Accepted Manuscript

Improvement of the texture and quality of cooked gluten-free pasta

Virginia Larrosa, Gabriel Lorenzo, Noemi Zaritzky, Alicia Califano

PII: S0023-6438(16)30118-9
DOI: 10.1016/j.lwt.2016.02.039
Reference: YFSTL 5321

To appear in: LWT - Food Science and Technology

Received Date: 10 June 2015

Revised Date: 17 February 2016
Accepted Date: 18 February 2016

Please cite this article as: Larrosa, V., Lorenzo, G., Zaritzky, N., Califano, A., Improvement of the texture
and quality of cooked gluten-free pasta, LWT - Food Science and Technology (2016), doi: 10.1016/
j.lwt.2016.02.039.

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 ACCEPTED MANUSCRIPT
1 Improvement of the texture and quality of cooked gluten-free pasta

5 Virginia Larrosa a, Gabriel Lorenzo b,c*, Noemi Zaritzkyb,c, Alicia Califanob

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a
8 Facultad de Bromatología, Universidad Nacional de Entre Ríos. Pte. Perón 64,

9 Gualeguaychú (2820), Argentina.

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b
10 Centro de Investigación y Desarrollo en Criotecnología de Alimentos (CIDCA),

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Facultad de Cs. Exactas, UNLP-CONICET. 47 y 116, La Plata (1900), Argentina.
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12 Depto. Ingeniería Química, Facultad de Ingeniería, UNLP, Argentina.
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16 *Corresponding author: TE/Fax: 54(221)4254853, 47 y 116 (1900) La Plata, Buenos.

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17 Aires, ARGENTINA Email: lorenzogabriel@gmail.com

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20 List of abbreviations

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22 D: overall desirability value

23 EP: egg-protein content

24 G’: storage modulus

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25 G’’: loss modulus

26 GF: gluten-free

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27 GN0: plateau modulus

28 LBG: locust bean gum

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29 OCT: Optimum cooking time

30 SEM: standard error of the mean

31 TOM: Total organic matter

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32 W: water content

33 XG: xanthan gum

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35 ABSTRACT

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37 The effects of egg-proteins and water content on viscoelastic and quality properties of

38 cooked gluten-free pasta were analyzed. Cooking properties included the

39 determination of optimum cooking time (OCT = 10 minutes), water absorption, cooking

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40 loss, and total organic matter. Cutting force and texture profile parameters were also

41 evaluated. Springiness, resilience, and adhesiveness were mainly controlled by the

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42 egg-protein content in the dough, while cooked pasta hardness and the plateau

43 modulus were negatively correlated with dough moisture. The obtained results were

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44 mathematically modeled, and a multiresponse optimization process was performed

45 using individual desirability functions based on target properties of wheat flour pasta.

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These functions were combined into a single composite response (global desirability)
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47 to determine the precise amount of the different components in the formulation to

48 obtain high quality gluten-free cooked pasta. Optimized dough was prepared, cooked,
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49 and the predicted properties were experimentally validated.

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57 Keywords: gluten-free pasta, textural properties, cooking quality, viscoelastic

58 behavior, optimization.

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61 1. INTRODUCTION

62 Pasta manufacturing industry, like all industries, caters to the wants and needs of their

63 consumers. High quality cooked pasta from durum wheat semolina maintains good

64 texture, resists surface disintegration, does not release an excessive amount of organic

65 matter into the cooking water, retains a firm structure, and does not show surface

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66 stickiness (Liu, Shepherd, & Rathjen, 1996). This is clearly related to the fact that

67 gluten in wheat flour is the main structure-forming protein, thus its absence in gluten-

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68 free (GF) pasta results in technological and quality problems.

69 The technological process adopted in GF pasta production has a significant influence

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70 on the quality of the final product as well as the raw materials used. One of the usual

71 methodologies to produce GF pasta is to obtain pregelatinized starch through heat and

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cool stages, thus forming a rigid network based on the retrograded starch (Cabrera-
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73 Chávez et al., 2012; Marti, Caramanico, Bottega, & Pagani, 2013; Marti, Seetharaman,

74 & Pagani, 2010).

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75 However, despite the great efforts made in the last few decades to produce GF pasta
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76 with sensory characteristics similar to durum-wheat products, the GF pasta currently on

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77 the market is still far from what the consumer is looking for (Marti & Pagani, 2013).

78 Basically, in GF pasta, the role of gluten could be replaced by choosing suitable

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79 formulations and recipes using the correct amount of proteins, hydrocolloids and

80 moisture to achieve the desirable quality attributes after the traditional hydrothermal
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81 treatment, but also making the dough easy to handle under industrial conditions
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82 (Larrosa, Lorenzo, Zaritzky, & Califano, 2013).

