Food Research International 35 (2002) 435443 www.elsevier.

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Glass transitions for freeze-dried and air-dried tomato

V.R.N. Telisa,*, P.J.A. Sobralb
a

do Rio Preto, SP, Brazil Departamento de Engenharia e Tecnologia de Alimentos, Universidade Estadual Paulista, 15054-000, Sao Jose b FZEA-ZAZ, Universidade de Sa o Paulo, 13630-000, Pirassununga, SP, Brazil Received 22 March 2001; accepted 28 June 2001

Abstract Glass transition temperatures of freeze-dried tomato conditioned at various water activities at 25  C were determined by dierential scanning calorimetry (DSC). Air-dried tomato with and without osmotic pre-treatment in sucrose/NaCl solutions was also analyzed. Thermograms corresponding to the low water activity domain (0.11 4 aw 4 0.75) revealed the existence of two glass transitions, which were attributed to separated phases formed by sugars and water and other natural macromolecules present in the vegetable. Both transitions were plasticized by water and experimental data could be well correlated by the Gordon-Taylor equation in the low-temperature domain, and by the Kwei model in the high-temperature domain. For higher water activities, the lowtemperature glass transition curve exhibited a discontinuity, with suddenly increased glass transition temperatures approaching a constant value that corresponds to the Tg of the maximally freeze-concentrated amorphous matrix. The unfreezable water content was determined through the melting enthalpy dependence on the moisture content. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Tomato; Glass transition; DSC; Water activity; Drying

1. Introduction The quality of dried products is greatly aected by process- and/or storage-induced changes. Some of these involve changes in the physical state of the material and include shrinking of cells, loss of rehydration ability, wettability, migration of solids, case hardening and loss of volatile aroma components. Chemical changes, as enzymatic reactions, non-enzymatic browning and oxidation of lipids, pigments, and vitamins are also aected by physical structure, mainly due to its inuence on molecular mobility, which changes diusivity of the relevant molecular species (Karel, 1991; Nijhuis, Torringa, Muresan, Yuksel, Leguijt, & Kloek, 1998). In various food and biological materials the solids may be in an amorphous metastable state which is very sensitive to changes in temperature and moisture content. This amorphous matrix, which may be formed of food polymers and other food components, such as sugars, may exist either as a very viscous glass or as a

* Corresponding author. Fax: +55-17-221-2299. E-mail address: vanianic@eta.ibilce.unesp.br (V.R.N. Telis).

more liquid-like rubber. The change from the glassy to the rubbery state occurs as a second-order phase transition at a temperature known as the glass transition temperature (Tg). There are several drying techniques, among them the most commonly applied are hot air (convective), freeze and spray drying. In most drying conditions, a signicant amount of the dried product remains in the amorphous state, mainly due to insucient time for crystallization to occur at the given drying conditions. Depending upon the drying rate, the product can also be constituted of some crystalline material (Bhandari & Howes, 1999; Del Valle, Cuadros, & Aguilera, 1998). The glass transition temperature is strongly plasticized by water (Roos & Karel, 1991c). This behavior can be showed in a glass curve or in a state diagram where phase transition temperatures (glass transition and melting) are plotted versus moisture content (or solids concentration). Glass curves of animal (Aguilera, Levi, & Karel, 1994; Inoue & Ishikawa, 1997; Sobral, Menegalli, & Guilbert, 1998) or vegetal (Anglea, Karathanos, & Karel, 1993; Fan, Mitchell, & Blanshard, 1996; Zelesnak & Hoseney, 1987) products are relatively abundant in literature.

0963-9969/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S0963-9969(01)00138-7

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Nomenclature Hde H m aw k k0 q r Td Tg Tg
0

Tgs Tgw Tm Xg0

Xs Xw

enthalpy of devitrication (J g1) enthalpy of ice melting (J g1) water activity parameter in Eq. (1) parameter in Eq. (4) parameter in Eq. (4) correlation coecient peak devitrication temperature ( C) midpoint glass transition temperature [ C or K, in Eq. (1)] glass transition temperature of the maximally freeze-concentrated material ( C) glass transition temperature of the dry solids (K) glass transition temperature of pure water (K) onset melting temperature ( C) water fraction of the maximally freezeconcentrated material (g water/g moist solids) solids fraction (g dry solids/g moist solids) water fraction (g water/g moist solids)

are becoming of crucial importance. Quantifying the mobility changes induced by glass transition may be the route for the elucidation of the link between the process and product quality. The aim of this work was to determine phase transitions for freeze-dried tomato as a function of moisture content and to establish the state diagram for this material. The eect of air-drying fresh and osmotically pre-treated tomato halves on the glass transition temperature was also investigated.

