thermochimica

acta
ELSEVI ER Thermochimica Acta 294 (1997) 71-79
Me c h a n i c a l and t he r mal anal ys i s o f rai si n c o mp o n e n t s l
D. M. R. Ge o r g e t , M. Gu a r d o , A. Ng, A. C. Smi t h*, K. W. Wa l d r o n
Institute of Food Research, Norwich Laboratory,, Colney, Norwich NR4 7UA, UK
Abs t r ac t
Moisture content is known to change the mechanical properties of raisins. The progressive chemical removal of cell
components was carried out to assess their contribution to the overall raisin properties. It was achieved by preparing an alcohol
insoluble residue which was then sequentially extracted and its carbohydrate composition analysed. The removal of structure
and geometry effects was undertaken by pressing uniform mouldings of the raisin and its insoluble components, which were
conditioned over saturated salt solutions at room temperature. Dynamic mechanical thermal analysis (DMTA) of the
mouldings indicated their decreasing stiffness with increasing temperature as well as the occurrence of the glass transition,
which was complemented by Differential scanning calorimetry (DSC). The data from DSC and DMTA were interpreted in
terms of contributions from the raisin cell-wall components and sugars and showed the glass transitions of the cell-wall
polymers to be consistent with published results on grapes and wood. ~) 1997 Elsevier Science B.V.
Keywords: DSC; DMTA; Raisin; Cell wall; Glass transition
1. I n t r o d u c t i o n been revi ewed [8], but recent l y Sa and Sereno [9] have
taken a bi opol ymer sci ence appr oach and measur ed
Various propert i es of raisins have been studied, the moi st ure dependence of the glass transition of
r angi ng f r om their di et ary fibre cont ent [1], charact er- grapes by DSC. Bi opol ymer i c mat eri al s have been
isation of t he pect i c subst ances [2], their sorpt i on i ncreasi ngl y studied over the past decade usi ng DSC
i sot herms [3,4] to their mechani cal propert i es [5,6]. [10,11]. Ot her t echni ques such as DMTA have also
Lewi cki and Wol f [7] used a compr essi on- r el axat i on been used and studies have i ncl uded wood, proteins,
test descri bed in [5], and vari ous specific t erms deri ved starches, pol ysacchari des, sugars and vari ous mi xt ures
f r om it, to measure the effect of moi st ure cont ent [12,13]. Exci sed plant tissue has also been studied in
changes. Canel l as et al. [6] consi der ed the effect of recent experi ment s at this l aborat ory [14]. The com-
st orage t i me on raisins hel d at di fferent t emperat ures, position, structure and geomet r y of fruit and veget abl e
They measur ed changes in mechani cal propert i es by tissue compl i cat es their mechani cal anal ysi s in terms
t he mass- nor mal i sed War ner - Br at zl er force. Studies of stress and strain units, whi ch are necessary for
of the preparat i on of raisins f r om the native grape have model l i ng. One appr oach whi ch has been useful in
si mpl er process-fabri cat ed structures has been to
r emove the structure and si mpl i fy the geomet r y by
pressi ng test pi eces of uni f or m geomet r y [15]. Thi s
*Corresponding author. Fax: 01603 507723; e-mail: andrew.
smith@bbsrc.ac.uk, appr oach had earlier been demonst r at ed for si mpl e
1Presented at the First UK National Symposium on Ther mal bi opol ymer s [16]. However, in deal i ng with plant
Analysis and Calorimetry, Leeds, 17-18 April 1996. material, anal ysi s of their composi t i on is a c0mpl i -
0040-6031/97/$17.00 4) 1997 Elsevier Science B.V. All rights reserved
PI I S0040- 603 1 (96)031 46- 2
72 D.M.R. Georget et al./Thermochimica Acta 294 (1997) 71-79
cated issue since extraction techniques may introduce 2.2. Sample preparation
artefacts through the labile nature of the component s.
