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Short Communication
Microwave-assisted alkaline modification
of red seaweed galactans
Diego A Navarro, Carlos A Stortz*
Departamento de Qumica Organica-CIHIDECAR, Facultad de Ciencias Exactas y Naturales, UBA, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Abstract
The production of 3,6-anhydrogalactose units from galactose 6-sulfated residues by alkaline treatment is an important reaction undergone
by many red seaweed galactans, used commercially to enhance their gelation behavior, and thus their industrial value. A novel technique
utilizing microwave irradiation to carry out the alkaline modification of three structurally different galactans is described. The reaction is
accelerated several times with respect to that performed with conventional heating. The effect of the sodium hydroxide concentration was
investigated, showing a higher rate around a 2 M base concentration.
q 2005 Elsevier Ltd. All rights reserved.
In recent years an increasing number of papers reporting (Stortz & Cerezo, 1993). The porphyran was retrieved
the use of microwave irradiation to speed up chemical from the seaweed Porphyra columbina as reported
reactions have appeared (Gabriel.et al., 1998; Lidstrom (Navarro & Stortz, 2003;; Noseda et al., 2000). The
et al., 2001; Stadler et al., 2002)some of them applied to polysaccharides were characterized by reported procedures
polysaccharides (Kunlan et al., 2001; Singh et al., 2003; (Stortz & Cerezo, 1993, 2000; Stortz, Bacon, Cherniak, &
Zhou et al., 2004). It was shown that the heating Cerezo, 1994). In order to proceed with the reactions, the
mechanisms are different in conventional and microwave polysaccharides were reduced with NaBH4 and recovered
ovens (Gabriel et al., 1998; Lidstrom et al., 2001). Recently, by dialysis and lyophilization. In a typical reaction, 20 mg
an extraction procedure for carrageenan aided by micro- of reduced polysaccharide in 10 ml of NaOH of the desired
wave heating was published (Uy, Easteal, Farid, Keam, & concentration were allowed to react for the period indicated
Conner, 2005). In the present work, we report a study of the above. No additional sodium borohydride was added to the
microwave-assisted alkaline modification (with a domestic reaction vessel to avoid production of hydrogen inside the
microwave oven) of three different red seaweed galactans, oven. The modified polysaccharides were recovered after
achieving a complete cyclization of 6-sulfated units very dialysis (molecular weight cut-off 60008000) and
rapidly and with no signs of degradation. lyophilization.
b-Gal sulfated on Yield (%) Final ratio A/Ga Microwave Half-lifeb (min) Conventional
reaction time (min) reaction time
(min)c
Cd C-4 82.9 1.00 0.5 4.5 120180
Porphyran 96.4 0.90 1.0 23 180300
l-Carrageenan C-2 87.6 0.85 8.0 117170 960
a
Ratio 3,6-anhydrogalactose/galactose in the final product. For porphyran, the ratio 3,6-AnGal/(GalC6-O-Me-Gal) is reported.
b
Half-life by conventional heating at 80 8C in 1 M NaOH (Ciancia et al., 1993; Noseda et al., 2000).
c
Usual reaction time by conventional heating (Navarro & Stortz, 2003).
d
Partly cyclized m/n-carrageenan (Stortz & Cerezo, 1993).
190 D.A. Navarro, C.A. Stortz / Carbohydrate Polymers 62 (2005) 187191
40
% 3,6-AnGal (molar)
30
20
10
0
0.0 0.5 1.0 0.0 0.5 1.0 1.5 0 2 4 6 8 10
Time (min) Time (min) Time (min)
Fig. 4. 3, 6-Anhydrogalactose generated by microwave heating at different times of reaction using 2 M NaOH. (a) Partly cyclized m/n-carrageenan C, (b)
porphyran, and (c) l-carrageenan T1.
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