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Retrogradation behaviour of milled and brown rice pastes during ageing

Retrogradation behaviour of milled and brown rice pastes during ageing
Retrogradation behaviour of milled and brown rice pastes during ageing

Retrogradation behaviour of milled and brown rice pastes during ageing

M.Mariotti *,N.Sinelli,F.Catenacci,M.A.Pagani,M.Lucisano

Department of Food Science and Microbiology (DiSTAM),University of Milan,Via G.Celoria 2,20133Milan,Italy

a r t i c l e i n f o

Article history:

Received 1January 2008Received in revised form 9July 2008

Accepted 5September 2008Keywords:Rice Gel

Retrogradation Viscoamylograph

Dynamic rheological test FT-NIR spectroscopy

a b s t r a c t

Retrogradation of gelatinised starch is the main phenomenon that in?uences the texture of cooked rice.The rate of retrogradation is affected by several factors including amylose and amylopectin ratio,protein and ?bre.The objective of this study was to analyse the pasting properties and the retrogradation behaviour of six traditional and ?ve aromatic Italian rice varieties.The pasted gels,after cooling,were evaluated by dynamic rheological measurements for up to 7days of storage at 4 C.The samples were also analysed by a NIR spectrometer.The pasting properties and the retrogradation behaviour of milled rice ?ours strongly depended on the rice varieties.During gel ageing,a noticeable increase of G 0and G 00was observed only for the milled rice varieties Asia,Gange,Fragrance and Vialone Nano,characterised by a high amylose content.No further hardening was found either for the other milled varieties or for all the brown samples.The methods used in this work (dynamic oscillatory rheometry and FT-NIR spectros-copy)turned out to be very useful in the de?nition of rice starch gels ageing.

ó2008Elsevier Ltd.All rights reserved.

1.Introduction

During gelatinisation,starch granules swell to several times their initial size as the result of the loss of crystalline order and water absorption;they are partially ruptured,releasing amylose,and form a three-dimensional network with the swollen granules embedded into the matrix.A starch paste can therefore be regar-ded as a composite material consisting of swollen granules dispersed in a continuous biopolymer matrix (Noel et al.,1993).The properties of each phase and the interactions between the components are important elements in determining the rheolog-ical behaviour of pasted gels.These properties depend on several factors,including the type and the concentration of starch,the amylose/amylopectin ratio,the temperature pro?le applied to the pastes,and the presence and concentration of other soluble and insoluble compounds such as protein,salts,lipids,and ?bre (Lii et al.,1995,2004).

The swollen starch granules form a strong packed gel structure with a high shear resistance whose intensity increases on cooling due to starch retrogradation.In fact,if the starch concentration is suf?ciently high,the paste can convert into gel upon cooling (Tester

and Morrison,1990).Retrogradation of gelatinised starch involves the reordering of the amylose chains in short-term ageing (Dou-blier and Choplin,1989)and a slower reorganisation of amylopectin after longer periods (Biliaderis and Zawistowski,1990;Lai et al.,2000).

The Brabender Micro-Visco-Amylograph (MVA)and the Rapid Visco Analyser (RVA)are currently used as standard analytical tools to assess the pasting characteristics of starch and ?our suspensions in water.Several parameters evaluated from the pasting pro?les of milled rice ?our have been shown to correlate with the eating quality (Bergman et al.,2004)and with the end-use of rice ?our.Relationships have been observed between the amylographic measurements and the amylose and protein content (Sandhya Rani and Bhattacharya,1989)and the instrumental parameters used to measure the textural properties of rice ?our pastes.

Dynamic oscillatory rheometry is useful for monitoring struc-ture development during gelling and ageing without breaking the structural elements formed in the sample upon ageing.In a dynamic test,the storage modulus (G 0),loss modulus (G 00),complex modulus (G *)or complex viscosity (h *)are determined using a sinusoidal strain cycle.Many authors have used rheological methods to monitor the changes that occur during the heating of starches and ?ours (Hagenina and Ding,2005;Hamed et al.,2008;Lii et al.,1995,1996;Rao et al.,1997;Svegmark and Hermansson,1991)and to evaluate the viscoelasticity of starch pastes (Lii et al.,1995;Sandhya Rani and Bhattacharya,1989;Yoo,2006)and gels (Biliaderis and Zawistowski,1990;Chun and Yoo,2004).