Sequential cell-wall analysis has been devel oped in 2.2.1. Preparation ofalcohol-insoluble residue (AIR)
this laboratory [ 17,18] and in this study has been used Whol e raisins, skin and flesh were extracted for an
to partition the various classes of cell-wall compo- AI R as described by Martin-Cabrejas et al. [17].
nents. Samples were homogeni sed in a Waring blender with
This paper reports a study of the effect of moisture boiling ethanol (85% v/v final concentration) for
content on the mechani cal properties of raisins and 2 min and then homogeni sed with an Ystral homo-
their component s with the objective of identifying the geniser for 1 min before boiling for 5 rain. The homo-
basis of their moi st ure-dependent texture. Raisins genat e was filtered through 100 lam nylon mesh. The
were exami ned in whole and also when separated into residue was re-extracted twice in boiling ethanol (85%
skin and flesh. The progressive chemical removal of v/v), and twice in boiling ethanol (100%). The final
cell component s was achieved by preparing an alco- residue was washed three times with acetone and air-
hol-insoluble residue which was then sequentially dried overnight.
extracted using treatments devel oped in this labora-
tory. The progressive chemi cal removal of cell corn- 2.2.2. Sequential extraction of AIR
portents enabled a study of the contribution of the The sequential extraction was carried out according
insoluble residues to the mechani cal properties of the to the met hod of Redgwell and Selvendran [18]
whole raisin. Each material was equilibrated at dif- (Fig. 1). AI R (65.4 g) from whole raisins was sus-
ferent relative humidities, using saturated salt solu- pended in wat er for 2 h at 20C. The water-insoluble
tions at room temperature, to generate sampl es of residue (WIR) was extracted sequentially with 50 mM
different moisture contents. Differential scanning cycl ohexane-t rans-l , 2-di ami ne-N, N, N' , N' -t et raace-
cal ori met ry (DSC) was carried out to classify transi- rate (CDTA, Na salt) pH 6.5 for 6 h at 20C (CDTA- 1)
tions for equilibrated and sealed specimens. The and 2 h at 20C (CDTA-2), then 50 mM Na2CO3
removal of structure and geomet ry effects was under- containing 20 mM NaBH4 for 6 h at I C (Na2CO3-
taken by pressing uniform mouldings of the raisin and 1) and 2 h at 20C (Na2CO3-2); and then 0.5 M KOH
its excised fractions and the sequentially extracted containing 20 mM NaBH4 to leave a KOH-i nsol ubl e
insoluble component s, which were then also condi- residue (KOHIR). After each extraction the soluble
tioned to different moisture contents. Dynami c component s were filtered through glass fibre paper
mechani cal thermal analysis (DMTA) was used to GF/ C (Whatman), neutralised where required, dia-
obtain the stiffness of the test pieces as a function lysed exhaustively and freeze-dried. Small aliquots
of temperature. The data from DSC and DMTA were of residue (10%) from each step of the sequential
interpreted in t erms of contributions from the raisin extraction were also neutralised, dialysed exhaustively
component s, and a compari son made with published and lyophilised; these were then used to fabricate
results on grapes and wood. speci mens for DMTA.
2.3. Compositional analysis
2. Ma t e r i a l s a n d me t h o d s
2.3.1. Sugar analysis f rom cell wall material
2.1. Materials The neutral sugars were analysed following the
met hod described by Selvendran et al. [19] using a
Sun-dried seedless raisins (cv Thompson) were Carl o Erba gas liquid chromatograph. The monosac-
obtained. Whol e raisins were separated into their skin charides released by acid hydrolysis were reduced and
and flesh by using t weezers and a blade. Whol e raisins, anal ysed as alditol acetates. The separations were
skin and flesh were frozen i mmedi at el y in liquid N2 carried out on a 3 m 2.2 mm col umn containing
and stored at - 4 0 C until required. The average 3% OV-225 at 200C in ~45 min.
weights of whole raisin, skin and flesh were 0.48 g, The uronic acids were det ermi ned colourimetri-
0.12 g and 0.36 g respectively, cally, according to the met hod of Bl umenkrant z and
D.M.R. Georget et al . / Thermochi mi ca Acta 294 (1997) 71-79 73
Hot Alcohol (85%) ~ Alcohol Soluble Component s
~ (Cell wall material)
Water ~ Water Soluble Polysaccharides (WSP)
~ (Cell wall wi t hout wat er
sol ubl e pol ysacchari des)
CDTA ~ CDTA Soluble Polysaccharides (CSP-1,2)
CDTA I ns ol ubl e Re s i due (CIR-1,2) [(Cell wall wi t hout ionic
(6h, 2 0 " C/ 2 h 20*C) [ cross-l i nked pect i nsl
Na2CO 3 ~ Na2CO3 Soluble Polysaccharides (NSP- 1,2)
Na2CO 3 I ns ol ubl e Re s i due (NIR- 1,2) (Cell wall without esterified
(6h, I*C) ( 2h 20"C) pectins)
............... K OH . . . . . . . . . . . ] . . . . . I, 7 ? ? o l u b ~ Polysaccharldes NNeuU~a~ SO~cUibli~tKeOHgSH)p)
. . . . . . ..... (Mainly cellulose)
Fig. 1. Sequential extraction of raisin AIR.