83 Starch has to assume a structuring role, which is related to the tendency of its

84 macromolecules to re-associate and interact after gelatinization, resulting in newly

85 organized structures that retard further starch swelling and solubilization during

86 cooking. Protein quantity and quality have received considerable attention as the most

87 important factors affecting both wheat pasta properties (D'Egidio, Mariani, Nardi,

88 Novaro, & Cubadda, 1990), and GF pasta (Marti et al., 2014). In some cases, also low
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89 amounts of emulsifiers (Chillo, Laverse, Falcone, & Del Nobile, 2008) and hydrocolloids

90 (Singh, Raina, Bawa, & Saxena, 2004) are added. Nowadays, the most used

91 ingredients in gluten-free pasta production are: rice and corn flours (Arendt, Morrissey,

92 Moore, & Dal Bello, 2008; Larrosa, Lorenzo, Zaritzky, & Califano, 2012), flours from

93 pseudo cereals (Chillo et al., 2008; Fiorda, Soares Jr, da Silva, Grosmann, & Souto,

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94 2013) starches of different origin (Huang, Knight, & Goad, 2001), dairy products and

95 vegetable proteins (Marti et al., 2014; Mirhosseini et al., 2015).

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96 The amount of water used in pasta processing should be optimized to achieve pasta

97 color and textural characteristics according to market preferences (Fu, 2008; Hou,

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98 Otsubo, Okusu, & Shen, 2010). It has been informed that insufficient water produce

99 streaky and/or flaky dough sheet surfaces (diminishing pasta color), resulting in softer

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cooked pasta texture (Hou et al., 2010). Using above optimum levels of water in the
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101 formulation also has adverse quality effects, as doughs will be stickier to handle and

102 difficult to sheet tending to produce poor quality finished pasta (Fu, 2008; Hatcher,
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103 Kruger, & Anderson, 1999; Hou et al., 2010).

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104 In previous works, Larrosa et al. (2013) optimized gluten-free (GF) pasta dough
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105 composition to achieve the desirable textural and rheological properties of the

106 uncooked dough, evaluating its handling properties such as extensibility, ease of
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107 processing, smoothness, and non-adhesiveness. The aim of the present work was to

108 improve the GF pasta dough formulation previously proposed (Larrosa et al., 2013) by
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109 studying cooked quality attributes at the optimal cooking time. To fulfill this global
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110 objective three steps were completed: i) the relationship between egg-proteins and

111 water contents and quality features of cooked GF pasta was analyzed; ii) the precise

112 amount of components to obtain a high quality GF cooked pasta was predicted based

113 on the response of those characteristics that were significantly affected by composition;

114 iii) the predicted optimal formulation was prepared and the cooked GF pasta was

115 characterized, to validate the procedure.

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117 2. MATERIALS AND METHODS

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119 2.1. Materials

120 Corn flour and corn starch were purchase from Herboeste (Bs As, Argentina) and

121 Saporiti (Bs As, Argentina), respectively. Dry egg and dry egg-white were kindly

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122 provided by Ovobrand SA (Brandsen, Argentina). Used hydrocolloids were food-grade

123 commercial xanthan (XG) and locust been gums (LBG) obtained from Sigma- Aldrich

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124 Co. (St. Louis, MO). Analytical grade NaCl, sunflower oil (AGD, Bs As, Argentina), and

125 cold distilled water were also used.

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127 2.2. Experimental design

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A two-way factorial design was employed to analyze the effect of water and protein
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129 content on the quality of cooked pasta (Larrosa, Lorenzo, Zaritzky, & Califano, 2015).

130 Three levels for moisture content (34.8 g/100g, 36.13 g/100g, and 37.5 g/100g) and
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131 two for egg-proteins (2.7 g/100g and 6.6 g/100g) were adopted (Table 1). An additional
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132 central point was included and replicated three times to better interpret the interaction
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133 of components and evaluate curvature in the mathematical models (W2EP2).

134 Water plus egg-proteins contents (dry whole-egg + dry egg-white, 10:1) ranged
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135 between 37.5 g/100g and 44.1 g/100g, thus the corn starch and corn flour mixture

136 varied from 56.2 g/100g to 49.6 g/100g, accordingly. The ratio between corn starch and
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137 corn flour was 4:1 in all formulations

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138 As a control, wheat pasta formulated with 67 g/100g of commercial wheat flour (Molino

139 Cañuelas, Bs As, Argentina) and 33 g/100g fresh eggs was also prepared.

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141 2.3. Pasta dough sample preparation

142 The basic formulation of the dough was taken from a previous work where composition

143 was optimized to obtain a good quality uncooked pasta dough (Larrosa et al., 2013): 1

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144 g/100g NaCl, 2.8 g/100g sunflower oil, 2.5 g/100g of a mixture of XG and LBG in a 2:1

145 ratio.