Another interesting method for acquiring information about molecular changes during gel ageing is near infrared re?ectance

Abbreviations:FT-NIR,Fourier transform near infrared re?ectance;G 0,storage modulus;G 00,loss modulus;MSC,multiplicative scatter correction;MVA,Brabender Micro-Visco-Amylograph;NIR,near infrared re?ectance;PCA,principal component analysis;Rice varieties:AP,Apollo;AS,Asia;AU,Augusto;BA,Balilla;FR,Fragrance;GA,Gange;GI,Giano;GL,Gladio;RO,Roma;SE,Selenio;VN,Vialone Nano;RVA,Rapid Visco Analyser.

*Corresponding author.Tel.:t390250319186;fax:t390250319190.E-mail address:manuela.mariotti@unimi.it (M.

Mariotti).Contents lists available at ScienceDirect

Journal of Cereal Science

journal homepage:

https://www.doczj.com/doc/fd695022.html,/locate/jcs

0733-5210/$–see front matter ó2008Elsevier Ltd.All rights reserved.doi:10.1016/j.jcs.2008.09.005

Journal of Cereal Science 49(2009)171–177

(NIR)spectroscopy,a rapid and non-destructive analytical tech-nique for studying food product characteristics.The IR spectrum is obtained by a change in the molecular dipole moment during vibration.NIR spectroscopy(780–2500nm)applied to food samples gives information on the molecular bonds and therefore on the functional groups of the molecules.Spectrum bands involve many of the general stretching,bending motions of the molecule, and the overall spectrum may act as a?ngerprint of molecular status(Cen and He,2007;Williams and Norris,2002).Champagne et al.(2001)used NIR spectroscopy as a rapid and cost-effective analytical tool to assess rice quality and sensory attributes.Some studies have proposed calibration models for the determination of amylose and protein content in rice(Delwiche et al.,1996;Sohn et al.,2004).Windham et al.(1997)pointed out that NIR spec-troscopy gave the best prediction results for the textural attributes perceived in the initial oral phases of sensory evaluation such as adhesiveness and stickiness.These attributes were mainly related to changes in spectra due to the different protein,starch and lipid content of the rice.Sinelli et al.(2006)demonstrated the feasibility of using NIR spectroscopy to pro?le rice during cooking and to evaluate the optimal cooking time of milled,parboiled and quick cooking rice.In a limited number of studies,NIR spectroscopy has been used as a rapid and non-destructive technique for evaluating the gelatinisation and retrogradation behaviour of cooked rice(Cho et al.,1998).

The objectives of this study were to analyse the pasting prop-erties and the retrogradation behaviour of six traditional and?ve aromatic Italian rice varieties,both as brown and milled grains,via dynamic oscillatory rheometry and NIR spectroscopy,and to investigate the possibility of using NIR spectroscopy as a rapid and non-destructive method to monitor textural changes of rice gels during ageing.

2.Experimental

2.1.Rice samples

Six traditional Italian rice varieties–Augusto(AU),Balilla(BA), Gladio(GL),Roma(RO),Selenio(SE),Vialone Nano(VN)–and?ve aromatic rice varieties–Apollo(AP),Asia(AS),Gange(GA),Giano (GI)and Fragrance(FR)–were provided by C.R.A.,Experimental Institute for Cereal Crops(Vercelli,Italy).The samples were har-vested in October–November2005and stored at18 C for 6months.The paddy rice was then dehulled and milled with a model SKD Satake Pearler(Satake Corporation,Hiroshima,Japan). The resulting brown and milled kernels were then ground in a laboratory scale mill(IKA Universalmu¨hle M20,Jank and Kunkel GmbH and Co KG,IKA Laborteknic Staufen,Germany)to give?ours able to pass a500m m mesh sieve.

2.2.Chemical analyses

The moisture content of the rice?ours was determined according to the of?cial standard method AACC44-15A(2000).The total nitrogen content was determined according to the of?cial standard method AOAC920.87(1999);the protein content was calculated adopting 5.95as a conversion factor.The amylose content was determined by the method UNI ISO6647(1991)and expressed as the proportion by weight of amylose to total rice (%db).All these determinations were made at least in duplicate.The amount of total starch,damaged starch and the alpha-amylase activity of the samples were determined enzymatically using the ‘‘Total Starch Assay Kit’’,the‘‘Starch Damage Assay Kit’’and the ‘‘Alpha-amylase Assay Procedure’’,respectively,by Megazyme International Ireland Ltd.(Bray Business Park,Bray,Co.Wicklow,Ireland).The results of these evaluations are the average of four replicates at least.

