Retention and release kinetics of aroma compounds from white sauces made with native waxy maize and potato starches: Effects of storage time and composition

Accepted Manuscript Retention and release kinetics of aroma compounds from white sauces made with native waxy maize and potato starches: Effects of storage time and composition

Grażyna Bortnowska, Zuzanna Goluch-Koniuszy PII:

S0268-005X(18)30205-4

DOI:

10.1016/j.foodhyd.2018.06.046

Reference:

FOOHYD 4523

To appear in:

Food Hydrocolloids

Received Date:

03 February 2018

Accepted Date:

27 June 2018

Please cite this article as: Grażyna Bortnowska, Zuzanna Goluch-Koniuszy, Retention and release kinetics of aroma compounds from white sauces made with native waxy maize and potato starches: Effects of storage time and composition, Food Hydrocolloids (2018), doi: 10.1016/j.foodhyd. 2018.06.046

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ACCEPTED MANUSCRIPT 40

Retention, columns (-)

Enthalpy, lines (kJ/mol)

1.200000018

0.800000012 Rapeseed oil, 3 wt%. Skimmed milk powder, 10 wt%

30

0.400000006

20

0

10 2

3

4

Waxy maize starch concentration (wt%)

Ethyl acetate (EA) EA

Hexanal (HE) HE

Graphical abstract

5

R-(+)-limonene (RL) RL

ACCEPTED MANUSCRIPT 1

Retention and release kinetics of aroma compounds from white sauces made with native

2

waxy maize and potato starches: Effects of storage time and composition

3 4

Grażyna Bortnowskaa*, Zuzanna Goluch-Koniuszyb

5 6

a

7

b Department

Department of Food Technology, West Pomeranian University of Technology in Szczecin, Poland of Animal Food Technology, Wrocław University of Economics, Poland

8 9

ABSTRACT

10

Retention (R) of ethyl acetate (EA), hexanal (HE) and R-(+)-limonene (RL) in white sauces

11

(WS) during 10-days refrigerated storage period was analyzed quantitatively using static

12

headspace gas chromatography-mass spectrometry in relation to: starch type (waxy maize

13

starch, WMS; potato starch, PS), starch concentration (2-5 wt%) and rapeseed oil (RO)

14

content (3 or 9 wt%). The Avramis equation was implemented to determine release rate

15

constants (k) and release mechanism parameters (n). The enthalpy (H) of aroma compounds

16

(AC) affinity was calculated using vant Hoffs model, from the variations of equilibrium

17

partition coefficients (kg/m) of AC, determined between the air (g) and matrixes (m) at

18

temperatures ranged from 20 to 50 °C. The R values were significantly (p < 0.05) affected by

19

both starch type (ST) and starch concentration (SC) and generally were greater in samples

20

stabilized with PS than WMS, most probably due to the higher amylose content. Increase of

21

RO amount, enhanced R values, particularly regarding HE and RL. Irrespectively of the ST,

22

the k values showed descending tendency with raising SC and were higher for EA than for

23

more hydrophobic AC (HE, RL). In all WS, the release mechanism was found to be

24

controlled by molecular diffusion and the n values were in ranges: 0.59– 0.82 and 0.56–0.81,

25

in WS composed of 3 and 9 wt% RO, respectively. The magnitudes of H related to the

1

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energy required for partitioning of AC from WS to the headspace, were greatly dependent on

27

both AC properties and WS composition, particularly ST and SC.

28 29

Keywords: Aroma compounds; Gas chromatography; Release kinetics; Retention; Starch;

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White sauce

31 32

*Corresponding author. E-mail: [email protected]

33 34

1. Introduction

35 36

White sauces (WS) are oil-in-water emulsions, frequently used in the formulation of

37

ready-to-eat products to improve their flavor and conduct heat during thermal treatment. The

38

basic components of WS are: milk, oil and thickeners, mostly starches or flours (Hernández‑

39

Carrión et al., 2015; Sanz, Tárrega, & Salvador, 2016). The major milk proteins are caseins:

40

s1, s2, ,  and whey proteins: -lactoglobulin, -lactalbumin, bovine serum albumin,

41

immunoglobulins, lactoferrin (Livney, 2010). Starch exists in its native form as semi-

42

crystalline granules that are essentially composed of two polyglucans. Amylopectin (AP) is

43

the major component in most starches. The extensively branched structure consists of short

44

chains of -(1,4)-linked D-glucosyl units that are interconnected through -(1,6)-linkages.

45

Amylose (AM) is essentially linear with much longer chains than in AP (Considine et al.,

46

2011; Vamadevan & Bertoft, 2015). The amylose content of the starch varies with its

47

botanical source. Typically starch from genetically unmodified potato varieties contains 17-22%

48

amylose, whereas waxy maize starch is composed of about 99% amylopectin, so it is

49

fundamentally amylose free biopolymer (Copeland, Blazek, Salman, & Tang, 2009; Tomasik,

50

2009). Milk proteins, in both soluble and dispersed forms, are commonly known to be 2

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excellent emulsifiers because they exhibit good surface-active properties by reducing the

52

tension at the oil−water interface (Ye, 2011). Starch is used as thickening agent and to form

53

desired by the consumer texture (Bortnowska et al., 2016; Sanz et al., 2016). Moreover, the

54

interactions of milk proteins themselves and with starch molecules can provide benefit to the

55

WS (Considine et al., 2011; Matignon et al., 2015).

56

The presence of aroma compounds (AC) determines peculiar sensory attributes of food

57

products and influences thus on the consumer acceptability (Taylor, 2002; Aguiló-Aguayo,

58

Montero-Calderón, Soliva-Fortuny, & Martín-Belloso, 2010; Chen, Guo, Wang, Yin, & Yang,

59

2016). Typically, food aroma is a mixture of hundreds AC, in majority low molecular weight

60

(< 400 g/mol) organic compounds. The chemical structures of AC vary widely including:

61

alcohols, aldehydes, ketones, acids, terpenes, esters and others. There are also large

62

differences regarding physicochemical properties with the most important for foods such as:

63

hydrophobicity (log P), solubility, saturated vapor pressure, molecular weight and molecular

64

volume (Naknean & Meenune, 2010; Rao & McClements, 2012; Reineccius, 2006). For the

65

current studies: ethyl acetate (EA), hexanal (HE) and R-(+)-limonene (RL) were chosen

66

because they belong to different chemical classes, represent a wide range of physicochemical

67

properties and exhibit different behavior towards starch and proteins, moreover are

68

ingredients of many foodstuffs or are used for their aromatization (Heilig, Heimpel, Sonne,

69

Schieberle, & Hinrichs, 2016; Lafarge et al., 2014). EA is very often employed in fruit-

70

flavored dairy formulations such as yogurt (Longo & Sanromán, 2006). The presence of

71

hexanal is related to fat oxidation reactions in processed foods, but it is also present in fruits,

72

vegetables as well as dairy and grain products (Aguiló-Aguayo et al., 2010; Chambers IV &

73

Koppel, 2013). Whereas, RL is the major constituent of citrus fruit essential oils (Li & Lu.,

74

2016; Rao & McClements, 2012; Reineccius, 2006). It was found that R-(+)-limonene

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exhibits chemopreventive and chemotherapeutic action against several types of carcinomas,

76

such as melanoma, prostate and stomach (Vandresen et al., 2014).

