. R.; Sala,
L. F. Polyhedron 1996, 15, 1517–1523.
36. Buchanan, J. G.; Dekker, C. A.; Longo, A. G. J Chem
Soc 1950, 3162–3167.
9
91.
5. Kumar, A.; Mehrotra, R. N. J Org Chem 1975, 40, 1248–
252.
6. (a) Sen Gupta, K. K.; Sen Gupta, S.; Mandal, S. K.
Carbohydr Res 1985, 139, 185–190; (b) Sen Gupta,
K. K.; Sen Gupta, S.; Mandal, S. K. 1986, 145, 193–
1
1
1
37. Travelyan, W. E.; Procter, D. P.; Harrison, J. S. Nature
1950, 166, 444–451.
2
00.
38. Jones, J. R.; Waters, W. A. J Chem Soc 1963, 352–356.
39. Shankar, R.; Joshi, S. N. Indian J Chem 1963, 1, 289–
291.
1
1
1
2
7. Virtanen, P. O. I.; Lindross- Heinanen, R. Acta Chem
Scand B 1988, 42, 411–413.
8. Virtanan, P. O. I.; Kurkisuo, S.; Nevala, H.; Pohjola, S.
Acta Chem Scand A 1986, 40, 200–206.
9. Khan, Z.; Kabir-ud-Din. Int J Chem Kinet 1999, 31,
40. Saccubai, S.; Santappa, M. Indian J Chem 1970, 8, 533–
535.
41. Sengupta, K. K.; Chakladar, J. K.; Pal, B. P.; Mukherjee,
D. C. J Chem Soc, Perkin II 1973, 7, 926–929.
42. Mehrotra, R. N. J Chem Soc B 1968, 642–644.
409–415.
0. Das, A. K. Coord Chem Rev 2004, 248, 81–99.
International Journal of Chemical Kinetics DOI 10.1002/kin