146 The mixing protocol adopted to prepare GF dough was previously described by Larrosa

147 et al. (2013). Once the laminated dough was obtained, representative subsamples

148 were cut from these sheets and kept in airtight polystyrene containers to avoid moisture

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149 loss until assessment of their functional characteristics. Ambient temperature was kept

150 at 20 ºC throughout dough preparation.

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151 Two different geometries were used: band pasta (tagliatelle, 8x2x150 mm) and lasagna

152 sheet (80x80x2 mm). Tagliatelle shaped pasta was used to analyze texture and the

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153 other quality parameters, while rheological properties were determined using circles

154 (35 mm diameter) cut from the lasagna sheet, to entirely cover the measuring surface

155 of the sensor.

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156

157 2.4. Cooking properties

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158 2.4.1. Pasta quality evaluation

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159 The optimal cooking time for each formulation was determined using method AACC 66-
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160 50 (AACC, 2000). The cooking tests were performed for various cooking times for each

161 pasta sample in order to determine the optimal cooking time (OCT). Briefly 25 g of
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162 tagliatelle was cooked in 300 ml of boiling distilled water. OCT was when the white core

163 in the pasta was still present but disappeared after squeezing between two glass
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164 slides. Once the OCT was evaluated, the pasta sample was optimally cooked and the
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165 solid loss and water absorbed during cooking were determined by triplicate.

166 Cooking loss (g loss/100g initial dough) was measured by evaporation of the cooking

167 water to dryness in an oven-tray (100 °C). Absorbed water was measured as the

168 weight increase of tagliatelle before and after cooking, and was expressed as percent

169 weight gain with respect to the weight of uncooked pasta (Bonomi et al., 2012).

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171 2.4.2. Total organic matter (TOM)

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172 Total organic matter (TOM) is the amount of organic matter released from the cooked

173 pasta during exhaustive rinsing. 25 g drained pasta was washed with 500 ml water to

174 remove the substance coating the surface of cooked pasta. Then the washing water

175 was analyzed for TOM (D'Egidio et al., 1982) using a commercial test for Chemical

176 Oxygen Demand analysis (Hach Cat. Nº 24159, Hach Co., CO, USA). Water samples

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177 digestion (2 h, 150 °C) was performed in a Hach COD Reactor 45600, and absorbance

178 was measured (Hach DR 2000 photometer). TOM value was expressed as g

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179 starch/100g dough. Measurements were done in triplicate.

180

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181 2.5. Color analysis

182 The color of raw and cooked pasta was measured using a Minolta Chroma Meter (CR-

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400, Minolta Co., NJ, USA). CIE color parameters lightness (L*), redness (a*), and
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184 yellowness (b*) were determined. At least three different regions of the lasagna sheets

185 were measured.

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186
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187 2.6. Rheological analysis: Viscoelastic Oscillatory measurements

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188 Dynamic oscillatory tests were performed on lasagna sheets cooked until the OCT in a

189 RS600 Rheometer (Haake, Germany) with parallel plate geometry (PP35S, 1.6 mm
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190 gap), following the protocol adopted by Larrosa et al. (2015). Three replicates of each

191 sample were analyzed.

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192 To analyze the effect of composition on the rheological characteristics of cooked GF

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193 pasta, an empirical time-concentration superposition method was applied, using the

194 plateau modulus (GN0) as the normalization factor. This parameter can be considered

195 as a characteristic parameter of this region and it was evaluated for each formulation

196 as follows: first the discrete relaxation spectra (Gi, λi) described by the generalized

197 Maxwell model was calculated from the mechanical spectra using the software IRIS

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198 (Rheo-hub 2007); afterwards, the plateau modulus (GN0) was computed as the sum of

199 the relaxation moduli (Larrosa et al., 2015).

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201 2.7. Texture analysis

202 Texture analysis were performed in a TAXT2i Texture Analyzer (Stable Micro

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203 Systems,UK). For every formulation at least ten repeated measurements were done

204 and mean values were reported. Measurements were carried out on cooked samples

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205 dipped in cool water soon after cooking in order to stop the cooking process.

206 2.7.1. Cutting force

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207 This test was used to determine the maximum force (N) needed to cut the cooked

208 pasta (100% compression). Each analysis was carried out on five strands of cooked

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tagliatelle at room temperature (25ºC) using the Light Knife Blade A/LKB probe to
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210 simulate the bite action of incisive teeth (speed=0.5 mm/s).