2.3.Pasting properties

The pasting properties of the different rice?ours were measured using an MVA(Brabender OHG,Duisburg,Germany)that provides an accurate control of the time-temperature and shear pro?le.Fifteen grams of the sample were dispersed in100mL of distilled water,scaling both?our and water weight on14%?our moisture basis.The suspensions were subjected(stirring at 250minà1and using a300cm g f cartridge)to the following standard temperature pro?le:heating from30up to95 C,holding at95 C for30min,cooling from95to50 C,holding at50 C for 30min and cooling to30 C.A heating/cooling rate of1.5 C/min was applied.The following indices were considered:gelatinisation temperature(temperature at which an initial increase in viscosity occurs; C),peak viscosity(maximum paste viscosity achieved during the heating cycle;BU),?nal viscosity(paste viscosity ach-ieved at the end of the cooling cycle;BU),and setback(index of viscosity increase during cooling,corresponding to the difference between?nal viscosity at30 C and viscosity after the holding period at95 C;BU).

2.4.Gel preparation

The rice pastes prepared in the MVA were poured immediately into plastic vessels for the rheological test and into glass vials for NIR spectroscopy and sealed during the retrogradation period.The samples were cooled at room temperature for2h and then stored at4 C up to7days.Rheological and spectroscopic measurements were carried out on the samples at?xed times.

2.5.Rheological measurements

Dynamic rheological measurements were performed with

a Physica MCR100Rheometer(Anton Paar,Ost?ldern,Germany)at

25 C,using a corrugated plate system(2.5cm diameter)at a gap of 1mm.The sample was loaded between parallel plates,the excess was wiped off with a spatula and a thin layer of paraf?n oil was applied to the edge of the exposed sample to prevent moisture loss during measurements.Before starting the test,the gel was allowed to rest for5min after loading in order to equilibrate.Dynamic shear data were obtained from frequency sweeps over the range of0.1–10Hz at3%strain.The strain value was obtained from preliminary amplitude sweep tests.Rheological parameters(storage modulus, G0;loss modulus,G00;tan d,as the ratio between G00and G0)were obtained from the Physica Universal Software US200.All the rheological measurements were performed at least in duplicate.

2.6.NIR measurements

Spectral data were collected over the range12,500–3600cmà1 in re?ectance mode using a Fourier transform near infrared re?ectance(FT-NIR)spectrometer(MPA;Bruker Optics,Ettlingen, Germany)equipped with an integrating sphere.Measurements were carried out at room temperature and triplicate spectra were collected on each sample with a resolution of32cmà1.

The average spectra were standardised using the multiplicative scatter correction(MSC)method and then transformed into second derivative(Savitzky Golay,smoothing points?10).Principal component analysis(PCA)was performed as an explorative anal-ysis on all data sets(traditional and aromatic rice varieties)in order to display the data structure and to reduce the dimensionality of the spectra to a small number of components(Naes et al.,2000).

M.Mariotti et al./Journal of Cereal Science49(2009)171–177 172

Chemometric analysis was performed using The Unscrambler software package (Version 9.6,CAMO,ASA,Norway).3.Results and discussion 3.1.Chemical composition

Table 1shows the chemical composition of the different rice varieties (A:brown rice samples;B,milled rice samples).The protein content of brown rice ranged from 6.66to 9.64g/100g db and from 6.04to 10.58g/100g db for the milled grains,respec-tively.Higher differences could be observed for amylose content and alpha-amylase activity,two constituents that have a strong

in?uence on the pasting properties of rice and consequently on the retrogradation behaviour (Zhou et al.,2002a,b ).Amylose,evaluated only on milled samples,varied from 18.26to 27.86g/100g db;a similar range of variation is also expected for brown https://www.doczj.com/doc/fd695022.html,ling induced a proportional increase of starch content and a strong reduction of the enzymatic activity that was reduced by about one order of magnitude.

3.2.Pasting properties

The pasting properties of brown and milled rice ?ours were evaluated to account for the importance of rice

components

Table 1

20406080100AU BA GL RO SE VN AP AS GA GI FR

G e l a t i n i s a t i o n t e m p e r a t u r e (°C )

200400600800100012001400

F i n a l v i s c o s i t y (B U )

P e a k v i s c o s i t y (B U )

200

40060080010001200

1400

S e t b a c k (B U )

Fig.1.Main viscoamylographic indices for brown and milled rice varieties.

