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Journal of Cereal Science 56 (2012) 147e152

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Journal of Cereal Science

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Effect of parboiling on physical and chemical characteristics and non-enzymaticbrowning of emmer (Triticum dicoccon Schrank)

Maria Cristina Messia, Giovanna Iafelice, Emanuele Marconi*

DISTAAM, Università degli Studi del Molise, Via De Sanctis snc, 86100 Campobasso, Italy

a r t i c l e i n f o

Article history:Received 13 June 2011Received in revised form26 April 2012Accepted 15 May 2012

Keywords:ParboilingT. dicoccon SchrankMaillard reactionPhysical and chemical characteristics

Abbreviations: HI, Hardness index; NP, Not Pearle* Corresponding author. Tel.: þ39 0874 404616; fax

E-mail address: marconi@unimol.it (E. Marconi).

0733-5210/$ e see front matter � 2012 Elsevier Ltd.http://dx.doi.org/10.1016/j.jcs.2012.05.006

a b s t r a c t

Parboiling is a popular technology applied to rice to increase its milling yield, nutritional value andresistance to spoilage by insects and mould. This process was applied to Triticum dicoccon Schrank toinduce physical, chemical and organoleptic modifications in order to increase its use and productdiversification.

Hulled and dehulled emmer samples, subjected to different parboiling conditions, were characterizedby analyzing the physical and chemical modifications and the non enzymatic browning.

The results showed that although parboiled grains were darker than the untreated reference sample,due to the development of non-enzymatic browning and the diffusion of the pigments contained in thehusk and bran, during hydrothermal treatment glumes have a protective action on the caryopsis integrityand against thermal damage.

� 2012 Elsevier Ltd. All rights reserved.

1. Introduction

Hulled wheat (emmer, Triticum dicoccon Schrank) denotes anyof the wild or cultivated Triticum populations that retain the hullduring threshing. Their kernels are covered by tough paleas andspikelet glumes, thus the threshing product is spikelets, and notgrains. Emmer predominantly has awn and spikelets consisting oftwowell-developed kernels and the emmer glumes, which are longand narrow with sharp beaks (Marconi and Cubadda, 2005).

The increasing popularity of hulled wheats (spelt, emmer andeinkorn) as environmentally friendly cereal crops for production ofniche cereal-based products is stimulating research into theirutilization in both traditional and new foods such as pasta, break-fast cereals and extruded products. Parboiled cereals and pseudo-cereals may also be attractive to consumers as an innovative andnutritious food (Abdel Aal and Hucl, 2005; Cubadda and Marconi,2001; Fregeau Reid and Abdel Aal, 2005; Hidalgo et al., 2008;Rooney and Awika, 2005; Singh and Dodda, 1979).

Parboiling treatments are generally applied to rice (Oryza sativaL.), paddy or brown rice to increase its milling yield, nutritionalvalue and resistance to spoilage by insects and mould (Elbert et al.,2001). During the process, physical and chemical changes in the

d; P, Pearled.: þ 39 0874 404652.

All rights reserved.

kernel take place such as reduction of rice stickiness, increase inhardness and starch gelatinization.

The higher nutritional value of parboiled rice compared tonon-parboiled rice is due to the migration of bran components(vitamins, minerals) into the endosperm during hydrothermaltreatment (Bhattacharya, 2004; Lamberts et al., 2006a), and hasprompted researchers to apply a parboiling process to other cerealsand pseudocereals (sorghum, millet, oat, barley, buckwheat, wheat,einkorn) (Bayram et al., 2004; Hidalgo et al., 2008; Koksel et al.,1999; Mohapatra and Rao, 2005; Serna-Saldivar et al., 1994;Skrabanja et al., 1998; Young et al., 1990, 1993) to investigate thepossibility to obtain rice-like products with nutritional, economicand sensory advantages comparable to those obtained with rice.