2. Materials and methods 2.1. Raw material Ripe, fresh tomatoes (Lycopersicon esculentum Mill.) of the Santa Clara cultivar were obtained at the local do Rio Preto, SP, Brazil). The tomamarket (Sa o Jose toes were sorted visually for color, size and physical damage. The fruits were cut into halves and parenchyma and seeds were removed. Representative samples were used to measure moisture content (vacuum oven), resulting in 94.34 0.12% (w.b.), and sugars (Fehling method), resulting in 2.53 0.16% total sugars out of which 2.16 0.09% were reducing sugars. All measurements were made in triplicate. 2.2. Freeze-dried samples Tomato halves (including the skin) were cut into cubes of 1 cm side, frozen in liquid nitrogen, and then freeze-dried for about 48 h in a Heto FD3 equipment (Heto Lab Equipment), with samples containers operating at 4104 mbar and 21  C (samples temperature not controlled). 2.3. Air-dried samples Tomato halves were dried in a pilot scale tray drier that consists of three basic partsan airow rate control system, a drying air heating section and a drying chamberand is equipped with a process control system based on Fieldbus technology, supplied by SMAR Industrial Equipment Ltda. A centrifugal fan was used to force the air through the drying chamber. The fan was driven by an electric motor with the airow rate being controlled by a frequency modulator (Siemens, model MMV). Dry bulb and wet bulb temperatures of the air stream were measured on-line using temperature transmitters (SMAR, model TT302). The drying air was heated by passing through electric resistances controlled by a power converter (Therma, model TH 6021A/80). Samples were placed onto a perforated square metal tray, placed perpendicular to the airow. Thermocouples connected with temperature transmitters

State diagrams for aqueous solutions of pure components and model systems are also easily found in literature: sugars (Roos, 1995), starch hydrolysis products (Levine & Slade, 1986), and proteins (Cocero & Kokini, 1991). However, quantitative data for natural foods are relatively scarce. Complete state diagrams for this kind of material are found only for onion, grape and straw & Sereno, 1994), apple (Sereno, berry (Roos, 1987; Sa , & Figueiredo, 1998), and pineapple (Telis & Sobral, Sa 2001). Tomato is a worldwide important agricultural commodity, being the second horticultural product in cultivated area and the rst in industrialized volume (Camargo Filho & Mazzei, 1996). Dried tomato products are used as components for pizza and various vegetable and spicy dishes, and the increasing interest in the antioxidant activity of lycopenethe most abundant carotenoid in tomatoeshas been promoting several research activities on fresh tomato and tomato products (Zanoni, Peri, Nani, & Lavelli, 1999; Shi, Le Maguer, Kakuda, Liptay, & Niekamp, 1999; Tavares & Rodriguez-Amaya, 1994). The higher industrial use of dried products has increased the level of requirements, particularly in terms of functional properties. Also, there is an increasing consumer demand for processed products that keep more of their original characteristics, in such a way that preserving quality attributes of dehydrated foodstus

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(SMAR, model TT302) were placed before and after the tray. In order to integrate the instruments with the Fieldbus system, a 4 to 20 mA current converter (SMAR, model IF302) was used. The equipment operation was monitored and controlled by means of a computer running the software AIMAXTM-WIN. Drying runs were conducted at four temperatures (40, 50, 60 and 70  C) with xed airow (1.5 m/s). At regular time intervals the samples were taken out, weighed and returned to the drier. Drying was stopped when the samples weight showed to be fairly constant with time. 2.4. Osmotic pre-treatment

atmosphere (100 ml/min of N2). The reference was an empty pan. Liquid nitrogen was used for sample cooling before the runs. The midpoint (Tg) temperature of glass transition, peak (Td) temperature of devitrication, onset (Tm) temperature of ice melting, and enthalpy of devitrication (Hde) and ice melting (Hm) were calculated with the help of the software Universal Analysis V1.7F (TA Instruments). All the DSC traces were obtained in triplicate.