77

During the processing and storage losses of AC occur, which quantitatively and sometimes

78

qualitatively change their fraction in food (Secouard, Malhiac, Grisel, & Decroix, 2003). It

79

has been suggested that characteristic aroma is mainly affected by the type and concentration

80

of AC in the food headspace. Thus controlling AC release, represents a significant challenge

81

for the industry (Naknean & Meenune, 2010). There are two major factors that control the rate

82

of AC release from products, namely the volatility (thermodynamic factor) and the resistance

83

to mass transfer from product to the air (kinetic factor). Thermodynamic factor determines the

84

retention or partitioning of AC between the food and air phases under equilibrium conditions

85

(Boland, Buhr, Giannouli, & Van Ruth, 2004; De Roos, 2003; Heilig et al., 2016). The rate at

86

which equilibrium can be achieved is determined by the mass transfer coefficient, which is a

87

measure for the velocity at which the solute diffuses through the phase (De Roos, 2003;

88

Harrison, Hills, Bakker, & Clothier, 1997; Seuvre, Philippe, Rochard, & Voilley, 2007). In

89

general, at thermodynamic equilibrium, the concentration of AC in the headspace is

90

dependent on: their hydrophobicity, food composition, interactions with non volatile

91

compounds (especially carbohydrates and proteins), temperature and others (Boland et al.,

92

2004; De Roos, 2003; Heilig et al., 2016). The binding of AC to starch has been classified

93

into two types, formation of inclusion complexes (entrapping in the amylose helixes through

94

hydrophobic bonding) and polar interactions involving hydrogen bonds with hydroxyl groups

95

of starch (Arvisenet, Le Bail, Voilley, & Cayot, 2002; Boutboul, Giampaoli, Feigenbaum, &

96

Ducruet, 2002). Changes in the retention of AC due to formation of inclusion complexes with

97

high amylose starches have been reported by: Jouquand, Ducruet, & Le Bail (2006); Lafarge

98

et al. (2014); Yeo, Thompson, & Peterson (2016) and others. There are also some suggestions

99

in the literature that impact of matrix containing starch on the release of AC under

4

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equilibrium conditions appeared to be linked to their: hydrophobicity, chemical structure and

101

other physicochemical characteristics (Boland et al., 2004; Savary, Guichard, Doublier, &

102

Cayot, 2006; Van Ruth & King, 2003). Proteins interact with AC through non-specific

103

hydrophobic interactions or specific chemical interactions, e.g., covalent binding or hydrogen

104

bonding. However, the range of interactions is dependent on: the type of protein and AC,

105

presence of other food components, ionic strength, pH, temperature and others (Guichard,

106

2006; Livney, 2010; Reineccius, 2006). Numerous studies related to the microstructural,

107

physical stability and rheological properties of WS have been carried out (Bortnowska et al.,

108

2016; Hernández‑Carrión et al., 2015; Sanz et al., 2016), however those dealing with the

109

stability of AC, particularly in relation to thermodynamic and kinetic aspects, in systems

110

thickened with starch composed of different amylose/amylopectin ratio, have not been found.

111

The objective of this work was to investigate: (i) retention and release of selected aroma

112

compounds (AC) from flavored white sauces (WS) during refrigerated storage time and (ii)

113

the effect of temperature on the affinity of AC in WS depending on their composition.

114 115

2. Materials and methods

116 117

2.1. Materials

118 119

Native waxy maize starch (99.2 wt% amylopectin) and potato starch (19.4 wt% amylose)

120

were donated by Ingredion GmbH (Hamburg, Germany). Rapeseed oil (7 wt% saturated, 65

121

wt% monounsaturated, 28 wt% polyunsaturated fatty acids) and skimmed milk powder (10.2

122

wt% moisture, 37.6 wt% proteins, 51.4 wt% carbohydrates, 0.7 wt% fat) were bought from a

123

local retailer. Potassium sorbate and sodium chloride were obtained from Hartim (Szczecin,

124

Poland). The aroma compounds (purity  98%): ethyl acetate (EA), hexanal (HE) and R-(+) 5

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limonene (RL) were purchased from Sigma-Aldrich (Poland) and their physicochemical

126

characteristics are presented in Table 1.

127 128

2.2. White sauces preparation

129 130

Skimmed milk was prepared 24 h in advance by dissolving skimmed milk powder in

131

distilled water and stored under refrigeration (4 oC). Then, the milk was homogenized with

132

rapeseed oil at 7000 rpm for 20 s, using a laboratory-scale T 18 basic Ultra-Turrax package

133

homogenizer (IKA Werke GmbH Co. KG, Germany). Next, appropriate amount of waxy

134

maize starch (WMS) or potato starch (PS) were added and the systems were heated in a water

135

bath, to 90 oC (5 oC/min) at stirring speed of 1500 rpm. Subsequently, required quantities of

136

sodium chloride and potassium sorbate were put into the sauces and they were kept at 90 oC

137

for 10 min under mild agitation. Freshly prepared white sauces (WS) were cooled down up to

138

4 oC. Then the aroma compounds (EA, HE or RL) were separately incorporated, each added

139

at a concentration of 500 mg/L and the WS were manually mixed and stored in closed bottles

140

at 4 oC until analysis. The basic composition of the WS was as follows: rapeseed oil (3 or 9

141

wt%), skimmed milk powder (10 wt%), WMS or PS (2−5 wt%), sodium chloride (0.25 wt%)

142

and potassium sorbate (0.1 wt%). The experiments were conducted at fixed temperature of 4

143

oC

unless otherwise stated.

144 145

2.3. Physicochemical characteristics

146 147

Freshly prepared samples were placed in 50 ml graduated cylinders and creaming was

148

determined visually from the serum appearing at the bottom of samples during 10-days

149

refrigerated storage period. Creaming index was expressed as: CI (%) = (Vs/Vi)  100, where:

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Vi, initial volume of the emulsion and Vs, volume of serum measured after a certain time of

151

storage. Creaming rate (kc, day-1) was assessed using a first order kinetics equation: CI (%) =

152

CIeq [1− exp(−kct)], where: CIeq, equilibrium creaming index and t, storage time (day)

153

(Santana, Perrechil, Sato, & Cunha, 2011). The rheological properties of the white sauces

154

(WS) were determined using a strain/stress controlled AR-G2 rheometer (TA Instruments,

155

New Castle, DE, USA), equipped with a cone-plate geometry (2o cone angle, 60 mm diameter,

156

62 m gap) and a Peltier heating system. The apparent viscosity (a, Pa s) was measured at

157

shear rate of 1 s-1. Oscillatory (dynamic) tests (0.01−50 Hz) were conducted inside the linear

158

viscoelastic region (0.1 Pa), storage modulus (G, Pa), loss modulus (G, Pa) and complex

159

modulus: G* (Pa) = (G2 + G2)1/2 were recorded versus frequency. Bohlins parameters were

160

estimated from the equation: G* = A1/z, where: z, coordination number (dimensionless) and

161

A, proportional coefficient (Pa s1/z). Sauter mean diameter: d3,2 = nidi3/nidi2 and volume-

162

weighted mean diameter: d4,3 = nidi4/nidi3, where: ni, number of the particles with diameter

163

di, were determined using a laser diffraction technique (Mastersizer 2000, Malvern

164

Instruments Ltd., United Kingdom). The surface load of milk proteins (s) was calculated

165

according to Su & Zhong (2016), using the equation: s = Msd3,2/6Voil, where: Ms, protein

166

mass adsorbed at interface; Voil, volume of rapeseed oil. The physicochemical parameters: A,

167

z, a and d4,3, calculated during refrigerated storage period, were fitted to power law model: Y

168

= Btc, where: B, scaling factor; c, exponent and t, storage time, thus determined values of: BA,

169

Bz, Ba, Bd4,3, were taken for further calculations.

170 171

2.4. Thermodynamic study of aroma compounds release

172 173

Thermodynamic behavior of aroma compounds (AC), in white sauces (WS), was studied

174

with regard to retention and air/matrix partition coefficient. For the studies of AC retention 7

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during refrigerated storage, WS (200 mL) were transferred into 400 mL glass jars and stored

176

(without agitation and closing) in refrigerated container (equipped with ventilation system) at

177

constant temperature (4 oC) for 10 days. At fixed time intervals WS samples were subjected to

178

chromatographic analysis and the external standard method was used to quantify the residual

179

amount of AC (Kolb & Ettre, 1997; Bortnowska, 2012). The retention (R) of aroma

180

compounds was calculated from the equation: R = Mt/Mt=0, where: Mt, mass of aroma

181

compound at fixed time intervals and Mt=0, initial amount of aroma compound in the system.

182

The gas-matrixes (white sauces) partition coefficients: kg/m = Cg/Cm, where: Cg and Cm,

183

concentration of aroma compounds in the headspace and in the matrix, were determined at: 20,

184

30, 40 and 50 C, according to general procedures described by Chen et al. (2016) and Terta,

185

Blekas, & Paraskevopoulou (2006). Vant Hoffs law was used to calculate enthalpy (H, kJ/

186

mol): dlnkg/m/dT = H/RgT2, where: Rg, gas constant (J/mol K) and T, absolute temperature

187

(K) (Chen et al., 2016; Meynier, Garillon, Lethuaut, & Genot, 2003). Before chromatographic

188

analyses, headspace vials (22.3 mL) were filled with 5 0.01 mL of the WS and immediately

189

closed using a cap fitted with a Teflon-coated seal. The pre-equilibration was performed at

190

experimentally used temperatures and time of 6 h was sufficient to reach equilibrium for each

191

matrix and aroma compound.