This study reports on the possibility to subject hulled wheat toa parboiling process that is traditionally applied to raw rice, asemmer and rice are both hulled cereals. The characterization ofemmer during parboiling was carried out by analyzing thechemical-physical composition and specific processing markers ofintensity of heat treatments.

2. Materials and methods

2.1. Samples

Hulled and dehulled emmer grains of T. dicoccon Schrank(Dicocco Molise, Colli selection) were used for parboiling trials.

M.C. Messia et al. / Journal of Cereal Science 56 (2012) 147e152148

2.2. Parboiling tests

The emmer parboiling process was carried out using the modelLABPAR (Colombini & Co. srl, Abbiategrasso, Milano, Italy) par-boiling pilot plant.

3 kg of hulled and dehulled emmer grains were parboiledfollowing different conditions as reported in Fig. 1.

The first type of parboiled emmer (Fig. 1, scheme 1) was ob-tained by treating hulled emmer in water at 50 �C for 6 h to favourimbibition; the steeped cereal was treated with steam underpressure (1.5 kg/cm2) for 20 min and then dried using a vacuum at50 �C until 12% of the moisture content remained in the grain.

A second type of parboiled emmer was produced by steepinghulled emmer at 50 �C for 6 h (Fig. 1, scheme 2).

At the end of the process, the cereal was subjected to a pre-cooking treatment of 10 min in water at high hydrostatic pressure(1.5 kg/cm2). The successive steam treatment was carried out usingsteam under pressure (1.5 kg/cm2) for 15min, and then dried undervacuum at 50 �C until the moisture content was reduced to 12%.

Parboiledgrains (Fig.1, schemes1and2)weresuccessivelydehulledand then pearled to remove the same amount of outer layers (15%).

A third type of parboiled emmer (Fig. 1, scheme 3) was obtainedtreating dehulled grains. Emmerwas steeped inwater at 50 �C for 4 h;itwas then treatedwith steamunder pressure (1.5 kg/cm2) for 20minfollowedbydrying as for the above samples. At the endof theprocess,parboiled dehulled emmer was pearled removing 15% of by-product.

The dehulling of different hulled samples (before or aftersteaming) was carried out by a G.390/R dehuller (Colombini & Co.srl, Abbiategrasso, Milano, Italy).

Successively, 100 g of each parboiled dehulled sample werepearled with G.150/R rice whitening machine (Colombini & Co. srl,Abbiategrasso, Milano, Italy) to obtain pearled products.

Pearlin

Hulled em

Pre-coo(10 min; 1.5

Steam (15 min; 1.5

Air dry va (50°C; mois

Dehullin

Steepin(50°C; 6

Schem

PARBOIPEARLED E

Pearling

Hulled emmer

Steeping(50°C; 6h)

Steaming (20 min; 1.5 kg/cm2)

Air dry vacuum (50°C; moisture 12%)

Dehulling

Scheme 1

PARBOILED PEARLED EMMER

Fig. 1. Conditions used for parboilin

2.3. Kernel texture (hardness index)

The emmer kernel texture (degree of hardness or softness) wasdetermined according to AACC method 55-31 (AACC, 2000) byinstrumental measurement of the force required to crush emmerkernels. Analyses were carried out on 300 kernels by SKCS (SingleKernel Characterization System) model 4100 (Perten Instruments,Huddlinge, Sweden).

2.4. Test weight

The test weight was determined by a Schopper chondrometerequipped with a 250 mL cylinder.

2.5. Kernel translucency

Kernel translucency and white/opaque core were evaluated on50 kernels using a farinator, a device that allows 50 kernels to beheld firmly while a blade is moved through to cut them trans-versely (ICC method 129). The percentage of vitreous kernels isdetermined by examining the cross-section of the kernels. Vitreouskernel appears dark and translucent, while opaque and nonvitreous kernel appears starchy.