3. Results and discussion 3.1. Freeze-dried tomato Glass transitions of tomatoes submitted to osmoconvective drying were also obtained. In order to prepare these samples, a xed osmotic treatment was used. Tomato halves were immersed in a solution of 10% NaCl and 35% sucrose (distilled water and food grade solutes were employed) at 30  C, being continuously agitated. A 1:10 (w/w) tomato/solution ratio was used. After 2 h, samples were withdrawn from the solution, rapidly rinsed and slightly wiped with absorbent paper. Posterior air-drying was carried out at the same conditions applied to fresh samples. 2.5. Calorimetric analyses Powdered freeze-dried and manually grounded airdried tomato samples of about 1 g ( 0.01 g), always in triplicate, were conditioned at 25  C ( 0.1  C), using saturated salt solutions (LiCl, MgCl2, K2CO3, Mg(NO3), NaNO2, NaCl, (NH4)2SO4, KCl, BaCl2) to maintain the water activity (aw) between 0.11 and 0.90, according to a sorption isotherm methodology (Spiess & Wolf, 1983). After equilibrium was reached (after about 3 weeks), samples of about 10 mg ( 0.1 mg) were taken for DSC analysis and the remaining material was used for determining the equilibrium moisture content, accomplished by drying in a vacuum laboratory oven at 100 mmHg and 70  C, for 48 h. Freeze-dried samples with water contents corresponding to water activities higher than 0.90 were also analyzed. They were obtained by direct addition of liquid water to tomato powder and equilibration at 4  C for 24 h before DSC analyses (Telis & Sobral, 2001). The water activity of these samples was determined at 25  C, with the help of an AquaLab CX2 device (Decagon Devices, Inc.). Phase transitions were determined by dierential scanning calorimetry, with a DSC TA2010 controlled by a TA5000 module (TA Instruments, Newcastle, NJ), provided with a quench cooling accessory. The aliquots, conditioned in hermetic TA aluminum pans, were heated at 10  C/min, between 120 and 100  C, in inert The thermograms of freeze-dried tomato, obtained in a single scan, corresponding to the low water activity domain (0.11 4 aw 4 0.75) are shown in Fig. 1. The traces revealed the existence of two glass transitions, noticeable as deviations in the base line. In the samples of aw=0.11 these two transitions were very close, in such a way that they could be taken as a single event. As was expected in view of the plasticizing eect of water in the hygroscopic region (Slade & Levine, 1991), both glass transitions shifted toward lower temperatures with increasing water content. The lowest temperature transitions correspond to the glass transition of a matrix formed by sugars and water, while those observed at the highest temperatures, less visible and less water-plasticized, could be attributed to macromolecular constituents of tomato. Two glass transitions were also observed in thermograms of freeze-dried persimmon (Sobral, Telis, Habitante, & Sereno, 2001) and in protein-based edible lms (Gontard & Ring, 1996; Souza,

Fig. 1. Thermograms of freeze-dried tomato at low aw and Xw: (a) 0.11, 0.1883; (b) 0.33, 0.2098; (c) 0.43, 0.2389; (d) 0.53, 0.2652; (e) 0.64, 0.3036; (f) 0.75, 0.3709.

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Sobral, & Menegalli, 1998). This phenomenon, due to phase separation between polymers and between proteins and plasticizers, respectively, is typical of systems formed by blends of polymers (Verghoogt, Ramsay, & Favis, 1994). Thermograms obtained for isolated tomato fruit cuticles, a composite material of polymerized cutinbiopolymer constituted of waxes, phenolics, pectin and celluloseand a wide variety of monomeric waxes, also exhibited a lower temperature Tg at 30  C and an additional one around 3045  C (Luque & Heredia, 1997). At 0.80 and 0.84 of aw, well visible devitrication peaks appeared after Tg and before Tm (Fig. 2). This phenomenon results from the rapid cooling of highly viscous solutions, which leads to non-equilibrium ice formation, partial freeze-concentration, and ice formation during rewarming (Karel, Anglea, Buera, Karmas, Levi, & Roos, 1994). Devitrication exotherms at and Sereno (1994) with aw=0.84 were reported by Sa grape, by Roos (1987) with strawberry and by Telis and
Table 1 Phase properties of samples conditioned at 0.80 and 0.84 of water activitya