192 193

2.5. Static Headspace Gas Chromatography-Mass Spectrometry (SH-GC-MS)

194 195

SH-GC analyses were performed on an AutoSystem XL gas chromatograph (Perkin-Elmer,

196

Switzerland). After equilibration, the headspace sample of 1 mL was automatically withdrawn

197

using a Perkin-Elmer TurboMatrix 16 autosampler and injected with splitless mode into a PE-

198

5MS capillary column (30 m  0.25 mm i.d.  0.25 m film thickness) in GC. Helium (purity

199

> 99.99%) was used as the carrier gas at a flow of 0.8 mL/min. The GC was programmed 8

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from 50 oC to 150 oC at the rate of 10 oC/min. The temperature of the transfer line was held at

201

150 oC. The mass spectrometer, quadrupole type (TurboMass) operated in the electron impact

202

mode with an electron energy of 70 eV, collecting data at a rate of 1 scan/s over a range of 40-

203

450 amu (atomic mass unit). The aroma compounds (A) were identified by comparison with

204

spectra and retention times of single authentic AC.

205 206

2.6. Calculations of the release parameters and losses of aroma compounds

207 208

Release rate constants (k) and release mechanism parameters (n) were computed by fitting

209

retention (R) values to the Avramis equation: R = exp[−(kt)n], where: t, storage time

210

(Bortnowska, 2012). Half-life release (t1/2) was calculated from the equation: t1/2 = [(−ln

211

0.5)1/n]/k. The percentage of the lost aroma compounds during 10-days refrigerated storage

212

period of white sauces, was defined using the equation: L (%) = [(Mt=0 − Mt=10 days)/Mt=0] 

213

100, where: Mt=0 and Mt=10

214

compounds.

days,

initial and after 10-days storage period amount of aroma

215 216

2.7. Statistical analysis

217 218

All experiments were performed in triplicate and the results were expressed as mean values.

219

Tukey’s test was used to determine significant (p < 0.05) differences between means. The

220

effects of oil content, starch type and concentration on the values of measured parameters

221

were analyzed by a two-way analysis of variance (ANOVA). Correlation coefficients (r) were

222

determined using Pearson’s correlation. Statistical analyses were carried out using Statistica

223

8.0 software (StatSoft Inc., USA.

224 9

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3. Results and discussion

226 227

3.1. Creaming stability of white sauces

228 229

Stability of white sauces (WS) prepared with waxy maize starch (WMS based sauces,

230

WMS-BS) or potato starch (PS-BS) was measured at one-daily intervals in relation to the

231

kinetics of gravitational phase separation expressed as creaming rate (kc) (Table 2).

232

Irrespectively of the starch type (ST) the values of kc demonstrated declining tendency with

233

raising starch concentration (SC) and the correlation (r) values between these two parameters

234

were as follows: WMS-BS (r = −0.995, p < 0.01), PS-BS (r = −0.996, p < 0.01) and WMS-BS

235

(r = −0.993, p < 0.01), PS-BS (r = −0.997, p < 0.01) with regard to WS composed of 3 and 9

236

wt% RO, respectively. ANOVA revealed, that both SC and ST, significantly affected kc

237

magnitudes, however taking into account F-values, predominant effect was observed

238

regarding SC: 3 wt% RO [F(3,16) = 396.9, p < 0.001] and 9 wt% RO [F(3,16) = 409.6, p <

239

0.001]. Samples thickened with PS demonstrated higher values of kc than those prepared with

240

WMS. These differences can be interpreted in terms that amylose retrogrades over minutes to

241

hours and amylopectin over hours to days, depending on the ability of the branched chains to

242

form associations (Copeland et al., 2009; Vamadevan & Bertoft, 2018). The higher amount of

243

amylose in PS than WMS most probably induced greater syneresis and consequently

244

differentiated kc values were detected. It has to be also underlined that in WS composed of 5

245

wt% starch (irrespectively of the type) creaming did not occur. The observed slowing down

246

serum separation of WS with raising thickener concentration can be explained by relatively

247

high capacities of starch to absorb water during the gelatinization process, as well general

248

trend towards an increase in apparent viscosity (a) (Table 3). Presumably at the temperature

249

(90 oC) applied for WS preparation, amylose and amylopectin were released from starch

10

ACCEPTED MANUSCRIPT 250

granules, whereas upon cooling milk proteins aggregates were entrapped in the gelled starch

251

matrix and as the result ascending tendency of a with raising SC was observed (Bortnowska

252

et al., 2016; Considine et al., 2011). However, it was also found that with the storage time, the

253

a values decreased (Table 3), probably due to the breaking down of the existing hydrogen

254

bonds between water and hydroxyl groups of starch molecules and formation of new intra-

255

and intermolecular interactions (Tako, Tamaki, Teruya, & Takeda, 2014). The values of Ba

256

(for definition of Ba see section 2) were taken to study the effects of viscosity on phase

257

separation of the WS. It was found that irrespectively of white sauces composition, the kc

258

values were negatively correlated with Ba as follows: 3 wt% RO (WMS-BS, r = −0.965, p <

259

0.05; PS-BS, r = −0.968, p < 0.05) and 9 wt% RO (WMS-BS, r = −0.979, p < 0.05; PS-BS, r

260

= −0.985, p < 0.05). This generally is in good agreement with the suggestion arises from the

261

Stokes law that velocity of separation is negatively correlated with viscosity of the system

262

(Reineccius, 2006).

263 264

3.2. Retention and release of aroma compounds from white sauces at thermodynamic

265

equilibrium

266 267

3.2.1. Effects of storage time and composition of white sauces on the retention of aroma

268

compounds

269 270

Retention (R) of ethyl acetate (EA), hexanal (HE) and R-(+) limonene (RL) was

271

investigated under equilibrium conditions during 10-days refrigerated storage period (RSP) of

272

white sauces (WS). The effects of starch type (ST) and starch concentration (SC) on the R

273

values, after 10-days RSP, depending on rapeseed oil concentration are illustrated in Fig. 1A

274

and B. The R magnitudes of aroma compounds (AC) were in majority significantly (p < 0.05) 11

ACCEPTED MANUSCRIPT 275

correlated with raising SC. However, taking into account WS prepared with waxy maize

276

starch (WMS-BS) and 3 wt% rapeseed oil (RO), the highest correlation value (r) was found

277

regarding HE (r = 0.999, p < 0.001) and the lowest one in the case of RL (r = 0.987, p < 0.05).

278

Similar relationship was observed concerning WMS-BS composed of 9 wt% RO: HE (r =

279

0.996, p < 0.01) and RL (r = 0.969, p < 0.05). WS made with potato starch (PS-BS)

280

demonstrated also relatively high r values regarding HE: 3 wt% RO (r = 0.995, p < 0.01); 9 wt%

281

RO (r = 0.998, p < 0.01), whereas much lower r values were determined for RL: 3 wt% RO (r

282

= 0.971, p < 0.01); 9 wt% RO (r = 0.923, p > 0.01). ANOVA revealed that SC had significant

283

effect on R values, particularly in systems containing 3 wt% RO: WMS-BS [F(3,24) = 101.6,

284

p < 0.001]; PS-BS [F(3,24) = 87.4, p < 0.001]. This probably was associated with the fact that

285

at higher oil content the effect of thickener concentration was less noticeable, specifically in

286

relation to AC exhibiting relatively high hydrophobicity (Fig. 1A and B). Moreover, ANOVA

287

showed that ST particularly significantly affected HE retention with F-values as follows: 3 wt%

288

RO [F(1,16) = 28.1, p < 0.001] and 9 wt% RO [F(1,16) = 24.7, p < 0.001]. The effects of

289

microstructure of WS on the AC retention were determined in relation to Bohlins parameters.