As boe- Hans en [20] modi fi ed by Sel vendran et al. Moi st ure upt ake was measur ed by wei ghi ng the
[19,21 ] usi ng a Per ki n- El mer spect romet er, sampl es before and duri ng humi di fi cat i on until the
equi l i bri um has been obt ai ned.
2.3.2. Determination of moisture content
A vacuum oven was utilised to det ermi ne the 2.5. Sample preparation by hot press f or DMTA
moi st ure cont ent of skin and flesh at 70C as a funct i on measurements
of time, as used by ot hers for raisins [8,22]. Thi s
was shown to be t he most effect i ve t emperat ure in 2.5.1. Hot press
t he present work. Values were al so obt ai ned by The hot press was made up of a rect angul ar moul d
Karl Fi scher titration met hod [23], carri ed out ri ng bet ween t wo compact i on dies, as descri bed in
usi ng an AF7LC Coul omet r i c Ti t rat or Orion. The detail el sewhere [15]. The t emperat ure was cont rol l ed
moi st ur e cont ent was cal cul at ed on wet wei ght basis by a devi ce compr i si ng a heat i ng and a cool i ng
% (wwb). syst em. Each die was cover ed wi t h an acetate sheet
and ~ 1.5 g of the powder pl aced bet ween the dies. A
2.4. Conditioning at different relative humidities rect angul ar sheet, 28 mm l ong and 22 mm wide, was
obt ai ned and cut into strips. The sampl es were con-
Raisins ( ~ 1. 8- 4 g) were condi t i oned over saturated di t i oned at di fferent relative humi di t i es and their wat er
salt sol ut i ons at r oom t emperat ure. Each test was cont ent s det ermi ned as descri bed above.
carri ed out in duplicate. The f ol l owi ng salts were
used: P205 (aw = 0), Li CI (aw = 0. 113), 2.5.2. Sample preparation
MgCI 2- 6H20 (aw = 0. 328), K2CO3 (aw = 0. 432), Raisins were cut in small pi eces and dried in a hot
NaCI (aw = 0. 753), and KC1 (aw ---- 0. 843) [24]. box oven at 80C for 17 or 19 h and reduced t o powder
74 D.M.R. Georget et al./Thermochimica Acta 294 (1997) 71-79
wi t h a mor t ar and pestle. The same pr ocedur e was 30
used to obt ai n powder f r om skin and flesh. The
mat eri al was pressed as descri bed earlier wi t h a .Q
pressure o f 35 kN at 100C f or 15 min.
20:
Two di fferent met hods were tested in order to make g
sampl es of t he AI R, WI R and KOHI R f or DMTA. The
powder was gr ound usi ng a coffee gri nder to r educe
the part i cl e size and used di rect l y or when hydr at ed to ~ o
50- 70% (wwb). The same pressi ng condi t i ons as ~ I 0
above were appl i ed except t hat the t emperat ure was .~
50C, and the resul t i ng sheet was cut and condi t i oned
as descri bed in t he previ ous section.
I I I I I r I I r I I I I I I
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
2.6. Differential scanning calorimetry (DSC) Wat er acUvity/aw
For this study, whol e raisins were t est ed and when Fig. 2. Sorption isotherm of raisins.