2.6. Cooking assessment

Two grams of emmer were cooked in 20 mL of water inordinary-size pyrex test tubes. After the desired cooking period, thetube was cooled in a beaker of water for 1 min. The emmer wasthen collected over a wire screen, spread, stirred over filter papersheets for 30 s and weighed. The optimal cooking time was deter-mined removing a few grains at different intervals, and noting the

Pearling

Dehulled emmer

Steeping(50°C; 4h)

Steaming (20 min; 1.5 kg/cm2)

Air dry vacuum (50°C; moisture 12%)

Scheme 3

PARBOILED PEARLED EMMER

g

mer

king Kg/cm2)

ing kg/cm2)

cuum ture 12%)

g

gh)

e 2

LED MMER

g hulled and dehulled emmer.

M.C. Messia et al. / Journal of Cereal Science 56 (2012) 147e152 149

time at the moment that the white/opaque core of grain dis-appeared when squeezed between two test glasses (Bhattacharyaand Sowbhagya, 1971; Kar et al., 1999).

Quantification of substances lost in cooking water was carriedout gravimetrically as reported by Nardi et al. (1997).

2.7. Colour

The colour was measured using CIE (Commission Internationalede l’Eclairage, 1976) L*, a*, b* colour system, where L* describesbrightness, a* is redness and b* is yellowness. Colour measure-ments were performed in triplicate with a colorimeter modelCR300 (Minolta Italia, S.p.A., Milan).

2.8. Proximate analysis

2.8.1. MoistureMoisture contentwas determined according to ICCmethod 109/1

(ICC, 1995).

2.8.2. ProteinProtein content (N � 5.7) was determined according to the

Dumas combustion method, AACC method 46-30 (AACC, 2000),using a Leco nitrogen determiner, model FP 528 (Leco Corp., St.Joseph, MI, USA). Cereal flour was weighed (200mg) in tinfoil (Lecotinfoil cups 502-186), using a foil holder (Leco 604-493) andtwisting the ends of the foil to form a teardrop-shaped pocket.

2.8.3. Dietary fibreDietary fibre was determined according to Prosky et al. (1988).

Duplicate test portions of sample were gelatinized with heat-stablealpha-amylase and then enzymatically digested with protease andamyloglucosidase to remove protein and starch.

2.8.4. AshAsh content was determined according to ICC method 104/1

(ICC, 1995).

2.8.5. LipidLipids were determined according to AACC method 30-20

(AACC, 2000).

2.8.6. CarbohydrateCarbohydrate content was calculated by difference.

2.9. Furosine

The furosine content was determined by HPLC according toResmini et al. (1990) and ISO 18329/IDF 193 (2004). Samples,

Table 1Physical properties of parboiled emmer.*

Sample Dehullingyield (%)

Translucency(%)

Hardnessindex (SKCS)

100wei

NP NP NP P NP

Parboiled hulled emmerwithout pre-cooking

70 98 107a 114a 48a

Parboiled hulled emmerwith precooking

74 99 107a 110a 47a

Parboiled dehulledemmer withoutprecooking

e 94 117a 121a 48a

Reference emmer (not treated) 66 0 79b 72b 50a

NP, Not Pearled; P, Pearled.* Different superscript letters within a column indicate statistical differences P � 0.05

corresponding to about 30e70 mg of protein, were hydrolysed innitrogen with 8 ml of 8 N HCl at 110 �C for 23 h. Afterwards, thehydrolysate (0.5 ml) was purified on a Sep-Pak C18 cartridge(Waters Corp., Milford, MA), diluted and analysed by HPLC (Dionex,Sunnyvale, CA, USA) equipped with an Alltech furosine-dedicatedcolumn (250 � 4.6 mm) (Alltech, Derfield, IL, USA). Furosine stan-dard (Furosine dihydrocloride SC494, 10 mg) was purchased fromNeoMPS (Strasbourg, France).

2.10. Statistical analysis

Data reported for all parameters are the average values of tworesults obtained from analysis of two different aliquots of eachsample. Statistical significance is also reported (P < 0.05): samplesthat were significantly different are indicated with different letters.