211 2.7.2. Texture profile analysis (TPA)

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212 The texture of cooked pasta was determined with two compression cycles test using a
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213 25 mm diameter flat-ended cylindrical probe (P/25). The experimental procedure was
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214 as follows: 5 tagliatelle were placed on the base and were compressed twice to give a

215 two complete compression-relaxation-tension profile curve. The test speed was set on
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216 0.5 mm/s and the compression distance was 30% of the original size (Olivera &

217 Salvadori, 2009). From the force–time curve, hardness, cohesiveness, adhesiveness
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218 (negative force of the first compression cycle), springiness, chewiness, and resilience
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219 were obtained (Szczesniak, 2002).

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221 2.8. Statistical analysis

222 A second order complete polynomial equation was used to fit the behavior of each

223 measured variable as a function of dough composition (Myers, Montgomery, &

224 Anderson-Cook, 2009):

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226 Y = β 0 + β1C1 + β 2 C 2 + β11C12 +β 22 C 2 2 + β12 C1C 2 + β112 C12 C 2 + β122 C1C 2 2 (1)

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228 where Ŷ is the response variable, β0 is the constant term, β1 and β2 are the linear

229 coefficients, β11, β22, β12, β112, β122 are quadratic and interaction coefficients. C2 and C1

230 are the water and egg-protein contents expressed as coded variables.

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231 Data were modeled adopting backward stepwise analysis and only the variables

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232 significant at P < 0.05 were selected for the model construction.

233 To validate the assumptions used in the analysis of variance (ANOVA), residual

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234 analysis was performed after model fitting was done. The adequacy of the model was

235 verified using a “lack of fit” test and the “Adequate Precision” coefficient (Montgomery,

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236 2012).
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237 After all the variables have been regressed as a function of egg-proteins and water

238 concentration in the dough, optimal formulation of GF pasta was obtained by

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239 Derringer’s desired function methodology (Derringer, 1980). The method involves
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240 transformation of each predicted response, Ŷ , to a dimensionless partial desirability

241 function, di, which includes the researcher’s priorities and desires when building the
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242 optimization procedure. The partial desirability functions are then combined into an
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243 overall desirability function D, defined as the geometric mean of di values (Derringer,

244 1980; Larrosa et al., 2013). The formulation that gives the highest D was considered as
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245 the “optimum”.

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246 Quality attributes similar to those of cooked wheat pasta were considered as target

247 values for the optimization process to establish the best formulation to produce cooked

248 gluten-free pasta. The attributes considered were: cooking loss, TOM, cutting force,

249 hardness, springiness, adhesiveness, and resilience.

250 Once the optimal formulation was computed, a batch of GF pasta was prepared using

251 the optimal ingredient levels and quality characteristics were determined as described

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252 above. Finally results were statistically compared to the values predicted by the

253 mathematical model.

254 Regression analysis, optimization, and response surfaces were accomplished using

255 the software Design-Expert® (Stat-Ease Inc., Minneapolis, USA). ANOVA and pairwise

256 comparisons (Tukey’s test) were computed using the SYSTAT software (SYSTAT, Inc.,

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257 Evanston, IL). Differences in means were considered significant when P<0.05.

258 Standard errors of the mean values are shown between parentheses

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259

260 3. RESULTS AND DISCUSSION

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261 Cooking process is a critical step in the perception of good quality pasta. Several

262 reactions are produced during pasta cooking as a result of the heat effect and water

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uptake (for example protein swelling, starch gelatinization, increase in pasta weight and
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264 volume). In the present work 10 minutes were established as the OCT for all the

265 assayed gluten-free formulations. These results agree with those reported by Yalcin
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266 and Basman (2008) for GF rice starch spaghetti prepared with different proportions of
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267 gelatinized starch.

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269 3.1. Rheological analysis

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270 Mechanical spectra of GF cooked pasta always showed a “gel like” behavior with a

271 storage modulus (G’) scarcely dependent on the frequency and a minimum in the loss
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272 modulus, G’’. This type of behavior is typically observed in elastic solids. The existence
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273 of both a plateau region in the G’ or a minimum in the G’’ vs. frequency curves, indicate

274 the formation of a gel structure due to the crosslinking by intermolecular interactions.

275 The normalized dynamic master-curves of G’ and G’’ can be seen in Fig. 1. All data fell

276 into a single master-curve in reasonable approximation. The plateau modulus (GN0),

277 used as a normalization factor, is a viscoelastic parameter defined for polymers as the

278 extrapolation of the entanglement contribution to the viscoelastic functions at high

279 frequencies (Larrosa et al., 2015). The fact that these master-curves could be achieved
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280 by applying an empirical vertical superposition method implies that the different

281 compositions did not modify the overall microstructural pattern of systems, but mainly

282 influenced the level of interactions among macromolecular components.

