Bio Bullet in (2015), Vol. 1(1): 34-39, Walia and Gupta 34
ISSN NO. (Print): 2454-7913ISSN NO. (Online): 2454-7921
Periodate oxidation of Ceiba pentandra and Morus nigrapurified non-cellulosic polysaccharides
Yogesh Kumar Walia* and Dinesh Kumar Gupta**
*Department of Chemistry, School of Basic & Applied Sciences,Career Point Univers ity, Hamirpur (H. P.) , INDIA
**Department of Chemistry, Govt. M. V. M., Bhopal , (M. P.) , INDIA
(Corresponding author: Yogesh Kumar Walia)(Publ ished by Research Trend, Website: www.biobul let in.com)
(Received 12 March 2015; Accepted 08 June 2015)
ABSTRACT: Periodate oxidation reaction is used in carbohydrate chemistry and isalso applicable to wood polysaccharides. Periodic acid is mainly capable ofcleaning alpha and beta glycols quantitat ively from wood polysaccharides.Compounds containing an aldehyde or ketonic group adjacent to an alcoholicgroup are also attacked by periodic acid in similar manner as glycols. Theestimation of the periodic acid used and the formic acid or formaldehyde producedwill indicate the number, in pairs, of free oxidizable groups (-CHOH, -CHO or =CO).Since periodic acid can easily be estimated volumetrically, oxidations with H 5 IO6 ,or HIO4 .2H2O are very useful in analytical chemistry.
Keywords: Periodate oxidat ion; oxidizable groups; non-cel lulosic polysacchar ides;Ceiba pentandra and Morus nigra.
In this study non-cel lulosicpolysacchar ides (hemicel luloses) 7 , 2 3 & 2 4of Ceiba pentandra and Morus nigra7 & 1 3
are used to study their per iodateoxidat ion. Per iodate oxidat ion react ionwas f irs t discovered by Malaprade 2 , whoobserved that per iodic acid is capable ofc leaning alpha and beta glycolsquant i tat ively f rom wood polysacchar ides.The c is-glycols attacked more rapidly thanthe trans-glycol but both glycols yield twoaldehydes, if more than two adjacent -CHOH groups are present, they areconverted into formic acid.Fluery and Lange have given a bettermethod for more extensive use of per iodicacid for oxidat ion of glycol, specif ic for 1,
2-diols also given var ious c lear ingreagents, part icular ly per iodic acid andlead tetra acetate. These reagents exhibitrelat ively sharp eff ic iency for thecleavage of bonds between adjacentcarbon atoms containing hydroxyl groups.Chatterjee et al., Kumar 5 and Sarkar etal.6 have used the per iodate oxidat ionmethod to determine the structure ofpolysacchar ides, this oxidat ion reagenthas the fol lowing required propert ies : thesuitable diameter of central atom ofoxidat ion reagent is about 2.5 to 3.010 -8cm, because this is capable to be largeenough to br idge the gap between thehydroxyl groups in a 1,2-diol ; the centralatom of oxidat ion reagent must be able tocoordinate at least two hydroxyl groups,
Bio Bulletin 1(1): 34-39(2015)(Published by Research Trend, Website: www.biobulletin.com)
Bio Bullet in (2015), Vol. 1(1): 34-39, Walia and Gupta 35
inspite of groups already attached to i t ;the valancy state of central atom must beexceeded by two units rather than by oneor three valancy of next lowest stablestate; the oxidat ion reagent must haveoxidat ion potent ial in the neighborhood -1.7 Volts as compared to the next loweststable valancy state and Periodic acid8spl i t 1,2 glycols and one molecule of acidis used for each pair of adjacent alcohol icgroups.Compounds containing an aldehyde orketonic group adjacent to an alcohol icgroup are also attacked by per iodic acidin s imilar manner as glycols. Thus analdopentose if i t had an open chainstructure would require four molecules ofper iodic acid and the products would befour molecules of formic acid and onemolecule of formaldehyde (f rom theterminal -CH2OH group). The est imation9
of the per iodic acid used and the formicacid and or formaldehyde produced wil lindicate the number, in pairs, of f ree
oxidizable groups ( -CHOH, -CHO or =CO).Since per iodic acid can easi ly beest imated volumetr ical ly, oxidat ions withH5 IO6 , or HIO4 .2H2O are very useful inanalyt ical chemistry.The amount of per iodic acid consumedcan easi ly be determined by t i t rat ionagainst a standard iodine solut ion.Simultaneously, the react ion products,viz. HCHO, HCOOH etc. are est imatedand thus we may know the completestructure5 of the compound.Mechanism of periodate oxidation:Oxidat ion1 0 with ortho-per iodic acid iscarr ied out in neutral or faint ly roomtemperature.The react ion proceeds through a cycl icintermediate either hydrate ion I ordehydrate ion I I.Glycol groups undergo cycl ic esterformation with the oxidant. The react ion isconsidered to be aldehyde type ofoxidat ion11 .
