"KNETICS AND OXIDATON OF SUGAR

(SUCROSE) IN ACIDIC AND ALKALINE

MEDIUM"
-ARTI MISHRA [M.Sc.-IV SEM, DSMNRU]

ABSTRACTS
1-Kinetics and Mechanistic Study of Permanganate Oxidation of L-
Citrulline in Acidic and Basic Media (DEC-2016):
Kinetics of oxidation of L-citrulline (Cit) by permanganate ion in both acidic and basic
media has been investigated spectrophtometrically at constant ionic strengths and at 25°C.
In both media the reactions exhibited first order dependence in [permanganate] and less
than unit order dependences in L-citrulline concentration. A fractional-second order
dependence with respect to [H+] and a fractional-first order dependence with respect to
[OH-] were revealed in acidic and basic media, respectively. Increasing ionic strength in
basic medium increased the oxidation rate of L-citrulline, whereas it had a negligible effect
on the oxidation rate in acidic medium. The rate-determining step in both media is
suggested to involve a one-electron change, but the stoichiometry (L-citrulline:
permanganate) was different, being 5:2 in acidic medium and 1:2 in basic medium. The
proposed oxidation mechanisms involve formation of 1:1 intermediate complexes between
kinetically active species of both L-citrulline and permanganate ion in pre-equilibrium
steps. The final oxidation products of L-citrulline were identified in both acidic and basic
media as the corresponding aldehyde (4-(carbamoylamino) butyraldehyde), ammonia and
carbon dioxide. The appropriate rate laws are deduced
2- Kinetics and mechanism of oxidation of L-sorbose and sucrose with
potassium permanganate in acedic medium by spectrophotometry
(APRIL-2016):
The oxidation of L- sorbose and sucrose with permanganate ion ( KMnO4) as oxidant
was observed in acidic medium by visible spectrophotometric method in the temperature
range (300-320) K. The reaction exihibit first oder kinetics with respect to change in
concentration of L- sorbose, sucrose, MNO4- and H+ followed by the change in
absorbance of oxidant at 546 nm. Negligible effect of ionic strength (µ) on the rate of
oxidation has also be noted which supports the presence of at least one neutral species in
the rate determining step. The various activstion parameters have been calculated. A
suitable mechanism consistent with experimental finding has been proposed.
3- Kinetics and Mechanism of Oxidation of Sucrose by N-
Bromonicotinamide NBN (2015):
Kinetics study of oxidation of sucrose, by aqueous alkaline solution of N-
Bromonicotinamide (NBN) has been carried out in the temperature range 308-323K.The
reaction exhibits first order in [NaOH] and [Sucrose] and zero order about oxidant.
Addition of nicotinamide (NA) has no effect. Increase in ionic strength of the medium
does not change the rate. Effect of temperature on the rate of oxidation has been followed
to show the validity of Arrehenius equation and various activation parameters have been
computed. The stoichiometry of the reaction was found to be 1:1. 1,2-enediol is found to
be the reactive intermediate. Arabinonic acid, glycolic acid and formic acid are the
products of oxidation.
4-Enzyme Cascade for Catalyzing Sucrose Oxidation in a Biofuel Cell
(2013):
Biofuel cells provide a safe and renewable means of powering small electronic devices. In
this work, we demonstrate a bioanode that is capable of extracting 4 electrons from a
single molecule of sucrose by way of a three-enzyme cascade. Invertase, fructose
dehydrogenase and glucose oxidase are immobilized in a ferrocene-modified linear
poly(ethylenimine) (LPEI) hydrogel onto the surface of a carbon electrode. Fuel sources
are generated in the polymer film by (1) hydrolyzing sucrose into fructose and glucose and
then (2) electroenzymatically oxidizing fructose and glucose to produce a current response.
A previously unreported synergistic effect is observed between glucose oxidase and
fructose dehydrogenase that results in a current response that is considerably higher than
expected. The newly described enzyme cascade generated 302 ± 57 μA/cm2 at 25 °C and
602 ± 62 μA/cm2 at 37°C and when poised against an air breathing platinum cathode in a
biofuel cell, the multienzyme-containing film generated 42 ± 15 μW/cm2 at 172 mV with a
maximum current density of 344 ± 25 μA/cm2 in 100 mmol/L sucrose at 25 °C. This is the
first example of an enzymatic biofuel cell that utilizes both fructose and glucose as
oxidation fuel sources.
楋敮楴獣愠摮洠捥慨楮浳 景漠楸慤楴湯漠 牦捵潴敳愠摮搠氭捡潴
敳戠⁹数浲湡慧慮整椠湯椠 湡愠楣楤⁣敭楤浵㉛ 崲
The oxidations of D-fructose and D-lactose were monitored spectrophotometrically by
potassium permanganate in acidic medium at λmax 545 nm. Reaction demonstrated that
the two oxidative species of permanganate were involved in an acidic oxidation of the
sugars. It was established that respective acids of sugars as well as arabinonic and formic
acid were the oxidation products. Respective acids of sugars were the results of reactive
oxygen species of permanganate ions in acidic conditions while arabinonic and formic
acids due to the cleavage of C-C bond through MnO4- species. It was first order kinetics
with respect to [MnO4-], [fructose], [lactose] and [H+]. Hg was used to accelerate the slow
oxidation of lactose. Effect of varying salt electrolyte concentration was insignificant
showing that the molecular species was involved in the rate determining step. Formic and
arabinonic acids and respective acids were analyzed through spot and spectroscopic
studies respectively. Reaction was monitored at different temperatures and
thermodynamics activation parameters were determined. A mechanism consistent with
kinetic studies, spectral evidences, stoichiometry of the reactions and product analysis has
been proposed for the oxidation of fructose and lactose in absence and presence of catalyst
respectively.
6-Kinetics and mechanism of oxidation of nicotinic acid by potassium
permanganate in aqueous acidic medium (2012):
The stoichiometry and kinetics of oxidation of nicotinic acid by potassium permanganate
has been investigated in aqueous acidic medium at 28±1oC, I = 0.5 mol dm-3 (Na2SO4),
[H+] = 1x10-1 mol dm-3. The results obeys the rate law -d[C6H5NO2]/dt = (a+b[H+])
[C6H5NO2] [MnO4-]
where a = 0.016 dm3mol-1s-1, b = 1.57 dm6mol-1s-1
The rate of reaction decreased with increase in ionic strength. Added cations and anions
catalysed the reaction. The result of spectroscopic and kinetic investigation did not
indicate intermediate complex formation because there was no change in λmax at 525nm.
A plausible mechanism has been proposed for this reaction