283 When formulations prepared with the same water content and different protein

284 concentrations were analyzed (W2EP1, W2EP2, and W2EP3) the shift factors were

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285 practically coincident since the plateau modulus did not significantly differ among

286 samples (Fig. 1a). However, GN0 diminished when initial water content increased as

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287 could be observed in the example shown in Fig. 1b. This behavior revealed a decrease

288 in the elasticity of the pasta when the dough contained larger amount of water.

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289

290 3.2. Cooking properties and color

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The weight of a cooked pasta indicates the water uptake and corresponds to a
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292 macroscopic event involving a complex molecular modification of starch and proteins,

293 mainly hydration (Nouviaire, Lancien, & Maache-Rezzoug, 2008; Sozer, Dalgic, &
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294 Kaya, 2007). Water absorption was not significantly affected by formulation; average
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295 value was 61.6(2.2) g/100g, similar to the water absorption informed by Vijayakumar
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296 and Boopathy (2012) who worked with pasta prepared with wheat, cassava, and soy

297 flours.
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298 Total organic matter lost (TOM), expressed in terms of starch is shown in Table 2 for all

299 the studied formulations. For GF pasta TOM ranged between 0.18 and 0.49 g/100g
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300 (dough basis), which according to D'Egidio et al. (1982) corresponds to a good quality
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301 cooked pasta (TOM<1.4 g/100g). According to Alamprese, Iametti, Rossi, and

302 Bergonzi (2005), the heat treatment of pasta causes denaturation of proteins, leading

303 to a stiffening of pasta structure, with a consequent reduction in the mass loss during

304 cooking.

305 Regression coefficients obtained for the predictive models for TOM and cooking loss

306 are shown in Table 3; lack of fit and precision adequacy values revealed that the

307 models were convenient. As EP decreases or water in the dough increases more
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308 organic matter is lost from the surface of the cooked pasta; the positive interaction term

309 reflects that the dependence of TOM with water concentration is stronger at higher EP

310 contents. Higher egg-proteins fraction in the formulation may form a more compact

311 network that does not allow for an easy release of organic matter during cooking,

312 leading to a reduction in the free organic matter released to the rinsing water.

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313 Cooking loss, related to solid leaching during cooking (D'Egidio et al., 1982), is widely

314 used as an indicator of the overall cooking performance considering it as an index of

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315 resistance to disintegration during cooking of pasta (Matsuo, Malcolmson, Edwards, &

316 Dexter, 1992). Low amounts of residue indicate high quality cooked pasta (Del Nobile,

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317 Baiano, Conte, & Mocci, 2005). In gluten-free pasta starch polymers are less efficiently

318 entrapped in the matrix because of the lack of gluten network, giving a final product

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with high losses during cooking (Marti & Pagani, 2013). Data in the present paper
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320 showed that the highest cooking losses corresponded to W3EP1, which could be

321 attributed to the lack of a well-structured protein reticule, hindering the excessive
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322 swelling of the starch granules and the consequent dispersion of components in the
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323 cooking water (Alamprese, Casiraghi, & Pagani, 2007). The smallest losses
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324 corresponded to formulation W1EP3. These results agree with Malcolmson, Matsuo,

325 and Balshaw (1993), who informed that cooking loss decreased significantly as protein
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326 level increased. In gluten-free pasta made from parboiled rice flour, Marti et al. (2014)

327 found that egg albumen was significantly more efficient to decrease cooking loss than
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328 using whey protein.

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329 Cooking losses varied from 6.2 g/100g to 13.8 g/100g (Table 2). Hoseney (1994)

330 informed that good quality pasta should present cooking losses <12 g/100g; thus it

331 could be concluded that all the formulations assayed could be considered acceptable

332 except W3EP1 (13.8 g/100g, SEM=0.81 g/100g).

333 It is noteworthy that there was a negative correlation between G’, G’’ and cooking loss

334 (R2=0.81, P<0.05 and R2=0.79, P<0.05, respectively). When more solids were leached

335 to the cooking water, elastic characteristics of pasta diminished.

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336 Cooking affected color parameters of GF pasta decreasing lightness from 86.04(0.44)

337 to 78.46(0.37), a* from 1.14(0.10) to 0.72(0.08), and b* from 26.29(0.31) to

338 22.16(0.26). On the other hand these parameters were not influenced by initial dough

339 composition.