M.Mariotti et al./Journal of Cereal Science 49(2009)171–177

173

removed during the milling process.The principal pasting charac-teristics of all rice varieties are summarised in Fig.1.

An increase in the gelatinisation temperatures was observed for the brown samples,suggesting that the kernel components removed during milling slowed down water absorption and starch disorganisation upon heating.Peak viscosity,which re?ects the swelling extent of the starch granules,was higher for milled rice in relation to their higher starch and lower protein content.The amylase activity of the brown?ours certainly played a signi?cant role in reducing peak viscosity,also taking into consideration the low heating gradient adopted(Mariotti et al.,2005).In addition, viscosity after cooling(?nal viscosity)was higher for the milled rice,in particular for those varieties that presented a higher percentage of amylose.The setback value,a parameter re?ecting the degree of retrogradation of starch paste,was differently affected by milling:AU,BA,GL and SE showed similar values for brown and milled?our,while VN,AS,GA and FR,characterised by a higher amylose content,showed a greater setback for the milled rice?ours.Moreover,considering the milled rice?ours,the amylose content was signi?cantly correlated(P<0.01)with the gelatinisation temperature(r?0.81),the?nal viscosity(r?0.90) and the setback(r?0.93),parameters that re?ect the short-term retrogradation behaviour of starchy gels.

3.3.Rheological measurements

In order to have a rheological characterisation of the gels of the different rice varieties,the effect of strain was investigated?rst.

For

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Fig.2.Evolution of G0and tan d of AS and SE varieties during ageing:(>)2h(room temperature),(,)1day(4 C),(:)2days(4 C),()3days(4 C),(-)4days(4 C),(C) 7days(4 C).

M.Mariotti et al./Journal of Cereal Science49(2009)171–177

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all samples,both freshly pasted and aged gels obtained from brown and milled rice,G 0and G 00remained constant up to 6–8%strain (Catenacci,2006).

The overall rheological behaviour of gels during their ageing is well depicted by considering the mechanical spectra (frequency sweeps)obtained for two varieties (AS and SE)and characterised by a completely different time-hardening kinetic,as shown in Fig.2.The strongest tendency of AS to retrograde,already clear from the viscoamylographic setback value (Fig.1),was even more evident after 7days ageing at 4 C.Indeed,a large difference between the G 0values of the two varieties,both for brown and milled pastes,could already be observed after the ?rst 2h of storage at room

temperature.Those behaviours were certainly related to the different amylose content of the two varieties.The reorganisation of the amylose chains,whose concentration for AS was 24.8%,affected not only the hardening of the milled rice gel,but,at a lower extent,also the G 0values of the brown samples.On the contrary,the pasted gel obtained from the SE ?our showed a lower increase in G 0upon ageing.The brown gel of this variety,whose amylose concentration was 18.4%,exhibited a G 0increase with time higher than the milled one,probably due to the gelling phenomena and to the higher water retention of the ?bre components.

m e (d a y s )

e (d a y s )

FR

160018002000G ' (P a )

e

(d a y s )

160G '' (P a )

e (d a y s )

18002000G ' (P a )

160G '' (P a )

FR

Fig.3.G 0and G 00values at 1Hz and 3%strain of brown and milled rice gels during ageing at 4

C.

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5000

6000

7000

8000

9000

10000

1100012000Wavenumber (cm -1)

2n d D e r (L o g 1/R )

Fig.4.Second derivative,after MSC standardisation,of NIR spectra of milled and brown rice pasted gels during ageing.

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Fig.5.Score plot of three varieties (AS,GA,SE)obtained by PCA applied to the 2nd derivative of all samples spectra during ageing.

M.Mariotti et al./Journal of Cereal Science 49(2009)171–177175

For the AS brown and milled gels,G 0was higher than G 00and tan d (G 00/G 0)varied between 0.10and 0.23,indicating the prom-inent solid character of these gels.Higher values (up to 0.73)were found for SE.Moreover,G 0and G 00magnitude increased with frequency with a stronger dependency for G 00,as described by Yoo (2006).From these observations,it resulted that the rice pastes displayed a weak gel-like behaviour,due to the association of ordered chain segments.

To compare the results obtained for all the varieties,G 0and G 00values at 1Hz and 3%strain were considered (Fig.3),as they well represent the textural modi?cations during ageing due to starch retrogradation (Catenacci,2006).