3. Results and discussion

3.1. Influence of parboiling on physical characteristics of emmer

Table 1 reports the physical properties of parboiled emmersamples. All samples were glassy and translucent, with a trans-lucency value approaching 100%. The data confirm that all par-boiling conditions ensure complete starch gelatinization.

Dehulling yield was higher for parboiled samples (70e74%)compared to untreated samples (66%). These results are supportedby hardness index (HI) values being higher for parboiled emmer.

A higher hardness index corresponds to a higher compactness ofthe kernel structure and thus a greater resistance to mechanicalstress. A similar behaviour was also found in rice due to parboiling(Raghavendra Rao and Juliano, 1970) and confirmed by the data weobtained for commercial brands of non-parboiled (HI <75) andparboiled rice (HI >100). The polishing yield was standardised tothe same level for each type of grain to remove the same amount(15%) of outer layers of the kernel (bran and aleurone) and tocompare the nutritional, cooking and sensory properties of treatedand untreated grains. To obtain this result, untreated emmerrequired significantly lower milling time (30 s) than parboiledemmer (1 min) due to its lower kernel hardness.

The value of the test weight was higher for samples of pearledparboiled emmer (78.2e79.2 kg/hl) than for the reference sample(76.9 kg/hl), and this can be correlated with chemical, physical,dimensional and structural changes of the kernel. Parboilingtreatment induces a “shortening” and an “enlargement” of thegrains, for parboiled rice (Kurien et al., 1964). The rounded shape ofthe kernels, which persists even after polishing samples, yieldsa product that can be appreciated by consumers.

The cooking behaviour of parboiled emmer can be characterizedby three parameters: optimal cooking time, percentage of

0 kernelght (g)

Test weight(kg/hl)

Diameter(mm)

Length(mm)

Diameter/length

P NP P NP P NP P NP P

43a e 78.2a 3.06a 2.84a 7.96b 6.98bc 0.38 0.40

42a e 79.2a 3.14a 2.75a 7.86b 7.08b 0.39 0.39

44a e 78.8a 3.11a 2.74a 7.42c 6.87c 0.42 0.40

43a 74.1 76.9b 2.83b 2.37b 8.20a 7.27a 0.34 0.32

.

Table 2Cooking time, cooking loss and water uptake of parboiled emmer.*

Sample Cookingtime (min)

Cookingloss (%)

Wateruptake (%)

Parboiled hulled emmerwithout precooking

20a 5.30b 132b

Parboiled hulled emmerwith precooking

21a 5.18b 125bc

Parboiled dehulled emmerwithout precooking

20a 5.32b 119c

Reference emmer (not treated) 18b 6.86a 143a

* Different superscript letters within a column indicate statistical differences(P � 0.05).

M.C. Messia et al. / Journal of Cereal Science 56 (2012) 147e152150

substances lost in cooking water and the amount of water absorbedduring cooking (Table 2).

Hydrothermally treated emmer required 20e21min to reach theoptimal cooking level, compared to 18 min for the same untreatedsample. This is probably due to the gelatinization and retrograda-tion of starch, which gives compactness and impermeability to theparboiled kernels, and slows down and limits water absorptionduring cooking as put in evidence in rice by Bhattacharya (2004).

The percentage of substances released in cooking water fromgrains is a good indicator of cooking quality, as it is a function of theresistance to cooking and stickiness. The amount of solutes lost inthe cooking water (starchy material) for the untreated emmer(6.8%) was significantly higher than that of the parboiled product(5.2e5.3%), presumably because hydrothermal treatment results ina decrease in solubilisation of starchy substances in cooking water.The reduced loss of solids involves a greater nutritional value ofemmer subjected to hydrothermal treatment compared tountreated product.

These results are in agreement with the results of Nardi et al.(1994) concerning the behaviour of parboiled rice during cook-ing: the percentage of substances released in the cooking waterfrom samples of parboiled rice was reported to be between 5.9 and9.1% compared to values of 9.3e13.3% for untreated rice.