340

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341 3.3. Texture

342 Cutting force test

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343 Cutting force is directly related to cooked pasta firmness. Table 2 shows the average

344 values of this force, ranging from 6.5 to 13.8 N for GF formulations and a significantly

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345 higher value of the firmness for the wheat pasta analyzed (29.1 N). The smallest

346 cutting force corresponded to W1EP1 which contained the lowest water and egg-

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proteins contents and thus the highest starch concentration.
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348 In Fig. 2 it can be appreciated the influence of both water and egg-proteins contents on

349 the cutting force of GF cooked tagliatelle; the obtained regression coefficients are
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350 shown in Table 3. At low EP, firmness showed a strong linear dependence on W
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351 content, low water content produced more firm products; conversely, at high EP there
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352 was a quadratic dependence on W reaching a minimum force at an intermediate water

353 fraction. On the other hand, at high water content, firmness was directly proportional to
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354 EP level.

355 Regarding the TPA parameters, Table 3 shows the computed regression coefficients
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356 for hardness, springiness, adhesiveness, and resilience, and Fig. 3 a, b, c, and d the
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357 corresponding response surfaces. From the regression coefficients, it can be seen that

358 both water and protein contents strongly affected hardness; maximum hardness

359 corresponded to intermediate water levels while it was minimum for high and low water

360 contents at intermediate protein concentration.

361 Raw dough initially containing the smallest amount of water also had the largest starch

362 content, which could explain the strong effect of initial water concentration on cooked

363 pasta hardness. Wheat control samples showed higher hardness values (41.8 N,
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364 SEM=1.6 N) than all GF tagliatelles demonstrating the importance of the gluten matrix

365 on tagliatelle texture.

366 Fig. 3b shows that as protein concentration increased the product became less elastic

367 (smaller springiness), regardless of water content. As smaller EP concentration

368 corresponded to larger amounts of starch in the product; it seems that denaturated

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369 egg-proteins contributed less to elasticity than the cooked corn-starch. The quadratic

370 dependence of springiness on water content was also noticeable, where intermediate

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371 contents corresponded to maximum springiness.

372 Cooked pasta resilience was strongly correlated to EP content and the corresponding

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373 response surface is shown in Fig. 3c. The main effect observed was that increasing EP

374 in the formulation resulted in GF pasta with larger capacity of recovery after being

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subjected to strain. Since interaction between components had a significant effect,
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376 pasta resilience exhibited a quadratic dependence on dough moisture enhanced at low

377 EP.
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378 Adhesiveness shows that in those formulations with low protein content there was a
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379 strong positive correlation with initial moisture level (Fig. 3d). A marked interaction was
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380 found, at high protein concentration lowering water content slightly increased pasta

381 adhesiveness. Pasta adhesiveness is related to the amount of starch granules that
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382 exudates from the pasta matrix into the cooking water and coats the surface of the

383 product (Dexter, Matsuo, & MacGregor, 1985). A positive relationship between cooking
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384 loss and adhesiveness was observed (R2=0.96, P<0.05).

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385 Comparing resilience and adhesiveness it could be concluded that high protein content

386 was necessary to achieve high quality GF pasta. Thus, proteins must maintain enough

387 resilience to cope with starch swelling during cooking. Conversely, when protein

388 content decreased in a high dough moisture, the protein network cannot withstand the

389 starch swelling, and as a consequence, the final cooked pasta resulted stickier and

390 more material was lost during cooking.

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391 Cohesiveness of cooked pasta is mainly dependent on competition between starch and

392 protein molecules to form a continuous network (Riva, Fessas, & Schiraldi, 2000; Sozer

393 et al., 2007). In the present work, cohesiveness ranged from 0.57 to 0.71 for all studied

394 samples and none of the GF formulations significantly differed from the wheat flour

395 control (P>0.05).

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396 Chewiness of gluten-free pasta could be related to the elastic force of the protein

397 matrix in the sample (Sozer et al., 2007); the highest chewiness value was 39.9(0.8)

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398 and corresponded to W1EP3 (highest level of proteins and lowest level of water).

399 Although a polynomial model did not adequately fit experimental data of chewiness, the

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400 analysis of variance showed that there was a significant EPxW interaction, at EP=+1

401 chewiness was inversely proportional to water content in the dough while the opposite

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effect was found at EP=-1. Control wheat flour dough presented an average chewiness
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403 of 26.8(1.0), which was in the range of the values of the GF pasta evaluated.

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405 3.6. Optimization and verification

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406 Individual predictive equations were calculated (Eq. (1), Table 3); computed lack of fit
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407 tests were always non significant, and “adequate precision” values were in all cases

408 above 4 indicating a high significance and adequacy of the models.