The rate and the extent of milled gel structure formation during ageing were highly dependent on the variety;in fact both G 0and G 00showed a more rapid increase with time for the aromatic milled rice gels obtained from AS,GA and FR that presented an amylose content higher than 23.9%.Gel hardening during 7days storage was strongly related to the amylose content:an exponential relation-ship between the amylose values and both the increase of G 0(r ?0.97,P <0.01)and G 00(r ?0.88,P <0.01)was found.The presence of the outer layer components of the grain made all the brown rice varieties less sensible to hardening during their storage at 4 C,independent of their amylose content.3.4.FT-NIR measurements

The retrogradation behaviour of brown and milled rice pasted gels during ageing was also investigated using the FT-NIR spectroscopy.

Raw spectra,after MSC standardisation,revealed only few peaks,while after a second derivative pre-treatment,several features became apparent (Fig.4).

The spectra were dominated by small peaks at approximately 10,583–10,383cm à1,and by major peaks at 8871–8655,7297,7097,5430,5245,and 4474cm à1.Absorbance at 8871and 8655cm à1is due to bands arising from C–H stretching vibration of starch molecules.The peaks at 7297and 7097cm à1arise from the C–H stretching vibrations of starch and cellulose molecules and the ?rst overtone of O–H of water,respectively.The absorption bands at 5245and 4474cm à1are due to the combination band of water and C–H stretching and bending of starch molecules,respectively (Barton II et al.,2002;Cho et al.,1998).

A preliminary examination of the spectra was performed by PCA applied to the second derivative of the spectra in the range 12,000–4000cm à1(data not reported ).The scatter plot of the ?rst two components (97%of the total variance)revealed a separation between the gel spectra of the milled rice,characterised by positive

PC1values,and of the brown rice of the same varieties.Moreover,only the PC1scores of the milled rice samples described a trend correlated with the storage time,with bigger variations for the milled rice than for the brown rice.As an example,from the projection of the score plot obtained from the PCA applied to the second derivative of all samples spectra,the scores of three varieties (AS,GA,and SE)are shown in Fig.5.Above all,the PCA scores of the milled AS,GA and SE rice gels showed a bigger vari-ation during aging than those of the brown rice samples.Moreover,the score variations appeared more important for the AS and GA milled gels,which are characterised,as already mentioned,by a stronger tendency to retrogradation.

The PCA loading plot was analysed in order to highlight which variables were involved in describing the retrogradation behaviour of the different rice varieties.As can be seen in the PC1and PC2loading plot (Fig.6),the major peaks arising from the ?rst overtone of the C–H stretching vibration of starch molecules (8880–8670cm à1),the ?rst overtone of O–H symmetric and asymmetric stretching of water (7251–7050cm à1),the O–H combination band of water (5430–5245cm à1)and the C–H combination band of starch were identi?ed as principal wavenumbers.As reported by Cho et al.(1998)these molecular modi?cations of starch and water can be attributed to the retrogradation process.In fact,the retro-gradation of gelatinised starch involves both water mobilisation and the reordering of gelatinised starch from the amorphous state to the crystalline form (Biliaderis and Zawistowski,1990;Lai et al.,2000).

4.Conclusions

As the extent of retrogradation strongly affects some physical properties of cooked rice,such as hardness and stickiness,which are taken into high consideration by consumers,the evaluation of this phenomenon has a signi?cant practical importance.Rice retrogradation also has an important technological implication:it is a key factor for de?ning the suitability of rice ?our to be used as an ingredient in gluten-free products.For instance,the retrogradation phenomenon could be useful in gluten-free pasta production to gain a rigid structure;the opposite is recommendable for main-taining crumb softness in gluten-free baked products.Thus,being able to de?ne the extent of this phenomenon for the many different kinds of rice ?our could be of great help in the de?nition of the end-use not only of the rice kernel but also of the corresponding ?our (i.e.suitability to be used as an ingredient in gluten-free products).The methods used in this work (dynamic oscillatory rheometry and FT-NIR spectroscopy)turned out to be very useful in the de?nition of rice starch gels ageing.In particular,NIR spectroscopy could be

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Fig.6.Loading plot of the two ?rst components obtained by PCA applied to the 2nd derivative of all samples spectra during ageing.

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promising as a rapid and non-destructive method to predict the G0 and the G00values of starch pastes during ageing using a high number of samples necessary for developing a robust method. Acknowledgements

The authors wish to acknowledge the precious contribution of Dr.Elisabetta Lupotto and CRA-RIS Vercelli to this research. References

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