Sobral (1999, 2001) with pineapple. Freeze-dried per , Figueiredo, simmon (Sobral et al., 2001) and apple (Sa & Sereno, 1999) also presented devitrication exotherms at aw=0.80. As an alternative to isothermal annealing, normally applied to eliminate devitrication peaks, it was tested the use of controlled, low cooling rates. The results are presented in Fig. 3. The quench cooling, traditionally used by employing liquid nitrogen, gives cooling rates around 25  C/min. When cooling was accomplished at substantially lower rates (1.0 or 0.5  C/min) a considerable reduction in the exothermic peak was attained (Table 1). Complete elimination of the recrystallization peak, however, was only obtained with the isothermal annealing at Td for 30 min. As expected, Td decreased as aw increased (Fig. 2; Table 1), probably due to the plasticizing eect of water. The height of the devitrication peak was higher for 0.84 of water activity than for 0.80. Telis and Sobral (2001) and Sobral et al. (2001) have also observed that

Properties Scanning method Uncontrolled cooling, without annealing Cooling rate of 1  C/min Cooling rate of 0.5  C/min Isothermal annealing at35  C for 30 min. Isothermal annealing at35  C for 60 min.
a

Water activity 0.84 0.80 0.80 0.80 0.80 0.80

Devitrication temperature ( C) 54.8 5.7 37.4 2.8 34.7 1.5 33.5 2.1

Devitrication enthalpy (J/g) 26.4 0.6 9.3 4.1 7.3 2.1 4.8 2.1

Glass transition temperature ( C) 82.6 1.8 74.0 2.0 73.6 0.8 72.4 1.8 58.5 0.5 58.4 0.1

Average standard deviation

Fig. 2. Thermograms of freeze-dried tomato at intermediate aw and Xw: (a) 0.80, 0.4145; (b) 0.84, 0.4475, respectively.

Fig. 3. Thermograms of freeze-dried tomato at aw=0.80: (a) rapidly cooled with liquid N2; (b) with controlled cooling rate of 1  C/min; (c) with controlled cooling rate of 0.5  C/min; (d) with annealing at Td for 30 min.

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maximum devitrication occurred in pineapple and persimmon samples conditioned at aw=0.84. The glass transitions of annealed samples were higher than that of the non-annealed ones (Table 1), due to the greater fraction of ice formed, and consequent con & Sereno, 1994; centration of the unfrozen solution (Sa Telis & Sobral, 2001). Fig. 4 exhibits the traces obtained in the high moisture content domain (aw 5 0.90). In these thermograms Tg appeared less visible, just before ice melting, because the enthalpy change involved in glass transition is practically negligible in comparison to the latent heat of melting. Glass transition temperatures remained practically constant in this range of water activities, being higher than values obtained for samples between 0.75 and 0.84. Similar results were obtained by Roos and Karel (1991b) with diluted sucrose solutions, Telis and Sobral (2001) with pineapple, and Sobral et al. (2001) with persimmon. 3.2. Air-dried tomato Thermograms of air-dried tomato at 40, 50, 60 and 70  C, with and without osmotic pre-treatment were obtained for samples at their original water activity without any conditioning after leaving the drier. In addition, samples with osmotic pre-treatment, dried at 40 and 70  C, were conditioned at selected water activities in the range of 0.11 to 0.65. These thermograms are presented in Figs. 58. The thermogram corresponding to osmotically treated tomato, without air-drying was included in Fig. 4. Fresh and osmotically pre-treated air-dried tomato thermograms showed the same transitions observed in

freeze-dried material, including two glass transitions (at high and low temperature) in samples conditioned in the low aw domain ( < 0.75; Figs. 58), which were already mentioned above. Fresh tomato, dried at 70  C (Fig. 5), even after remaining 7.5 h in the drier presented water activity as high as 0.82, maybe due to crust formation. In this intermediate water activity, domain a devitrication peak also appeared in the thermogram, reproducing the behavior of freeze-dried tomato conditioned at 0.80 and 0.84 of aw (Fig. 2). Osmotically pre-treated tomato, dried at 40 and 70  C, and conditioned at water activities of 0.33, 0.43 and

Fig. 5. Thermograms of air-dried tomato, without osmotic pre-treatment, at dierent drying temperatures and nal water activities: (a) 40  C, aw=0.44; (b) 50  C, aw=0.41; (c) 60  C, aw=0.45; (d) 70  C, aw=0.82.