separat ed i nt o skin and flesh. A powder was obt ai ned
and condi t i oned t o di fferent moi st ure cont ent s as
descri bed in the previ ous paragraphs. DSC anal yses
wer e carri ed out usi ng a Per ki n- El mer DSC 2 cal ori - 17.2% (wwb), respectively, as measur ed by the
meter. Each sampl e, ,,~5 mg, was accur at el y wei ghed Karl -Fi scher met hod whi ch was shown to provi de
and sealed her met i cal l y in an al umi ni um pan. An good agr eement wi t h a vacuum oven t reat ment at
empt y pan was used as the reference. Sampl es were 70C. The wat er-absorpt i on i sot herm is shown in
heat ed at a rate of 10C mi n 1, sensitivity 4. 18 mJ Fig. 2. The shape of this cur ve is report ed to be
(1 mcal ) s - ]. charact eri st i c of hi gh sugar foods, such as raisin whi ch
cont ai n ~ 7 0 % sugars on wet basis [4]. At l ow wat er
2.7. DMTA act i vi t y t he moi st ur e cont ent was low. The hi gh wat er
cont ent obser ved at hi gh rel at i ve humi di t y was due to
The dynami c mechani cal t hermal anal yzer (Pol y- the di ssol ut i on of the sugars [4]. At zero wat er act i vi t y
mer Laborat ori es) ( DMTA) was used wi t h the sampl e the moi st ure cont ent was ~ 5 % wwb, si mi l ar t o a val ue
in the si ngl e cant i l ever bendi ng mode at a f r equency of of 8% report ed by Lewi cki and Wol f [7]. The moi st ure
1 Hz and a strain of x/ 2 cor r espondi ng t o a nomi nal cont ent s (wwb) of the residues were: AI R - 6%, WI R
peak- t o- peak di spl acement of 23 ~tm to measure stiff- - 2%, and KOHI R - 2%.
ness. The heat i ng rat e was 2C mi n -~. The sampl es
wer e t ypi cal l y -,~28 mm long, 6 t o 7 mm wi de and 0. 9 3.2. AIR; carbohydrate composition
t o 1.6 mm t hi ck after condi t i oni ng to di fferent moi st -
ure cont ent s. The yi el d of AI R (fresh wei ght ) f r om whol e raisins,
skin and flesh was 6, 8, and 6%, respectively. The
car bohydr at e r ecover y of whol e raisins, skin and flesh
3. Res ul t s was 48, 28, and 45%, respect i vel y; the r emai nder
havi ng compr i sed i nt racel l ul ar prot ei n whi ch will
3.1. Conditioning results and water-absorption have co-preci pi t at ed wi t h the AI R duri ng ext ract i on
isotherm [l 7]. The car bohydr at e composi t i ons of whol e, skin
and flesh AI Rs were similar; in addi t i on to cel l ul osi c
The moi st ur e vari at i on of each sampl e changed gl ucose, t hey were ri ch in pect i c pol ysacchar i des as
rapi dl y duri ng t he first 10 days, f ol l owi ng whi ch little i ndi cat ed by t he levels of rhamnose, arabinose, gal ac-
changes were observed. The moi st ure cont ent s f or t ose and uroni c aci d (UA). They al so cont ai ned rela-
whol e raisin, skin and flesh wer e 16.0, 15.9, and tively l ow amount s of xyl ose and mannose.
D.M.R. Georget et al./Thermochimica Acta 294 (1997) 71-79 75
Table 1
Sequential extraction of raisins AIR
Recovery (%) Carbohydrate (mol%) Total (~rn/mg)
Rha Fuc Ara Xyl Man Gal Glc UA
AIR (100) 2 0 7 4 3 5 36 43 477
WSP (3) 2 25 4 3 25 7 33 424
WIR 07) 2 9 6 3 4 31 45 494
CSP-1 (7) 2 4 1 0 3 1 91 853
CIR-I (90) 3 10 7 3 5 43 29 442
CSP-2 (5) 3 7 1 0 3 2 84 170
CIR-2 (85) 2 9 7 3 4 40 33 472
NSP-I (4) 3 14 1 0 5 1 76 546
NIR-I (81) 2 9 8 4 5 49 23 442
NSP-2 ( 1 ) 4 18 1 0 7 3 67 398
NIR-2 (80) l 8 8 4 4 49 24 442
KOHNS (5) 1 6 42 4 8 22 14 587
KOHNP (20) 4 0 25 4 2 6 10 50 126
KOHIR (55) 2 0 8 4 4 4 59 19 537
Rha - rhamnose; Fuc - fucose; Ara - arabinose; Xyl - xylose; Man - mannose; Gal - galactose; Glc - glucose; UA - uronic acid.
AIR - alcohol-insoluble residue; WSP - water-soluble polysaccharides; WIR - water-insoluble residue; CSP - CDTA-soluble
polysaccharides; CIR - CDTA-insoluble residue; NSP - Na2CO3-soluble polysaccharides; NIR - Na2CO3-insoluble residue; KOHNS -
KOH-soluble polysaccharides - neutral soluble; KOHNP - KOH-soluble polysaccharides - neutral precipitate; KOHIR - KOH-insoluble
residue.