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MATERIALS AND METHODS
The method proposed by Fleury andLange1 2 was used for per iodate oxidat ionof non-cel lulosic polysacchar ides(hemicel luloses) of Ceiba pentandra andMorus nigra . The dr ied pur if iedhemicel lulose7 of both samples wereweighed about 0.1450 gm and suspendedin 250 ml of 0.02M sodium meta-per iodatesolut ion. The measur ing f lask was shakento form a col loidal solut ion which was keptin dark, in refr igerator and at lowtemperature range of 10 to 15 0 C. Fromthis 5.0 ml react ion mixture solut ion wasdrawn at intervals using Arsenite method
and est imated the excess of per iodate.The Arsenite method is as fol lows - Toeach al iquote 2.0 ml saturated solut ion ofsodium bicarbonate was added than about25.0 ml of 0.01N sodium arsenite solut ionand 2.0 ml of 20% potassium iodide wereadded. The react ion mixture was shakenand kept in dark for about 15 minutes andthen 5.0 ml of 0.01N solut ion of iodinewas added to i t . Then the excess of iodinewas t i trated against 0.1N hypo solut ion,0.1N starch was used as indicator nearthe end point. Paral lel a blank t it rat ionwas also made in s imilar way.
Moles of periodate consumed per anhydrose unit = N (V2 V1) 132 X A. F.1000 w 2Here: N = Normality of thio sulphate solut ion; V 2 = Volume of thio used with blank;V1 = Volume of thio used with sample and w = Weight of hemicel lulose (on O.D.basis) A. F.= Total Volume of periodate takenPeriodate volume withdrawn for each titrationRESULTS AND DISCUSSION
The exper iment descr ibed as above onapplying for the dr ied pur if ied
hemicel luloses of both Ceiba pentandraand Morus nigra and results so obtainedare recorded in Table 1 and Table 2.
Bio Bullet in (2015), Vol. 1(1): 34-39, Walia and Gupta 37
Table 1: Periodate consumption per anhydrose sugar unit of hemicelluloses ofCeiba pentandra .
Volume of thioused with blank
Volume of thioused with sample
Volume of thiosolution used
(V2 - V1) ml
Mole of iodateconsumed peranhydrose unit
mole.16.0 10.55 10.27 0.28 0.6124.0 10.55 10.24 0.31 0.6832.0 10.55 10.22 0.33 0.7248.0 10.55 10.19 0.36 0.7972.0 10.55 10.15 0.40 0.8896.0 10.55 10.11 0.44 0.96
120.0 10.55 10.05 0.50 1.10168.0 10.55 10.05 0.50 1.10216.0 10.55 10.05 0.50 1.10
Table 2: Periodate consumption per anhydrose sugar unit of hemicelluloses ofMorus nigra .
Time ofoxidation (hrs)
Volume of thioused with blank
Volume of thioused with sample
Volume of thiosolution used
(V2 V1) ml
Mole of iodateconsumed peranhydrose unit
mole16.0 10.55 10.31 0.24 0.5224.0 10.55 10.29 0.26 0.5732.0 10.55 10.27 0.28 0.6148.0 10.55 10.25 0.30 0.6672.0 10.55 10.23 0.32 0.7096.0 10.55 10.20 0.35 0.77
120.0 10.55 10.17 0.38 0.83168.0 10.55 10.17 0.38 0.83216.0 10.55 10.17 0.38 0.83
A graph has also been plotted againstamount of oxidant consumed in thereact ion and the t ime of oxidat ion asgiven in Figure 1 for pur if iedhemicel lulose of Ceiba pentandra andMorus nigra . From data recorded inTables 1 and 2 and the results obtainedby the analysis of data as well asobservat ions made from Fig . 1, it isevident that the moles of per iodateconsumption increases from 0.61 to 1.10and 0.52 to 0.83 by increasing the t ime ofoxidat ion from 16 to 120 hrs but i tbecomes constant f rom 120 to 216 hrs atthe values 1.10 and 0.83 of Ceibapentandra and Morus nigra respect ively. I tis also observed that moles of per iodateconsumption (1.10) of Ceiba pentandra isl i t t le higher than the value of Morus nigra
(0.83). The results of per iodate oxidat ionalso indicate that the structure of non-cel lulosic polysacchar ide is l inear orbranched. These results for Ceibapentandra indicate the presence of l inearstructure because a straight chain withsmall amount of branched glucomannan,l inked at 1 4(), would consume 1.10mole of per iodate for each anhydrohexose sugar and the same results ofMorus nigra indicate the presence ofl inear structure because a straight chainxylan, l inked 1 4(), would consume0.83 mole of per iodate for each anhydro -D-xylose units, plus an extra mole of eachand of the chain. In long, straight chainsthe effects of end groups is diminishedand per iodate consumption approachesone mole per mole of polysacchar ide.
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Fig. 1: Periodate consumption per anhydrose sugar unit of hemicel luloses.
This study also shows that non-cel lulosicpolysacchar ide contain adjacent freehydroxyl groups (because consumption ofper iodate ions dur ing oxidat ion react ion).But the approximate 8% of pur if iedhemicel lulose of Ceiba pentandra notcontain adjacent free hydroxyl groups, itis indicat ing the small amount ofbranching. These results show similar i tywith the results of Negi, Singh and J indal,Guha et al , Shukla, Hussain et al ,Shatalov et al . , Lundquist et al. andWillfor and Holmbom 22 .
The structure of non-cel lulosicpolysacchar ide is either l inear orbranched and the results for Ceibapentandra indicate the presence of l inearstructure because a straight chain withsmall amount of branched glucomannan,l inked at 1 4(), would consume 1.10mole of per iodate for each anhydrohexose sugar and the same results ofMorus nigra indicate the presence ofl inear structure because a straight chainxylan, l inked 1 4(), would consume0.83 mole of per iodate for each anhydro -
D-xylose units, plus an extra mole of eachand of the chain. In long, straight chainsthe effects of end groups is diminishedand per iodate consumption approachesone mole per mole of polysacchar ide.
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1.1 1.1 1.1
0.83 0.83 0.83
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220Time of oxidation (hrs)
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