Fig. 4. Thermograms of freeze-dried tomato at high moisture contents, Xw: (a) 0.5253; (b) 0.5967; (c) 0.6463; (d) 0.7427; (e) 0.7913; (f) 0.8969; (g) fresh tomato osmotically treated, Xw=0.9097.

Fig. 6. Thermograms of air-dried tomato, with osmotic pre-treatment, at dierent drying temperatures and nal water activities: (a) 40  C, aw=0.46; (b) 50  C, aw=0.43; (c) 60  C, aw=0.41; (d) 70  C, aw=0.47.

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0.53, also presented small endothermal peaks between 50 and 100  C (Figs. 7 and 8), with higher peak temperatures at increasing water activities. This phenomenon occurred probably due to melting of sugars crystallized during drying. More detailed study would be necessary to elucidate this fact. 3.3. State diagram Fig. 9 presents the state diagram obtained for freezedried tomato. In the low and intermediate moisture content domain (aw < 0.90), the plasticizing eect of water on the glass transition temperature was evident, with a great reduction of Tg caused by increasing

moisture content. In this range of aw, Eq. (1) could be adequately adjusted to experimental points, with the following parameters calculated by non-linear regression using Tgw=138 K: k=9.35 and Tgs=603.9 K, with r=0.998. Tg Xs Tgs k Xw Tgw Xs k Xw 1

On the other hand, the data obtained in the high moisture content domain (aw 5 0.9) showed a sudden increase in glass transition temperatures, approaching a constant value that corresponds to the maximally freeze-concentrated amorphous matrix (Tg0 =214.2 3.1 K or 59.0 3.1  C) and is represented by the horizontal arrow. Tg0 can be also determined on rewarming completely annealed samples, which is conrmed in Table 1. Similar glass curves were obtained for diluted sucrose solutions (Ross & Karel, 1991b), freeze-dried pineapple (Telis & Sobral, 2001), and freeze-dried persimmon (Sobral et al., 2001). The state diagram plotted in Fig. 9 also shows the onset melting temperature (Tm) from samples that exhibited water freezing. As expected, melting temperature increased with increasing water content and the experimental results could be well represented by a polynomial model [Eq. (2)], with r=0.993. Tm 186:3 158:1Xw 74:4X2 w 2

Fig. 7. Thermograms of osmotically pre-treated, air-dried tomato at 40  C conditioned at dierent aw and Xw: (a) 0.11, 0.1535; (b) 0.33, 0.1749; (c) 0.43, 0.1947; (d) 0.53, 0.2433; (e) 0.65, 0.3804.

The intersection of melting and glass transition curves would be expected to occur at Tg0 (Roos & Karel, & Sereno, 1994; Slade & Levine, 1991). 1991a; Sa According Eq. (2) this intersection would happen around 45.0  C (228.2 K), corresponding to a water fraction of 0.31. This temperature is higher than the value obtained with samples of high humidity (indicated by the arrow). The lack of experimental points in this

Fig. 8. Thermograms of osmotically pre-treated, air-dried tomato at 70  C conditioned at dierent aw and Xw: (a) 0.11, 0.1465; (b) 0.33, 0.1690; (c) 0.43, 0.1907; (d) 0.53, 0.2292; (e) 0.65, 0.3859.

Fig. 9. State diagram of dried tomato: Tg of freeze-dried samples (X); Tg of air-dried samples at various temperatures (*,*, 70  C; ^,^, 60  C; &,&, 50  C; ~,~, 40  C) with (open symbols) and without (solid symbols) osmotic pre-treatment; Tg of osmotically pre-treated, without air-drying samples (!); Tm of freeze-dried samples (+).