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409 A good quality pasta product should present certain degrees of firmness and elasticity,

410 appearance uniformity and structural integrity (Edwards, Biliaderis, & Dexter, 1995;
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411 Sozer et al., 2007), low TOM, cooking losses, and adhesiveness (Antognelli, 1980;
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412 D'Egidio et al., 1982; Dexter, Matsuo, & Morgan, 1983; Pomeranz, 1987). Table 4

413 shows the optimization criteria for each desirability function. Cooking loss, total organic

414 matter and adhesiveness were minimized. Hardness and cutting force were maximized

415 since all GF pasta were less firm than wheat control samples. The desirable ranges of

416 springiness and resilience were established according to control pasta (Table 2). The

417 optimum combination of ingredients to add in gluten-free dough formulation

418 corresponded to 6.6 g/100g egg-protein mix and 35.96 g/100g water, with an overall
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419 desirability D=0.603 which is acceptable considering the large number of responses

420 optimized simultaneously. Table 4 also shows the predicted responses for this

421 composition and the corresponding di function values.

422 Once the optimum formulation was determined, it was used to manufacture gluten-free

423 tagliatelle which were cooked as described above and all the response variables of this

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424 product were analyzed. Experimental values of each response are presented in Table

425 4. It could be observed that the model obtained using surface response methodology

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426 was satisfactory since all textural variables agreed with the predicted values (P > 0.05).

427 Cooking losses and total organic matter were overestimated by the model, but this

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428 result is not detrimental to the predictive model because the optimized formulation

429 resulted in a well-structured network enhancing the organic matter retention. This study

430
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allowed us to determine a composition to produce high quality cooked gluten-free
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431 pasta.

432
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433 4. Conclusions
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434 The effect of dough composition (water and protein content) of GF pasta on
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435 viscoelastic, textural, and quality attributes of the cooked product (water absorption,

436 cooking loss and total organic matter) was evaluated. Dough moisture mainly affected
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437 the elastic behavior of GF pasta leading to a significant decrease in the plateau

438 modulus when water content was increased. Springiness, resilience, and adhesiveness
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439 were mainly controlled by the egg-protein content in the dough, while cooked pasta
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440 hardness increased when dough moisture decreased and starch content increased.

441 The statistical methodology was effective and reliable in finding the optimal

442 composition (6.6 g/100g egg-protein and 35.96 g/100g water) to obtain high quality

443 gluten-free cooked pasta. Using this optimized composition pasta was prepared and

444 experimental results of the cooked product agreed closely with the predicted values of

445 the parameters.

446
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447

448 Acknowledgements

449 The authors are grateful to Ovobrand S.A., Argentina, who provided the dried egg and

450 the ovoalbumin protein for this study. The financial support of the Consejo Nacional de

451 Investigaciones Científicas y Tecnológicas (CONICET), Agencia Nacional de

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452 Promoción Científica y Tecnológica and Universidad Nacional de La Plata are also

453 acknowledged.

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454

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Table 1. Composition of the studied formulations. Protein and water contents are given

as percentages of the total fresh dough.

Composition (g/100g) Coded levels

Formulation Egg-protein Water

Dry egg Dry egg-white Water
(EP) (W)

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W1EP1 2.45 0.25 34.8 -1 -1

W2EP1 2.45 0.25 36.13 -1 0

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W3EP1 2.45 0.25 37.5 -1 1

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W2EP2 4.23 0.42 36.13 0 0

W1EP3 6 0.6 34.8 1 -1

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W3EP3 6 0.6 37.5 1 1
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Table 2. Cooking losses, total organic matter (TOM), and main textural parameters of the studied formulations of GF and wheat (control

formulation) pasta expressed as mean ± SEM.

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Cooking loss TOM g
Cutting force Adhesiveness
Formulation (g/100g pasta (starch/100g Hardness (N) Springiness Resilience

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(N) (N)
dough) pasta dough)

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W1EP1 10.49 ± 0.88 0.288 ± 0.021 12.98 ± 0.17 8.53 ± 1.81 0.913 ± 0.009 0.486 ± 0.021 0.81 ± 0.159

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W2EP1 11.60 ± 0.47 0.355 ± 0.019 10.27 ± 0.18 34.18 ± 1.38 0.938 ± 0.007 0.533 ± 0.008 1.41 ± 0.163

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W3EP1 13.76 ± 0.57 0.384 ± 0.005 7.00 ± 0.08 26.31 ± 2.92 0.911 ± 0.011 0.498 ± 0.022 1.82 ± 0.177

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W2EP2 (r1) 10.55 ± 0.26 0.559 ± 0.011 9.00 ± 0.15 13.76 ± 0.96 0.920 ± 0.007 0.619 ± 0.010 1.12 ± 0.171