290

After 10-days of RSP, the A values, depending on starch concentration (2-5wt%) were in

291

ranges: 3 wt% RO [WMS-BS (5.14−90.1 Pa s1/z), PS-BS (7.12−133.7 Pa s1/z)]; 9 wt% RO

292

[WMS-BS (5.23−105 Pa s1/z), PS−BS (8.01−139 Pa s1/z)], whereas the z values were as

293

follows: 3 wt% RO [WMS-BS (3.83−5.12), PS-BS (4.57−6.14)]; 9 wt% RO [WMS-BS

294

(4.18−5.59), PS-BS (4.81−6.46)]. Parameter A is considered as the magnitude of the

295

interactions between molecules of the sample, whereas z is the number of the cooperative

296

flow units in the structure which measures the extent (or level) of the three dimensional

297

network in the gel (Bortnowska et al., 2016). The found results probably can be interpreted on

298

the grounds that WS with raising SC and RO concentration were becoming more structured

299

(Fig. 2A-D) due to the formation of mixed gels made by interpenetrating milk proteins and

12

ACCEPTED MANUSCRIPT 300

starch networks as well as hydrophobic interactions between these two biopolymers, adsorbed

301

on the oil droplets (Considine et al., 2011; Hernández‑Carrión et al., 2015; Kett et al., 2013).

302

The retention (R) values were in majority significantly correlated with Bohlins parameters (A,

303

z) especially in relation to EA in samples containing 3 wt% RO: A (WMS-BS, r = 0.992, p <

304

0.01; PS-BS, r = 0.998, p < 0.01); z (WMS-BS, r = 0.998, p < 0.01; PS-BS, r = 0.997, p <

305

0.01). These results may suggest that with increasing SC the molecules of AC were

306

progressively entrapped in the gelled starch matrix (Arvisenet et al., 2002; Secouard et al.,

307

2003). Considering effects of aroma compound type on the retention, ANOVA showed the

308

following F-values: WMS-BS [F(2,24) = 74.6, p < 0.001]; PS-BS [F(2,24) = 86.2, p < 0.001]

309

and WMS-BS [F(2,24) = 85.4, p < 0.001]; PS-BS [F(2,24) = 99.2, p < 0.001] in WS

310

containing 3 and 9 wt% RO, respectively. Relatively low R values, irrespectively of the WS

311

composition were observed regarding EA, which in samples made with 3 and 9 wt% RO

312

ranged correspondently: WMS-BS (0.38−0.59); PS-BS (0.41−0.62) and WMS-BS (0.41-0.60);

313

PS-BS (0.42−0.64). Much higher R values were found regarding RL: 3 wt% RO [WMS-BS

314

(0.47−0.73); PS-BS (0.53−0.76)] and 9 wt% RO [WMS-BS (0.56−0.75); PS-BS (0.64−0.78)]

315

(Fig. 1A and B). The retention of AC was affected probably by several factors and

316

hydrophobic interactions with milk proteins, seems to be most likely (Livney, 2010; Meynier

317

et al., 2003). Hence, it would appear reasonable to speculate that the more hydrophobic

318

compound the greater is the retention. This assumably partly explain why the R values of RL

319

and HE were greater than EA. However, in some of the samples, particularly composed of 3

320

wt% PS, the R values of HE were higher (p < 0.05) than RL what can be related to their

321

chemical characteristics. HE as the aliphatic aldehyde is generally more reactive than RL.

322

Jung & Ebeler (2003) reported that, the volatility of HE was significantly decreased by the

323

addition of -lactoglobulin (-LG). This protein has two disulfide bridges and one free

324

sulfhydryl group (SH) that is buried within the native protein, but becomes exposed and 13

ACCEPTED MANUSCRIPT 325

active after denaturation of the protein, e.g., during heating (Livney, 2010; Matignon et al.,

326

2015). So the hypothesis could be given that HE interacted with proteins reactive groups

327

(NH2, SH) and condensation products (Schiffs base or thioacetals) could have been formed

328

(Reineccius, 2006). The found effects of starch composition on the AC retention are partly

329

consistent with those of Arvisenet et al. (2002) who also suggested higher retention of studied

330

AC in systems containing amylose-rich starch than in those composed of waxy starch. Starch

331

has been shown to form inclusion complexes with different AC. This activity could be

332

particularly attributed to interactions when the aroma compound is entrapped in the amylose

333

helix through hydrophobic interactions (Kenar, Compton, Little, & Peterson, 2016; Lafarge et

334

al., 2014; Naknean & Meenune, 2010). The amylose-HE complexes have been documented in

335

the literature, however there are suggestions that also amylopectin may exhibit similar to

336

amylose properties (Jouquand et al., 2006). Yeo et al. (2016) reported that formation of

337

inclusion complexes is dependent on both solubility in water (WSol) and hydrophobicity of

338

AC. The WSol of RL is relatively low, whereas its molar volume large (Table 1), therefore

339

most probably the interactions of this aroma compound were limited to hydrophobic ones

340

with lipids and denatured proteins (Boutboul et al., 2002). From these results, it can be

341

asserted that appropriate combination of: AC hydrophobicity (log P), RO content, ST and SC

342

may allow to generate reasonable retention of aroma compounds (Heilig et al., 2016).

343 344

3.2.2. Effects of the temperature and composition of white sauces on the aroma compounds

345

release

346 347

The release of aroma compounds (AC) from white sauces (WS) at thermodynamic

348

equilibrium as a function of temperature ranged from 20 to 50 oC was analyzed using the

349

vant Hoffs law (Seuvre, Turci, & Voilley, 2008). Figure 3A and B shows the enthalpy (H) 14

ACCEPTED MANUSCRIPT 350

values of AC representing energy that was required for their partitioning from WS to the

351

headspace (Chen et al., 2016). In general the H were in the same order of magnitude and

352

ranged from 29.6 to 38.7 kJ/mol and from 28.1 to 39.2 kJ/mol in WS composed of 3 and 9 wt%

353

rapeseed oil (RO), respectively. ANOVA revealed that H values were mostly affected by the

354

type of aroma compound as follows: 3 wt% RO (WMS-BS [F(2,24) = 7.04, p < 0.01]; PS-BS

355

[F(2,24) = 32.8, p < 0.001]) and 9 wt% RO (WMS-BS [F(2,24) = 24.6, p < 0.001]; PS-BS

356

[F(2,24) = 38.7, p < 0.001]). These results generally agree with the opinion shared by other

357

authors that depending on physicochemical characteristics of AC, they are released under

358

equilibrium conditions in different quantity from the same food matrices and consequently

359

their enthalpies are varied (Chen et al., 2016; Kopjar, Andriot, Saint-Eve, Souchon, &

360

Guichard, 2010). Increasing SC, induced smaller values of H and these two parameters were

361

in majority significantly correlated together, particularly in relation to EA: 3% RO [(WMS-

362

BS, r = −0.989, p < 0.05; PS-BS, r = −0.997, p < 0.01)]; 9% RO [(WMS-BS, r = −0.961, p <

363

0.05; PS-BS, r = −0.958, p < 0.05)]. Similar conclusions can be drawn comparing the results

364

presented by other researchers (Savary et al., 2006; Kopjar et al., 2010). According to the

365

ANOVA, higher F-values, regarding effects of SC, were observed in samples containing 9 wt%

366

RO: WMS-BS [F(3,24) = 10.9, p < 0.001]; PS-BS [F(3,24) = 9.84, p < 0.001] than in those

367

composed of 3 wt% RO: WMS-BS [F(3,24) = 3.14, p < 0.05]; PS-BS [F(3,24) = 7.19, p <

368

0.01]. The H magnitudes were also considerably affected by rapeseed oil concentration,

369

especially regarding HE and RL as follows: WMS-BS (HE [F(1,16) = 19.8, p < 0.001], RL

370

[F(1,16) = 4.81, p < 0.05]); PS-BS (HE [F(1,16) = 7.59, p < 0.05], RL [F(1,16) = 5.89, p <

371

0.05]). Higher F-values found for HE than RL, probably can be explained by the fact that HE

372

interacted with biopolymers (proteins, starch components) which were present in the systems

373

(Jung & Ebeler, 2003; Kenar et al., 2016; Lafarge et al., 2014). The enthalpy is considered to

374

be directly linked to the attraction or repulsion forces that retain or release the AC in their 15

ACCEPTED MANUSCRIPT 375

environment (Meynier et al., 2003). Therefore, the found results can be interpreted by the fact

376

that depending on: physicochemical characteristics of AC, microstructural and textural

377

properties of WS as well as interactions of AC with WS ingredients, the AC required different

378

amount of energy (H) for partitioning to the headspace (Chen et al., 2016; Seuvre et al.,

379

2008).