3.3. Sequent i al ext ract i on o f AI R wa l l s o f ol i ve (Ol ea europaea; [25]). At e a c h s t age o f
e xt r a c t i on, t he i ns ol ubl e r e s i due d e mo n s t r a t e d a cor -
Ce l l - wa l l p o l y me r s we r e e xt r a c t e d s e que nt i a l l y r e s pondi ng d e c r e a s e i n t he s ugar s s ol ubi l i s ed. Th e
f r o m t he wh o l e r ai s i n AI R us i ng t e c h n i q u e s wh i c h fi nal r e s i due wa s r i ch i n c e l l ul os i c gl uc os e , but al so
mi n i mi s e p o l y me r d e g r a d a t i o n [18]. I ni t i al e xt r a c t i on c o n t a i n e d s i gni f i c a nt pe c t i c ma t e r i a l as i ndi c a t e d by
i n wa t e r s ol ubi l i s e d p o l y me r s wh i c h we r e not c r os s - t he UA c o mp o n e n t .
l i nke d i nt o t he c e l l wal l . Subs e que nt l y, C DT A r e l e a s e d
p o l y me r s c r os s - l i nke d vi a Ca 2+ onl y. Th e Na2CO3 3.4. Di f f erent i al scanni ng cal ori met ry DSC
t r e a t me nt s s ol ubi l i s e d p o l y me r s by de - e s t e r i f i c a t i on
a nd 0. 5 M KOH e xt r a c t e d p o l y me r s wh i c h we r e pr ob- Re s ul t s obt a i ne d f or t he wh o l e r ai si ns, ski n and
abl y r e t a i ne d i n t he cel l wa l l by s t r ong es t er l i nka ge s f l esh c o n d i t i o n e d t o di f f e r e nt moi s t ur e c ont e nt s ar e
[18]. s h o wn i n Fi g. 3.
Th e p o l y me r s e xt r a c t e d by wat er , CDT A and
Na2CO3 we r e p r e d o mi n a n t l y pe c t i c i n nat ur e 3.5. Hot press and DMTA
( Tabl e 1). Th e wa t e r - s o l u b l e p o l y me r s c o n t a i n e d
h i g h e r l e ve l s o f g a l a c t o s e and a r a bi nos e c o mp a r e d It wa s di f f i cul t t o obt a i n r e p r o d u c i b l e DMT A
wi t h t he CDT A and Na z CO3 - s o l u b l e p o l y me r s , i ndi - scans f r om bl oc ks o f f l esh or wh o l e r ai s i ns , pos s i bl y
c a t i ng a h i g h e r l e ve l o f br a nc hi ng. Mo s t o f t he 0. 5 M b e c a u s e o f t he hi gh s ugar cont ent s . Re s ul t s f r om
KOH- s o l u b l e p o l y s a c c h a r i d e pr e c i pi t a t e d on neut r a- r ai s i n ski n bl oc ks ar e s hown i n Fi g. 4. Th e DMT A
l i s at i on ( KOH- NP ) , and c o n s i s t e d o f pe c t i c p o l y me r s s cans o f t he AI R, WI R and KOH r e s i due s a mpl e s
wi t h a s i gni f i c a nt neut r al c o mp o n e n t . I n cont r as t , t he f a br i c a t e d wi t h wa t e r a dde d t o t he r e s i due s s h o we d t he
p o l y me r s s ol ubi l i s e d by 0. 5 M KOH wh i c h r e ma i n e d be ndi ng mo d u l u s ( U) t o d e c r e a s e wi t h i nc r e a s i ng
s ol ubl e on ne ut r a l i s a t i on ( KOH- NS ) , we r e r i ch i n t e mpe r a t ur e ( Fi gs . 5- 7) . Da t a f r om t est s on t he s a m-
xyl os e , g l u c o s e a nd UA, i ndi c a t i ng a mi x t u r e o f xyl a n, pi es f a br i c a t e d di r e c t l y f r om t he r e s i due s we r e i nho-
x y l o g l u c a n and pe c t i c p o l y me r s . Co mp l e x e s o f t he s e mo g e n e o u s and por ous and g a v e l o we r mo d u l i as
p o l y s a c c h a r i d e s pe c i e s h a v e be e n i de nt i f i e d i n cel l e xpe c t e d.