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W2EP2 (r2) 10.01 ± 0.24 0.511 ± 0.048 9.27 ± 0.26 13.22 ± 1.07 0.926 ± 0.004 0.630 ± 0.018 1.22 ± 0.153

W2EP2 (r3) 10.28 ± 0.42 0.431 ± 0.033

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8.97 ± 0.20 14.81 ± 0.79 0.919 ± 0.009 0.628 ± 0.021 1.19 ± 0.106
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W1EP3 8.28 ± 0.56 0.183 ± 0.027 8.92 ± 0.19 6.09 ± 1.13 0.809 ± 0.041 0.633 ± 0.026 0.90 ± 0.184
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W2EP3 9.90 ± 0.46 0.267 ± 0.009 8.18 ± 0.19 23.49 ± 1.95 0.892 ± 0.017 0.645 ± 0.017 1.18 ± 0.077
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W3EP3 6.24 ± 0.20 0.425 ± 0.051 9.51 ± 0.21 20.74 ± 2.05 0.833 ± 0.015 0.524 ± 0.021 0.66 ± 0.072

Wheat control 4.76 ± 0.14 0.15 ± 0.013 29.1 ± 1.04 41.8 ± 1.6 0.95 ± 0.064 0.68 ± 0.043 0.84 ± 0.024
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Table 3. Regression coefficients for the predictive models for total organic matter (TOM), cooking loss, cutting force, hardness, springiness,

adhesiveness, and resilience. Statistical significance of the models (P), R2, lack of fit, and “adequate precision” coefficient, are also included.

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TOM (g Cooking loss
Cutting force Adhesiveness
Model terms starch/100g (g/100g pasta Hardness (N) Springiness Resilience

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Constant +0.49 10.08 +9.17 +13.91 +0.92 +1.1 +0.63

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Protein -0.035 - -1.05 -3.43 -0.038 -0.26 +0.047

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Water +0.069 - -1.26 +8.23 - +0.16 -0.023

Water* Protein +0.051 -1.21 +1.73 - - -0.36 -0.028

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Water2 +0.024 - +0.52 -13.53 -0.046 - -0.055

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Protein2 -0.18 - +14.84 - - -0.037

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(Water2)* Protein - -2.55 +0.75 - - - -
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Model (P) <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001

R2 0.611 0.801 0.878 0.761 0.719 0.89 0.654

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Lack of fit 0.7437 0.1735 0.442 0.093 0.067 0.085 0.330

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Adequate
7.979 17.577 38.89 17.99 9.72 10.57 9.11
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Table 4. Criteria used to obtain the desirability functions, predicted responses, and

individual desirability functions (di).

Predicted Individual Experimental

Parameter Objective
response desirability values di response

Cooking loss
Minimum 10.20 0.498 5.02 (1.32)

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(g/100 g)

Total organic

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matter (TOM, Minimum 0.99 0.734 0.19 (0.05)

g/100 g)

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Cutting force(N) Maximum 8.08ª 0.217 10.52a (1.00)

Hardness (N) Maximum 23.86ª 0.576 27.40a (1.41)

range
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Springiness (-) 0.880ª 1 0.94a (0.04)
(0.88-0.98)

Adhesiveness (N) Minimum 0.875ª 0.637 1.05a (0.59)

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Range
Resilience (-) 0.642ª 1 0.54a (0.12)
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(0.60-0.75)
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Standard errors of the mean are shown between parentheses

* Experimental responses with the same superscripts than predictive response indicate
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there are no significant differences (P< 0.05).

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FIGURE CAPTIONS

Fig. 1. Normalized dynamic master curves of the elastic (G’/ GN0, filled symbols) and

viscous (G’’/ GN0, empty symbols) moduli for cooked pasta. (a) water: 36.1 g/100 g and

(
) 2.7, () 4.65, and (
) 6.6 g/100 g egg-protein; (b) egg-protein: 2.7 g/100 g

and (
) 34.8, () 36.1, and (
) 37.4 g/100 g water; Continuous lines represent

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the fitting using Maxwell model. Inset plots correspond to GN0 values used to normalize

the mechanical spectra.

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Fig. 2. Effect of egg-proteins and water contents on the cutting force of cooked gluten-

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Fig. 3. Surface responses of: a) hardness, b) springiness, c) resilience, and
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d)adhesiveness as a function of egg-protein and water contents (g/ 100 g dough).
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HIGHLIGHTS

> Egg protein and water content affected the quality and texture of gluten-free pasta.

> Rheological properties were mainly controlled by dough moisture.

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> Composition was optimized using desirability criteria based on texture and quality.

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> Optimized pasta was prepared and the predicted behavior was experimentally

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validated.

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