380 381

3.3. Release of aroma compounds from white sauces during refrigerated storage

382 383

3.3.1 Effects of composition of white sauces on the release kinetics of aroma compounds

384 385

White sauces aromatized with ethyl acetate (EA), hexanal (HE) or R-(+) limonene (RL)

386

were subjected to the refrigerated storage (10 days) and then estimated under equilibrium

387

conditions retention (R) values were fitted to the Avramis equation. The determined release

388

rate constants (k) and release mechanism parameters (n) in relation to: starch type (ST) and

389

starch concentration (SC), aroma compound type and rapeseed oil (RO) content, are featured

390

in Tables 4 and 5. It was found, that in all studied samples the n values were lower than 1,

391

therefore it may be assumed that release of aroma compounds was generally controlled by the

392

diffusion mechanism (Bortnowska, 2012). Similar release mechanism of D-limonene from

393

nanoemulsions was reported by Li & Lu (2016). All n values demonstrated descending

394

tendency with increasing starch concentration (SC) and this was also confirmed by significant

395

(p < 0.05) negative correlation values. ANOVA revealed that n magnitudes were affected by

396

both SC and the type of aroma compound (p < 0.001), however there was no interaction

397

between these two parameters (F < 1). The found differences concerning n values most

398

probably were dependent on aroma compounds hydrophobicity, their location in emulsion

399

structure and reversible interactions with white sauces (WS) ingredients (Bortnowska, 2012). 16

ACCEPTED MANUSCRIPT 400

The results from ANOVA showed that both starch concentration (SC) and aroma compound

401

type (ACT) were significant on the values of release rate constant (k) and that there was a

402

significant interaction between them on k. However, taking into account F-values, SC mostly

403

affected release of aroma compounds in samples composed of 3 wt% RO: WMS-BS [F(3,24)

404

= 206.5, p < 0.001]; PS-BS [F(3,24) = 256.4, p < 0.001], whereas in those containing 9 wt%

405

RO, k values were more influenced by the ACT: WMS-BS [F(2,24) = 270.6, p < 0.001]; PS-

406

BS [F(2,24) = 401.5, p < 0.001]. Irrespectively of the rapeseed oil concentration and starch

407

type (WMS, PS), the k (kinetic constant) values (Aguiló-Aguayo et al., 2010), demonstrated

408

descending tendency with raising SC and the correlation coefficients (r) calculated between

409

these two parameters were in majority statistically significant (p < 0.05). Particularly high r

410

values were found regarding samples composed of 3 wt% RO and thickened with WMS: EA

411

(r = −0.994, p < 0.01); HE (r = −0.995, p < 0.01) and RL (r = −0.998, p < 0.001), most

412

probably because the diffusion of AC was less affected by interactions with amylose and

413

compact structure as possible in other investigated sets of samples (Fig. 2A- D). The declining

414

behavior of k values with growing SC can be attributed to the increasing apparent viscosity of

415

examined WS (Table 3). The correlations (r) calculated between k and Ba as well as n and

416

Ba (for definition of Ba see section 2) demonstrated negative and in majority significant (p <

417

0.05) values. However, it has to be highlighted that, notably high and statistically significant r

418

values (k−Ba) were found in WS containing 3 wt% RO: WMS-BS (EA, r = −0.969, p < 0.05;

419

HE, r = −0.968, p < 0.05; RL, r = −0.980, p < 0.05); PS-BS (EA, r = −0.987, p < 0.05; HE, r =

420

−0.966, p < 0.05; RL, r = −0.982, p < 0.05). Similar relationships was observed regarding

421

n−Ba correlations. These findings are in agreement with other studies, for example Secouard

422

et al. (2003) and Terta et al. (2006) reported decrease in aroma compounds release with

423

increasing viscosity caused by polysaccharide addition. This probably could have been

424

associated with the fact that with raising viscosity the diffusion rate is decreased (Cayot, 17

ACCEPTED MANUSCRIPT 425

Dury-Brun, Karbowiak, Savary, & Voilley, 2008; Seuvre et al., 2007). The impact of

426

microstructure on the release of aroma compounds was studied in relation to changes of

427

Bohlins parameters (A, z) during refrigerated storage of WS. It was found, that release rate

428

constants (k) were negatively, in majority statistically significantly (p < 0.05), correlated with

429

BA and Bz (for definition of BA and Bz see section 2). This may suggest that release of aroma

430

compounds (AC) was also delayed by the augmenting compact structure that was formed with

431

raising starch concentration (Fig. 2A-D). Taking into account the type of aroma compound, k

432

values were greater regarding EA than HE and RL, irrespectively of the applied starch type

433

and rapeseed oil concentration. This generally can be considered in terms of AC

434

physicochemical properties and the microstructural characteristics of WS. For example the

435

saturated vapor pressure of EA was found to be about fifty fold higher than RL, respectively

436

(Table 1). Moreover, EA (log P = 0.73) was probably mainly dissolved in the external phase

437

of the emulsion system, whereas HE (log P = 1.78) and RL (log P = 4.57) in the lipophilic

438

phase. The resistance to mass transfer is generally higher in oil than in aqueous phase (AP),

439

besides the lipophilic AC first have to be released from the oil phase to the AP before they

440

can be released from this phase to the headspace (Bortnowska, 2012; Cayot et al., 2008).

441

Mass transfer coefficient (hD) could have been also affected by the molar volume (MV) of AC

442

(Table 1) because with raising MV, the diffusion coefficient is decreased and thus values of

443

hD (De Roos, 2003; Harrison et al., 1997; Seuvre et al., 2007). It has been also suggested that

444

denatured whey proteins (at temperature above 79 oC) expose both SH groups and a

445

hydrophobic core, therefore they can interact together and with other milk proteins via

446

sulfhydryl-disulfide bonds (S-/S-S) exchange reactions and form a compact layer that

447

additionally prevents release of hydrophobic AC (Chen et al., 2016). The volume-weighted

448

mean diameter (d4,3) of the WS droplets was chosen for the evaluation of AC release (Table 6).

449

Studies revealed, that after 10-days refrigerated storage period, the values of d4,3 significantly 18

ACCEPTED MANUSCRIPT 450

(p < 0.05) increased. Similar trend was also reported by Su & Zhong (2016) in lemon oil

451

nanoemulsions fabricated with sodium caseinate and Tween 20. The increase in droplet

452

diameter was also observed with raising starch concentration (Table 6). The Bd4,3 coefficients

453

were calculated (for definition of Bd4,3 see section 2) to find relationship between droplet

454

diameter and k values, during refrigerated storage. It has been found that in all studied sets of

455

samples, the values of Bd4,3 were negatively correlated with those of k. For example in WS

456

containing 3 wt% RO, the correlation values (r) were as follows: WMS-BS (EA, r = −0.982, p

457

< 0.05; HE, r = −0.987, p < 0.05; RL, r = −0.979, p < 0.05); PS-BS (EA, r = −0.987, p < 0.05;

458

HE, r = −0.998, p < 0.05; RL, r = −0.983, p < 0.05). The negative correlation values may be

459

interpreted in terms of: flocculation (bridging or depletion), coalescence or increasing

460

adsorption of starch molecules on the interfacial (oil-water) layer. The coalescence process

461

could have been associated with the decrease in surface protein loading from approximately

462

from 31.2 to 11.3 mg m-2 (data not shown), comparing samples made with 3 wt% and 9 wt%

463

rapeseed oil (Santana et al., 2011; Ye, 2011). Whereas, the growing layer of thickener on the

464

oil droplets can be supposedly attributed to the interactions (hydrophobic, electrostatic, H-

465

bonding) between proteins and starch molecules. For example hydroxyl groups may

466

dissociate, leaving negative charges on starch molecules. The negatively charged starch

467

molecules may then repel each other causing dissociation of the double helices of

468

amylopectin, which leads to the exposure of more reactive sites on the macromolecule and

469

thus interact with proteins (Considine et al., 2011; Kett et al., 2013; Matignon et al., 2015).