7 6 D . M . R . G eor get et al . I T her mochi mi ca A cta 294 ( 1997) 71- 79
. . . . - . . . . . . . . . . . . .
3. 5 . . . - ' "
.o
o,
. o
. o
3 . ' " " " ' "
, . . . . . . . . . - .
2 . 5 : : . " " T.:'-:" :'~" ..'.-~_ . . . . . .
: 1 1 " 7 . . . . . . . . . . . . . . . .
,
o .... i ~i ." . . . .
. . . . . . . " . . z f f - . ' ; ' - ' - ' - ' - ' ; " ""
0. 5
. . . . i . . . . i , i i i i , , , , i . . . . i . . . . i . . . . i . . . . i . . . . i , , , , i . . . . i . . . . i , . .
2 3 0 2 4 0 2 5 0 2 6 0 2 7 0 2 8 0 2 9 0 3 0 0 3 1 0 3 2 0 3 3 0 3 4 0 3 5 0
Temperat ure, K
F i g . 3 . D S C s c a n s f o r r a i s i n s a t m o i s t u r e c o n t e n t s ( i n % w w b ) : w h o l e ( . . . . ) - 1 . 9 a n d ( - . - ) - 6 . 4 ; s k i n ( - - - ) - 1 . 6 a n d ( - - - - ) - 6 . 5 ; a n d
f l e s h ( ) - 2 . 8 a n d ( . . . . ) - 6 . 7 .
1 0 . 2 "
9 . 9 -
. . . . .
8 . 7 '
~ 8.4.
~ 8 . 1 .
~ 7. a,
7 . 5 .
7 . 2 -
- 8 0 - 9 - 8 - 7 - 3 6 - 2 5 - 1 4 8 1 9 3 0
T e m p e r a t u r e ( ' C )
F i g . 4 . D M T A E + o f r a i s i n s k i n b l o c k ( - - - ) - 3 . 7 , ( ) - 5 . 5 , a n d ( - - - ) - 6 . 7 % ( w w b ) .
4 . D i s c u s s i o n i n t he rai s i n D S C r e s p o n s e . Ho w e v e r , i t w a s di f f i c ul t t o
obt ai n r e p r o d uc i bl e D MT A s c a ns f r o m bl o c k s o f f l e s h
Pr e l i mi n a r y D S C s c a n s o n r e s i d ue s w e r e f e at ur e - or w h o l e r ai s i ns , p o s s i bl y be c a u s e o f t he hi g h s ug ar
l e s s , i ndi c a t i ng t he d o mi n a n c e o f t he s ug ar c o mp o n e n t c o n t e n t s . Wat e r has a p l a s t i c i s i n g e f f e c t o n al l s y s t e ms
D.M.R. Georget et al . / Thermochi mi ca Act a 294 (1997) 71-79 77
lO.O I f . 2 4 10.0- .24
9, 8 .22 9. 8- .22
. . ...' .20 .20
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . t . 1 8
9. 4- """' . . . . . . . . . - ' " : : ~ - . 16 ~ 9. 4" - . . . . . ~ . . . . . . ,16
g ..::>CI"" " - . -.14 ~ = . . . . . . . . . . . . . . . . . . . . . . . . 14
9 . 2 " . . " : " ' ' . ~ ~ - . . . . o 9 . 2 "
90 . .... / - m ~ ~ 9. 0 . . . . . . . . . . . . . . . " ...... ~o '~
:~ 8.8.
8.8- ; ....... . " -.o8 ~ ~ "" .08
8 8 ..................... ";"" -08 ~ 86 .. ~ 08
.04 "...,.. .-" ............... " .04
8. 4 " .02 8. 4' .02
-80 ~d4 -~8 -;~ -1'6 ; 1'6 ;2 ~8 d4 80 -80 -~ -~8 -~2 -;6 0 1'~ ;2 ~8 d4 80
Temper at ur e { 'CI Temper at ur e { 'C)
Fi g. 5. DMT A E' a n d t a n 6 o f AI R b l o c k at ( - - - ) - 5. 5, ( ) Fi g. 7. DMT A E r a n d t a n 6 o f KOHI R b l o c k at ( - - - ) - 1. 6,
- 10. 9, a n d ( - - - ) - 14. 4% ( wwb ) . Ar r o ws i ndi c a t e a p p r o p r i a t e ( ) - 16. 0, a n d ( - - - ) - 2 0 . 1 % ( wwb ) . Ar r o ws i ndi c a t e
s cal e, a p p r o p r i a t e s cal e.