传敤畢浮 湡⁤ 传慷畬敤⠠‶慊畮牡⁹〲
The kinetics of oxidation of glucose, galactose, fructose, maltose and sucrose by alkaline
permanganate anion has been studied. The reactions studied spectrophotometrically over a
wide range of experimental conditions show that the rate of the reactions is enhanced by
increase in pH, ionic strength, and temperature as well as the reactant concentrations. The
mechanism has been proposed to proceed via the formation of enediol intermediate
complexes and the order of reactivities of the sugars is fructose > glucose > galactose >
maltose > sucrose. The activation parameters were evaluated and lend further support to
the proposed mechanism.

8-KINETICS OF OXIDATION OF FRUCTOSE, SUCROSE AND

MALTOSE BY POTASSIUM PERMANGANATE IN NAHCO3/NAOH
BUFFER AND IRIDIUM(IV)COMPLEX IN SODIUM
ACETATE/ACETIC ACID BUFFER (DEC-2006):
The kinetics of oxidation of fructose, sucrose and maltose by potassium permanganate in
alkaline buffer and of fructose and sucrose by hexachloroiridate (IV) in acidic buffer have
been measured spectrophotometrically under pseudo-first-order conditions. The rates of
oxidation of the sugars follow the order maltose > fructose > sucrose, and increase with
pH in both acidic and alkaline media. Alkaline KMnO4 is a more powerful oxidizing agent
for the oxidation reactions than acidic Ir(IV) complex, and each oxidation reaction was
first order with respect to oxidant and sugar concentrations. Although sugar oxidation by
alkaline KMnO4 is independent of salt concentration, the same reaction by Ir(IV) in acidic
media may depend on salt concentration. The Arrhenius activation energy and other
thermodynamic activation parameters are reported and the results are interpreted on the
basis of the formation of a 1:1 intermediate complex.
9-Electrocatalytic oxidation of sucrose: analysis of the reaction
products(JANUARY-1997):
The analysis of sucronic acids produced by the electrocatalytic oxidation of sucrose is
described. The main reaction products, l′-monocarboxylic and 6-monocarboxylic acids of
sucrose, were identified by means of gas and liquid chromatography, mass spectrometry,
NMR and i.r. spectroscopy, and acid hydrolysis. The quantitative analysis of reaction
products other than the sucronic acids was realized by ionic chromatography (Dionex),
whereas that of the sucronic acids was carried out using their acid hydrolysis products
10-The periodate oxidation of sucrose in aqueous N,N-dimethylformamide
(1995):
Sucrose has been oxidized with sodium periodate in 0–50% aqueous N,N-
dimethylformamide (DMF). In 50% aqueous DMF the reaction is selective for the glucose
ring, yielding a dialdehyde. The increased selectivity is not due to conformational factors
but is ascribed to the dissociation of water from cyclic periodate ester species which makes
the reaction via the acyclic ester on fructose unfavourable.

11-Platinum Catalysed Oxidation of Sucrose(JAN-1991):

The platinum catalyzed oxidation of sucrose by oxygen has been studied. With platinum
on carbon at 100°C and at constant neutral pH, the oxidation is highly specific for the
primary hydroxyls at the 6- and 6′-positions of sucrose. There was no evidence of
oxidation of the 1′ hydroxyl. The 6,6′-dicarboxysucrose was resistant to attack by
invertase. The 6- and 6′-carboxysucroses could not be resolved from each other, but the
former component was hydrolysed rapidly by invertase and subsequently the 6′-carboxy
sucrose was isolated. The C spectrum of 6-carboxysucrose was then assigned by difference

12-Bromine oxidation of and sucrose(JANUARY-1980):

Sucrose and (1) were oxidised with bromine in aqueous solution at pH 7 and room
temperature. The resulting keto derivatives were converted into their more-stable O-
methyloximes, which were characterised by spectroscopic and chromatographic methods.
Oxidation of 1 occurred at C-3 and C-5, with a preference for C-5. In the sucrose
derivatives isolated after oxidation, those having a keto group in the glucopyranosyl
moiety preponderated. The axial fructofuranosyl aglycon protects position 3 in the
glucopyranosyl group and oxidation occurs only at C-2 and C-4. Small amounts of sucrose
oxidised at C-3 in the fructofuranosyl moiety were also found.