470

However, Harrison et al. (1997) reported that the time to establish the equilibrium across the

471

oil-water interface is generally very small, generally about several dozen milliseconds and

472

that the rate limiting step for aroma compounds release into the headspace would be mass

473

transfer across the macroscopic emulsion-gas interface. Hence, it would appear reasonable to

19

ACCEPTED MANUSCRIPT 474

speculate that in food emulsions, such as WS the release of aroma compounds is governed by

475

many factors which very often cannot be unambiguously defined.

476 477

3.3.2. Losses and half-life release of aroma compounds

478 479

Percentage of the lost aroma compounds (L%) during 10-days refrigerated storage period is

480

demonstrated in Fig. 4A and B. The L values were negatively correlated with increasing

481

starch concentration (SC) and particularly significant correlations values (p < 0.01) were

482

found regarding HE. Basically, larger losses (comparing to initial concentration) were

483

observed regarding ethyl acetate (EA) than hexanal (HE) and R-(+) limonene (RL). For

484

example, regarding EA and RL in WMS-BS (3 wt% rapeseed oil, starch 2-5wt%) were in

485

ranges: 61-41% and 53-27%, respectively. Application of potato starch decreased the L values

486

which for the same mentioned above systems and aroma compounds (AC) ranged from 59%

487

to 38% and from 47% to 24%. Increase in the concentration of rapeseed oil (from 3wt% to

488

9wt%) caused additional decrease of L magnitudes (Fig. 4A and B).

489

The half-life release (t1/2) magnitudes were calculated in relation to the time, required for a

490

quantity to reduce to half its initial value. ANOVA revealed that irrespectively of rapeseed oil

491

(RO) concentration, the HL values were mainly dependent on thickener concentration in

492

systems containing waxy maize starch (WMS): 3 wt% RO [F(3,24) = 288.9, p < 0.001]; 9 wt%

493

RO [F(3,24) = 297.5, p < 0.001], whereas in those made with potato starch the t1/2 aroma

494

compounds values were mostly affected by the type of aroma compound: 3 wt% RO [F(3,24)

495

= 270.2, p < 0.001]; 9 wt% RO [F(3,24) = 296.8, p < 0.001]. Increasing SC delayed release of

496

AC and contributed to ascending behavior of t1/2 values, reflected by r values, that were in

497

majority significant (p < 0.05) and ranged from 0.908−0.998. Changes of t1/2 regarding EA

498

with increasing starch content were much smaller than HE and RL, irrespectively on rapeseed

20

ACCEPTED MANUSCRIPT 499

oil (RO) concentration and starch type. For example in WS composed of 3 wt% RO,

500

depending on SC (2−5 wt%) were in ranges, WMS-BS: EA (7.71−18.4 days), HE (12.4−46.2

501

days), RL (10.6−52.3 days), whereas in those containing 9 wt% RO, PS-BS: EA (8.54−25.4

502

days), HE (17.1- 96.8 days), RL (25.7−104 days) (data not shown). These results suggests that

503

with reducing values of release rate constant and release mechanism parameter, the t1/2 can be

504

largely prolonged.

505 506

4. Conclusions

507 508

Both used in this experiment starches, i.e., waxy maize starch (WMS) and potato starch (PS)

509

proved good applicability to stabilize white sauces, particularly at concentrations ranged from

510

4 to 5 wt%. The retention of aroma compounds (ethyl acetate, EA; hexanal, HE and R-(+)

511

limonene, RL) was dependent on their hydrophobicity, rapeseed oil content, starch type and

512

starch concentration. Generally, higher retention values, after 10-days refrigerated storage

513

period, were found in white sauces prepared with 9 wt% rapeseed oil and potato starch, than

514

in counterparts composed of 3 wt% rapeseed oil and waxy maize starch. The release rate

515

constants (k) calculated using Avramis equation revealed descending tendency with raising

516

starch concentration and the lowest k values of all studied aroma compounds were detected in

517

white sauces prepared with 5 wt% starch, regardless of its type and rapeseed oil concentration.

518

The EA demonstrated higher k values than HE and RL, whereas the release kinetics of HE

519

and RL was greatly affected by the presence of amylose and rapeseed oil content, respectively.

520

In all studied samples release of aroma compounds was controlled by the diffusion

521

mechanism (n < 1). Increase of starch concentration and rapeseed oil content in bigger extent

522

contributed to the longer half–life release regarding HE and RL than EA. Losses of aroma

523

compounds during 10-days refrigerated storage period and the enthalpies of affinity (H) 21

ACCEPTED MANUSCRIPT 524

exhibited decreasing tendency with raising starch concentration and rapeseed oil content.

525

These results provide a further understanding of aroma compounds (AC) retention and release

526

behavior in white sauces, thickened with different native starches and can be very useful to

527

the food industry during the designing of new products with the reasonable prolonged

528

stability of AC .

529 530

Acknowledgement

531

The Authors are grateful to Professor Takeshi Furuta (Department of Chemistry and

532

Biotechnology, Tottori University, Tottori, Japan) for assistance with calculation of aroma

533

compounds release parameters using Avramis equation.

534 535

REFERENCES

536 537

Aguiló-Aguayo, I., Montero-Calderón, M., Soliva-Fortuny, R., & Martín-Belloso O. (2010).

538

Changes on flavor compounds throughout cold storage of watermelon juice processed by

539

high-intensity pulsed electric fields or heat. Journal of Food Engineering, 100, 43–49.

540

Arvisenet, G., Le Bail, P., Voilley, A., & Cayot, N. (2002). Influence of physicochemical

541

interactions between amylose and aroma compounds on the retention of aroma in food-like

542

matrices. Journal of Agricultural and Food Chemistry, 50, 7088-7093.

543

Boland, A.B., Buhr, K., Giannouli, P., & Van Ruth S.M. (2004). Influence of gelatin, starch,

544

pectin and artificial saliva on the release of 11 flavour compounds from model gel systems.

545

Food Chemistry, 86, 401-411.

546

Bortnowska, G. (2012). Effects of pH and ionic strength of NaCl on the stability of diacetyl

547

and (-)-alpha-pinene in oil-in-water emulsions formed with food-grade emulsifiers. Food

548

Chemistry, 135, 2021-2028.

22

ACCEPTED MANUSCRIPT 549

Bortnowska, G., Krudos, A., Schube, V., Krawczyńska, W., Krzemińska, N., & Mojka K.

550

(2016). Effects of waxy rice and tapioca starches on the physicochemical and sensory

551

properties of white sauces enriched with functional fibre. Food Chemistry, 202, 31-39.

552

Boutboul, A., Giampaoli, P., Feigenbaum, A., & Ducruet V. (2002). Influence of the nature

553

and treatment of starch on aroma retention. Carbohydrate Polymers, 47, 73-82.

554

Całus, H. (1987). Principles of chemical calculations (8th ed.). Warsaw, Poland, Scientific

555

and Technical Publishing House, (Chapter 16).

556

Cayot, N.. Dury-Brun, C., Karbowiak, T., Savary, G., & Voilley A. (2008). Measurement of

557

transport phenomena of volatile compounds: A review. Food Research International, 41, 349–

558

362.

559

Chambers IV, E., & Koppel, K. (2013). Associations of volatile compounds with sensory

560

aroma and flavor: The complex nature of flavor. Molecules, 18, 4887-4905.

561

Chen, X.-W., Guo, J., Wang, J.-M., Yin, S.-W., & Yang X.-Q. (2016). Controlled volatile

562

release of structured emulsions based on phytosterols crystallization. Food Hydrocolloids, 56,

563

170-179.

564

Considine, T., Noisuwan, A., Hemar, Y., Wilkinson, B., Bronlund, J., & Kasapis S. (2011).

565

Rheological investigations of the interactions between starch and milk proteins in model dairy

566

systems: A review. Food Hydrocolloids, 25, 2008-2017.

567

Copeland, L., Blazek, J., Salman, H., & Tang M.C. (2009). Form and functionality of starch.

568

Food Hydrocolloids, 23, 1527-1534.

569

De Roos, K.B. (2003). Effect of texture and microstructure on flavour retention and release.

570

International Dairy Journal, 13, 593-605.

571

Guichard, E. (2006). Flavour retention and release from protein solutions. Biotechnology

572

Advances, 24, 226-229.