! 10000
i 0. 0 ] .24 0
I
.22 0
9.8 O
.2o ~. 0
9, 6 ", 18 ~ D&
~" ~ 1 0 0 0
~ 94 : : : ' " " ] " ' " ~ . -.1416 "~ ~ ~ r 7 [~[~]
i 9. 2- "2~'2':'2 ". 12 r ~ [ ]
9 0 - 1 o "~ ~
...... : . . . . . . . . . . . . . . . . . . . . g4 ~ 1 0 0 A
8 8 o8
................... ~ zx
. . . . . . . . . . o o
8, 4 - - .02
-80 -64 -48 -32 -16 ; 1.6 32 48 64 80 10 1' 0 2' 0 3' 0 4 0
Temperature ('C} Wa t e r c o n t e n t / % w. w. b
Fi g. 6. DMT A E ~ a n d t a n ~ o f WI R b l o c k at ( - - - ) - 3. 0, ( )
- 11. 3, a n d ( - - - ) - 2 2 . 3 % ( wwb ) . Ar r o ws i ndi c a t e a p p r o p r i a t e Fi g. 8. E' at 2 0 C f r o m DMT A me a s u r e me n t s of: ( A) - wh o l e
s cal e, r ai s i n, ( I I , ) - r ai s i n s ki n, ( 1 ) _ AI R, ( & ) - WI R, ( [ 7 ) - KOHI R ,
a n d ( C) ) - wo o d [ 27] as a f u n c t i o n o f mo i s t u r e c ont e nt .
whet her r ai si n or r esi due, cons i s t ent wi t h pr evi ous account ed for a decr eas e in modul us , wher eas t he
obs er vat i ons on si ngl e c ompone nt s [13, 16] and mi x- f ur t her r emoval of wat er - i ns ol ubl e cr os s - l i nked pec-
t ures [15]. t i ns bet ween t he WI R and KOHI R had r el at i vel y l i t t l e
The modul us of t he r es i dues at l ow t emper at ur e is effect . The r easons f or t hi s are uncl ear but t he l ubr i -
cons i s t ent wi t h gl as s y val ues r epor t ed el s ewher e cat i ng ef f ect s of t he wat er - s ol ubl e pect i ns ma y
[ 13, 15, 16]. Whe r e a s t he st i f f ness of r ai si ns at 20C decr eas e t he modul us. The modul us o f wood is s ome
decr eas ed at a wat er cont ent of 5 - 1 0 % ( wwb) , t he fi ve t i mes hi gher t han t he WI R but showed s i mi l ar
modul us o f t he r esi dues, cont ai ni ng pr i nci pal l y pect i c de pe nde nc e on moi st ur e cont ent .
pol ys a c c ha r i de s and cel l ul os e, decr eas ed at hi gher Al l t an ~ peaks wer e br oad, i ndi cat i ng het er ogenei t y
wat er cont ent s ( Fi g. 8). Sugar addi t i on t o st ar ches of t he sampl e, al t hough t her e was s ome evi dence f or
[26] or cer eal mi xt ur es [15] has a s i mi l ar effect , t wo s epar at e peaks as obs e r ve d f or wood [27] and
The r emoval o f wat er - s ol ubl e non- cr os s l i nked pect i c a myl ope c t i n- gl ut e n mi xt ur es [28]. It is al so i nt er est -
pol ys a c c ha r i de s bet ween t he AI R and t he WI R i ng t hat Kal i chevs ky and Bl ans har d [29] not ed t he
78 D.M.R. Georget et al./Thermochimica Acta 294 (1997) 71-79
200 to detect by DSC. Conversely, the Tg wa s more easily
measured for high sugar raisin material by DSC
150.
~. compar ed to DMTA.
0
100-
~ <) ~ <~ Ac k n o w l e d g e m e n t s
5o , ~ O~o o ,
= We thank Bi ot echnol ogy and Biological Sciences
~n [ ] Research Council and the EU COMETT scheme for
-5o. [] [] funding.
o []
-IOO I'O 2'0 3'0 40
Water cont ent / % w.w.b References
Fig. 9. Tg as a function of moisture content: (i) by DSC; whole
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