The value of the absorption of water expresses the kernelsincrease in weight after cooking and provides an estimate of thetendency of grains to clump together and absorb broth andseasoning (Migliorini and Greco, 1999). The amount of waterabsorbed by parboiled emmer was less than the untreated sample,which is also consistent with previous results for parboiled rice(Nardi et al., 1994) and related to the higher compactness of theparboiled kernels.

3.2. Influence of parboiling on chemical composition of pearledemmer

The protein content of three different types of parboiled emmerremained unchanged from the corresponding untreated grain(Table 3). This is in contrast to pearled samples, which showeda higher protein content compared to the untreated sample, whichcan be attributed to the migration of soluble protein fractions from

Table 3Proximate composition (% d.m.) of parboiled emmer before and after pearling.*

Sample Protein (%) Lipids (%)

NP P NP P

Parboiled hulled emmer without precooking 15.1a 14.2a 3.1a 1Parboiled hulled emmer with precooking 15.0a 14.2a 3.1a 1Parboiled dehulled emmer without precooking 14.9a 14.2a 3.2a 1Reference emmer (not treated) 14.9a 13.8b 3.1a 2

NP, Not Pearled; P, Pearled.* Different superscript letters within a column indicate statistical differences (P � 0.0

the aleuronic layer of the caryopsis to the starchy endosperm, aswasdescribedbyDamir (1985) andSingh et al. (1999) forhydrothermallytreated rice. The lipid content of the parboiled emmer is comparableto that of the corresponding reference sample of untreated emmer. Itis likely that, even for emmer, hydrothermal treatment can break fatglobules (Mahadevappa and Desikachar, 1968), which are presentmainly in the germ and aleurone layer, and the subsequent redis-tribution and/or migration of fat to the cortical layers of the kernel,subjected to removal during the polishing process. Indeed, thepercentage of fat in the by-product, resulting from abrasion ofkernels of the individual samples of parboiled emmer, was higher(10.0e11.0%) than in the reference sample (9.0%).

Ash content of pearled and not pearled samples is significantlyinfluenced by parboiling both in pearled and in not pearled kernels.The ash content of parboiled is in fact higher than in the corre-sponding untreated grains, which can be attributed to the migra-tion of mineral substances from water to kernel (not pearledsamples) and from outer to inner layers of kernel (pearled kernels).

The significantly higher content of dietary fibre of parboiledsamples (13%) than reference samples not pearled and pearled(11%) is presumably due to the formation of resistant starch duringparboiling, and especially in the subsequent cooling phase of starchretrogradation, as also reported by Marsono and Topping (1993).The resistant starch is, in fact, a fraction of starch, which is resistantto enzymatic hydrolysis and is quantified in the insoluble fraction ofdietary fibre by the enzymatic-gravimetric method of Prosky et al.(1988). Such changes in the polysaccharide load of emmerpresumably improve the nutritional quality of the finished product(lower glycaemic index, higher fibre content).

3.3. Evaluation of browning of parboiled products

Bran components leach out and diffuse into endosperm duringsteaming, giving rise to parboiled kernels that have a darker colour.

The extensive availability of reducing sugars and a and 3aminogroups of amino acids and proteins allows the formation of Ama-dori compounds during heat treatment. The furosine assay is themost sensitive and the most accepted method for assessingformation of Amadori compounds during the early stage of theMaillard reaction. In fact, this marker has been successfully used toassess the intensity of heat treatment of different foods, such asliquid and powderedmilk (Messia et al., 2007; Resmini et al., 2003),pasteurised and powdered eggs (Caboni et al., 2005), as well asboth powdered infant formulas and cereals (Guerra Hernandezet al., 2002; Ramirez Jimenez et al., 2000). Nardi et al. (1998) andLamberts et al. (2006b, 2008) confirmed the occurrence of theMaillard browning reaction during parboiling in rice by measuringthe Maillard precursors and indicators and demonstrating a rathersmall contribution of enzymatic action during soaking.