23

ACCEPTED MANUSCRIPT 573

Harrison, M., Hills, B.P., Bakker, J., & Clothier, T. (1997). Mathematical models of flavor

574

release from liquid emulsions. Journal of Food Science, 62, 653-658, 664.

575

Heilig, A., Heimpel, K., Sonne, A., Schieberle, P., & Hinrichs, J. (2016). An approach to

576

adapt aroma in fat-free yoghurt systems: Modelling and transfer to pilot scale. International

577

Dairy Journal, 56, 101-107.

578

Hernández‑Carrión, M., Sanz, T., Hernando, I., Llorca, E., Fiszman, S.M., & Quiles, A.

579

(2015). New formulations of functional white sauces enriched with red sweet pepper: a

580

rheological, microstructural and sensory study. European Food Research and Technology,

581

240, 1187–1202.

582

Jouquand, C., Ducruet, V., & Le Bail, P. (2006). Formation of amylose complexes with C6-

583

aroma compounds in starch dispersions and its impact on retention. Food Chemistry, 96, 461–

584

470.

585

Jung, D.M., & Ebeler, S.E. (2003). Headspace solid-phase microextraction method for the

586

study of the volatility of selected flavor compounds. Journal of Agricultural and Food

587

Chemistry, 51, 200-205.

588

Kenar, J.A., Compton, D.L., Little, J.A., & Peterson, S.C. (2016). Formation of inclusion

589

complexes between high amylose starch and octadecyl ferulate via steam jet cooking.

590

Carbohydrate Polymers, 140, 246–252.

591

Kett, A.P., Chaurin, V., Fitzsimons, S.M., Morris, E.R., O’Mahony, J.A., & Fenelon M.A.

592

(2013). Influence of milk proteins on the pasting behaviour and microstructural characteristics

593

of waxy maize starch. Food Hydrocolloids, 30, 661-671.

594

Kolb, B., & Ettre, L.S. (1997). Static headspace-gas chromatography, theory and practice.

595

Wiley-VCH. Inc. New York, (Chapter 5).

596

Kopjar, M., Andriot, I., Saint-Eve, A., Souchon, I., & Guichard, E. (2010). Retention of

597

aroma compounds: an interlaboratory study on the effect of the composition of food matrices 24

ACCEPTED MANUSCRIPT 598

on thermodynamic parameters in comparison with water. Journal of the Science of Food and

599

Agriculture, 90, 1285–1292.

600

Lafarge, C., Cayot, N., Hory, C., Goncalves, L., Chassemont, C., & Bail, P.L. (2014). Effect

601

of konjac glucomannan addition on aroma release in gels containing potato starch. Food

602

Research International, 64, 412–419.

603

Li, P.-H., & Lu, W.-C. (2016). Effects of storage conditions on the physical stability of D-

604

limonene nanoemulsions. Food Hydrocolloids, 53, 218-224.

605

Livney, Y.D. (2010). Milk proteins as vehicles for bioactives. Current Opinion in Colloid &

606

Interface Science, 15, 73–83.

607

Longo, M.A. & Sanromán, M.A. (2006). Production of food aroma compounds: Microbial

608

and enzymatic methodologies. Food Technology Biotechnology, 44, 335–353.

609

Matignon, A., Neveu, A., Ducept, F., Chantoiseau, E., Barey, P., Mauduit, S., & Michon, C.

610

(2015). Influence of thermo-mechanical treatment and skim milk components on the swelling

611

behavior and rheological properties of starch suspensions. Journal of Food Engineering, 150,

612

1–8.

613

Meynier, A., Garillon, A., Lethuaut, L., & Genot, C. (2003). Partition of five aroma

614

compounds between air and skim milk, anhydrous milk fat or full-fat cream. LAIT 83, 223–

615

235.

616

Naknean, P., & Meenune, M.: 2010. Factors affecting retention and

617

compounds in food carbohydrates. International Food Research Journal, 17, 23-34.

618

Rao, J., & McClements, D.J.: (2012). Impact of lemon oil composition on formation and

619

stability of model food and beverage emulsions. Food Chemistry, 134, 749–757.

620

Reineccius, G. (2006). Flavor chemistry and technology. (second ed.). New York: Taylor &

621

Francis Group, (Chapters 6, 8, 13).

release of flavour

25

ACCEPTED MANUSCRIPT 622

Santana, R.C., Perrechil, F.A., Sato, A.C.K., & Cunha, R.L. (2011). Emulsifying properties of

623

collagen fibers: Effect of pH, protein concentration and homogenization pressure. Food

624

Hydrocolloids, 25, 604-612.

625

Sanz, T., Tárrega, A., & Salvador, A. (2016). Effect of thermally inhibited starches on the

626

freezing and thermal stability of white sauces: Rheological and sensory properties. LWT -

627

Food Science and Technology, 67, 82-88.

628

Savary, G., Guichard, E., Doublier, J-L., & Cayot, N. (2006). Mixture of aroma compounds:

629

Determination of partition coefficients in complex semi-solid matrices. Food Research

630

International, 39, 372-379.

631

Secouard, S., Malhiac, C., Grisel, M., & Decroix, B. (2003). Release of limonene from

632

polysaccharide matrices: viscosity and synergy effect. Food Chemistry, 82, 227-234.

633

Seuvre, A-M., Philippe, E., Rochard, S., & Voilley, A. (2007). Kinetic study of the release of

634

aroma compounds in different model food systems. Food Research International, 40, 480-492.

635

Seuvre, A.M., Turci, C., & Voilley, A. (2008). Effect of the temperature on the release of

636

aroma compounds and on the rheological behavior of model dairy custard. Food Chemistry,

637

108, 1176-1182.

638

Su, D., & Zhong, Q. (2016). Lemon oil nanoemulsions fabricated with sodium caseinate and

639

Tween 20 using phase inversion temperature method. Journal of Food Engineering, 171, 214-

640

221.

641

Tako, M., Tamaki, Y., Teruya, T., & Takeda, Y. (2014). The principles of starch

642

gelatinization and retrogradation. Food and Nutrition Sciences, 5, 280-291.

643

Taylor, A.J. (2002). Release and transport of flavors In Vivo: Physicochemical, physiological,

644

and perceptual considerations. Comprehensive Reviews in Food Science and Food Safety, 1,

645

45-57.

26

ACCEPTED MANUSCRIPT 646

Terta, M., Blekas, G., & Paraskevopoulou, A. (2006). Retention of selected aroma

647

compounds by polysaccharide solutions: A thermodynamic and kinetic approach. Food

648

Hydrocolloids, 20, 863-871.

649

Tomasik, P. (2009). Specific physical and chemical properties of potato starch. Food 3

650

(Special Issue 1), 45-56.

651

Vamadevan, & V., Bertoft, E. (2015). Structure-function relationships of starch components.

652

Starch/Stärke, 67, 55–68.

653

Vamadevan, V., & Bertoft, E. (2018). Impact of different structural types of amylopectin on

654

retrogradation. Food Hydrocolloids, 80, 88-96.

655

Van Ruth, S.M., & King, C. (2003). Effect of starch and amylopectin concentrations on

656

volatile flavour release from aqueous model food systems. Flavour and Fragrance Journal,

657

18, 407-416.

658

Vandresen, F., Falzirolli, H., Batista, S.A.A., da Silva-Giardini, A.P.B., de Oliveira, D.N.,

659

Catharino, R.R., Ruiz, A.L.T.G., de Carvalho, J.E., Foglio, M.A., & da Silva, C.C. (2014).

660

Novel R-(+)-limonene-based thiosemicarbazones and their antitumor activity against human

661

tumor cell lines. European Journal of Medicinal Chemistry, 79, 110-116.

662

Ye, A. (2011). Functional properties of milk protein concentrates: Emulsifying properties,

663

adsorption and stability of emulsions. International Dairy Journal, 21, 14-20.

664

Yeo, L., Thompson, D.B., & Peterson, D.G. (2016). Inclusion complexation of flavour

665

compounds by dispersed high-amylose maize starch (HAMS) in an aqueous model system.

666

Food Chemistry, 199, 393–400.

667

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ACCEPTED MANUSCRIPT Chemical compounds studied in this article: Ethyl acetate (PubChem CID: 8857) Hexanal (PubChem CID: 6184) R-(+)-limonene (PubChem CID: 440917) Potassium sorbate (PubChem CID: 23676745) Sodium chloride (PubChem CID: 5234)

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Fig 1

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Fig 2

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Fig 3

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Fig 4

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Fig. 1. Effects of starch concentration (waxy maize starch, WMS; potato starch, PS) on the retention of ethyl acetate (EA), hexanal (HE) and R-(+) limonene (RL) in white sauces composed of 3 wt% rapeseed oil, RO (A) and 9 wt% RO (B). Mean values marked with no common letters are significantly different (p < 0.05). Fig. 2. Representative appearance images demonstrating consistency of white sauces containing 3 wt% RO and thickened with: 2 wt% WMS (A), 5 wt% WMS (B), 2 wt% PS (C) and 5 wt% PS (D). For the definition of abbreviations, see Fig. 1. Fig. 3. Enthalpies (H) of affinity of the aroma compounds depending on starch type (WMS, PS) and concentration in white sauces prepared with 3 wt% RO (A) and 9 wt% RO (B). Mean values marked with no common letters are significantly different (p < 0.05). For the definition of abbreviations, see Fig. 1. Fig. 4. Percentage of the lost aroma compounds (L%) during 10-days refrigerated storage period in relation to white sauces made with 3 wt% RO (A) and 9 wt% RO (B), depending on starch type (WMS, PS) and concentration. Mean values marked with no common letters are significantly different (p < 0.05). For the definition of abbreviations, see Fig. 1.

Legends to Fig. 1., Fig. 3. and Fig. 4. EA-WMS HE-WMS RL-WMS EA-PS HE-PS RL-PS

ACCEPTED MANUSCRIPT Highlights  Amylose content affected stability of white sauces (WS) during storage time  Retention of aroma compounds (AC) was governed by starch type (ST) and concentration (SC)  Release kinetics of AC was dependent on their hydrophobicity and texture of WS  Mechanism release of AC was typical for molecular diffusion  Enthalpy of affinity of AC in WS was influenced by SC and rapeseed oil content

ACCEPTED MANUSCRIPT Table 1. Physicochemical characteristics of the aroma compounds: molecular weight (MW), molar volume (MV), hydrophobicity (log P), water solubility (WSol, 25 oC), boiling point (BP), density (D, 25 oC), saturated vapor pressure (Psat, 25 oC) and odor descriptor Aroma MWa MVc log Pb WSolb BPb Da Psat Odor descriptorb compounds (g/mol) (cm3/mol) (g/L) (oC) (g/mL) (Pa) Ethyl acetate 88.11 107.1 0.73 80.1 77.1 0.902 13105d ethereal-fruity Hexanal 100.2 140.6 1.78 5.64 129.6 0.815 1420b apple-herbaceous R-(+)-limonene 136.2 207.2 4.57 0.01 177.5 0.834 267b citrus a

Supplier information. b PubChem Database (pubchem.ncbi.nlm.nih.gov). c Estimated data by Całus (1987) method. d Lafarge et al. (2014).

ACCEPTED MANUSCRIPT Table 2. Creaming rate (kc, day-1) of white sauces, containing 3 or 9 wt% rapeseed oil (RO), depending on starch type (waxy maize starch, WMS; potato starch, PS) and concentration WMS-based sauces PS-based sauces RO (wt%) Starch concentration (wt%) 2 3 4 5 2 3 4 5 3 0.29aE 0.18aCD 0.07aB 0.00aA 0.34aE 0.21aD 0.13aBC 0.00aA 9 0.18bDE 0.12bCD 0.04aB 0.00aA 0.26bF 0.19aE 0.08aBC 0.00aA Values with different superscripts within the same column (a-b) and row (A-F) differ significantly (p < 0.05).

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Table 3. Apparent viscosity (Pa s) of white sauces, fresh prepared and after 10-days of refrigerated storage period depending on RO content, starch type and concentration RO Storage WMS-based sauces PS-based sauces (wt%) time Starch concentration (wt%) 2 3 4 5 2 3 4 5 3 Fresh 2.82bA 6.07cB 11.5cD 17.9bF 3.07bA 7.21cC 15.2bE 19.1cG aA aB aC aE aA aB aD 10 days 2.17 4.76 9.01 15.4 2.38 5.25 12.4 16.7aF bA dB dD bF cA dC dE Fresh 3.14 6.68 12.6 18.2 3.71 8.72 18.9 22.1dG 9 aA bB bD aE bA bC cE 10 days 2.41 5.24 9.95 15.6 2.86 6.29 16.3 18.4bF Values with different superscripts within the same column (a-d) and row (A-G) differ significantly (p < 0.05). For the definition of abbreviations, see Tab. 2.

ACCEPTED MANUSCRIPT Table 4. Release rate constants (k) and release mechanism parameters (n) of ethyl acetate (EA), hexanal (HE) and R-(+) limonene (RL) in white sauces (3 wt% RO) depending on starch type and concentration Aroma WMS-based sauces PS-based sauces Parameter compound Starch concentration (wt%) 2 3 4 5 2 3 4 5 cG cE cC bB cF cD cB -3 EA 83.4 66.2 44.6 32.6 76.8 59.5 33.2 25.9bA k  10 -1 aE aD aC aAB aD aC bB (day ) HE 49.5 35.8 21.1 12.1 39.6 25.1 15.4 8.31aA RL 59.1bD 41.3bC 26.6bB 10.8aA 43.5bC 30.9bB 10.1aA 6.85aA n (-) EA 0.82aB 0.80bB 0.76bB 0.72bA 0.81bB 0.79bB 0.73bA 0.71bA aC aC aBC aA aC aB aAB HE 0.75 0.72 0.68 0.63 0.73 0.68 0.65 0.59aA RL 0.78aC 0.74aBC 0.70aB 0.64aA 0.75aB 0.72aB 0.63aA 0.60aA Values, separately for k and n, with different superscripts within the same column (a-c) and row (A-G) differ significantly (p < 0.05). For the definition of abbreviations, see Tab. 2.

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Table 5. Release rate constants (k) and release mechanism parameters (n) of ethyl acetate (EA), hexanal (HE) and R-(+) limonene (RL) in white sauces (9 wt% RO) depending on starch type and concentration Aroma WMS-based sauces PS-based sauces Parameter compound Starch concentration (wt%) 2 3 4 5 2 3 4 5 cG cE cC bB cF cD cAB -3 EA 79.6 52.9 32.9 27.3 74.5 43.6 26.5 22.9bA k  10 -1 bF bD bC aAB bE bC bB (day ) HE 43.1 26.8 17.3 9.15 35.1 20.6 11.9 5.43aA RL 38.5aD 21.2aC 7.96aAB 6.52aA 22.7aC 10.3aB 6.96aA 4.98aA bC bC bAB bA bC bB bA n (-) EA 0.81 0.78 0.72 0.70 0.81 0.75 0.71 0.68bA HE 0.75aC 0.71aC 0.67aB 0.61aA 0.72aC 0.67bBC 0.63aAB 0.57aA RL 0.73aD 0.68aC 0.63aB 0.60aAB 0.68aC 0.61aB 0.59aA 0.56aA Values, separately for k and n, with different superscripts within the same column (a-c) and row (A-G) differ significantly (p < 0.05). For the definition of abbreviations, see Tab. 2.

ACCEPTED MANUSCRIPT Table 6. Droplet diameter (d4,3, m) of white sauces, fresh prepared and after 10-days of refrigerated storage period depending on RO content, starch type and concentration WMS-based sauces PS-based sauces RO Storage (wt%) time Starch concentration (wt%) 2 3 4 5 2 3 4 5 3 Fresh 2.13aA 2.61aC 2.79aD 2.91aE 2.01aA 2.44aB 2.62aC 2.73aD bA cC cD cE bA bB bC 10 days 2.61 3.02 3.26 3.42 2.52 2.83 2.99 3.08bC aA bC bD bD aA aB bC Fresh 2.27 2.81 3.02 3.14 2.25 2.59 2.82 3.11bD 9 cA dB dC cC cA bA cC 10 days 2.91 3.25 3.46 3.54 2.88 2.97 3.41 3.47cC Values with different superscripts within the same column (a-d) and row (A-E) differ significantly (p < 0.05). For the definition of abbreviations, see Tab. 2.