During hydrothermal treatment, emmer caryopsis underwentbrowning due to the Maillard reaction.

Emmer samples subjected to parboiling treatment, both huskedand not husked, showed a furosine content that was significantly

Ash (%) Dietary fibre (%) Carbohydrates (%)

NP P NP P NP P

.9a 1.94a 1.18a 13.3a 9.6a 66.7 73.1

.9a 1.90a 1.22a 12.9a 9.2a 67.1 73.5

.8a 1.93a 1.17a 12.7a 9.1a 67.3 73.7

.0a 1.82b 0.92b 11.1b 6.7b 69.1 76.6

5).

Table 4Furosine values and colorimetric indices for parboiled emmer.*

Treatment Furosine(mg/100g protein)

Colour

100-L* a* b*

NP P PP P P P

Parboiled hulled emmerwithout precooking

20.1c 15.2c 51.5b 21.0a 1.2a 15.0b

Parboiled hulled emmerwith precooking

31.2b 25.0b 52.6b 21.4a 1.0a 16.7a

Parboiled dehulled emmerwithout precooking

36.9a 31.1a 60.1a 21.6a 0.7b 16.0a

Reference emmer (not treated) 4.9d 5.9d 4.3c 14.2b 0.6b 12.2c

NP, Not Pearled; P, Pearled; PP, Pearling by-Product.* Different superscript letters within a column indicate statistical differences

(P � 0.05).

M.C. Messia et al. / Journal of Cereal Science 56 (2012) 147e152 151

higher than the respective reference samples (Table 4). In partic-ular, higher values of furosine were found in samples of parboiledhulled emmer with precooking (31.1 and 23.4 mg/100 g proteinrespectively for non-pearled and pearled samples) and parboileddehulled emmer without precooking (36.9 and 23.0 mg/100 g ofprotein, respectively, for pearled and non-pearled samples), moreexposed to heat during parboiling. The former is because it issubjected to an additional pre-cooking treatment, while the latteris due to direct contact with water imbibition and the absence ofglumes, steam and hot air. The higher furosine values in non-husked than husked samples can be attributed to the Maillardreaction, which involves the peripheral layer of the caryopsis, thehigher concentration of reducing sugars and the greater tempera-tures reached at the surface.

Pearling exerts a significant influence on the furosine content ofthe kernel since theMaillard reactionmostly involves outer layers ofthe kernel, both for the higher concentration of reducing sugars andhigher thermal stress reachedon thekernel surface, asdemonstratedby the high furosine values observed in pearling by-products.

The values of furosine in parboiled emmer were similar to thosefound in commercial parboiled durum wheat samples (27e36 mg/100 g of protein), whereas commercial parboiled rice had highervalues (65e78 mg/100 g of protein), similar to those reported byNardi et al. (1998).

Parboiled emmer browning can be clearly demonstrated bycolour analysis of caryopsis with parameters such as 100-L (brownindex), a* (red index) and b* (yellow index) (Table 4). In particular,the brown index was significantly higher in parboiled samples(100-L* ¼ 21.0e21.6) than reference untreated samples (100-L ¼ 14.2). Moreover, red (a*) and yellow (b*) indices were higherin samples subjected to parboiling both for the Maillard reactionand for the migration of polyphenolic substances from glumes byanalogy with rice as reported by Subrahmanyan et al. (1938).

4. Conclusions

During emmer parboiling, the presence of glumes had animportant role preserving the integrity and reducing the thermaldamage of the kernel. In addition, hydrothermal treatment makes itpossible to obtain an innovative product (parboiled emmer) withexcellent nutritional and cooking properties (firmness, bulkiness,stickiness, water uptake and solid loss in cooking water) and toincrease emmer use by the product diversification.

Acknowledgements

Authors wish to thank Dr. Sergio Colombini (Colombini & Co. srl,Abbiategrasso, Milano, Italy) for his support in the carrying out ofthe pilot plant tests.

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