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region of the diagram, however, led to the conclusion that this extreme of the melting curve would be better represented by the dotted line plotted in Fig. 9. A third approach to obtain Tg0 is based on the melting enthalpy dependence on moisture content (Roos & & Sereno, 1994). Fig. 10 shows that a Karel, 1991b; Sa linear relationship [Eq. (3), with r=0.994] exists between these quantities. Extrapolation of Eq. (3) to Hm=0 allowed calculation of the unfreezable water content (Xg0 =0.41 g water/g moist solids) corresponding to the maximally freeze-concentrated material. Hm 530:7Xw 216:5 3

Substitution of Xg0 on Eq. (1) resulted in Tg0 =200.1 K (73.1  C), which is lower than the value observed in the thermograms of high moisture samples. This trend was already showed for freeze-dried pineapple (Telis & Sobral, 2001) and freeze-dried persimmon (Sobral et al., and Sereno (1994) observed that 2001). Contrarily, Sa Tg0 calculated by this procedure was higher than experimental values obtained from thermograms of annealed samples, attributing this behavior to incomplete annealing. Glass transition temperatures for air-dried fresh and osmotically pre-treated tomato were also included in Fig. 9. In general, Tg values of air-dried samples, especially those corresponding to osmotically pre-treated ones, were lower than that observed for freeze-dried material at the same moisture content. As well as in the case of freeze-dried samples, the Gordon-Taylor model could be adjusted to describe glass transition temperatures of the osmotically treated material. Since no clear dierences were observed between Tg of samples obtained at dierent drying temperatures beyond those due to variable moisture content, single values of Gordon-Taylor parameters [Eq. (1)] were determined for the complete data set: k=6.10 and Tgs=415.7 K, with r=0.966.

Lower Tg values for osmotically pre-treated samples can be explained by gained solutes. For the same osmotic treatment conditions, Murari and Telis (2001) reported that NaCl content changed from 2.02% (dry basis) in fresh tomato to 16.01% (d.b.) in osmotically treated samples, while total sugars varied from 39.07% (d.b.) to 53.61% (d.b.), respectively. Glass transition temperature is known to decrease with decreasing molecular weight (Karel et al., 1994; Roos, 1995; Slade & Levine, 1991), in such a way that incorporated NaCl and sucrose would have caused the observed decrease in et al. (1999) reported a similar behavior for apple Tg. Sa osmotically treated in sucrose soluions. Baroni and Hubinger (2000) observed only small dierences between Tg of fresh and osmotically treated tomato and attributed this result to the short time adopted for the osmotic treatment, which led to low solute gain. This reasoning was also pointed out by Del Valle et al. (1998) to be responsible for small dierences in Tg resulting from osmotic treatment of apple cylinders in sucrose solutions. The inuence of solute gain is also detectable in the value of the constant k [Eq. (1)], which decreased from 9.35 in the case of freeze-dried tomato, to 6.10 for the osmotically treated vegetable, being closer to the value observed for pure sucrose, k=4.7 (Roos & Karel, 1991a). Air-dried samples without osmotic treatment presented glass transition temperatures somewhat lower than freeze-dried material and higher than osmotically treated ones. This could indicate structural dierences between air- and freeze-dried product. Nevertheless, additional experiments would be necessary in order to check this possibility. Fig. 11 presents the high temperature glass transition curves observed at low water activities (aw 4 0.65) for air-dried and freeze-dried tomato. It is interesting to note that an inversion has occurred in the location of

Fig. 10. Ice melting enthalpy of freeze-dried tomato.

Fig. 11. High temperature glass transition curves for tomato: freezedried (X) and air-dried at various temperatures (*, 70  C; ^,^, 60  C; &,&, 50  C; ~,~, 40  C) with (open symbols) and without (solid symbols) osmotic pre-treatment.

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the corresponding glass transitions. This is to say that osmotic treated samples showed the higher glass transition temperatures in these temperature domain, followed by air-dried samples without osmotic treatment, and nally by the freeze-dried samples. The existence of two glass transitions is attributed to separation of macromolecules present in the tomato, as already discussed in this paper. In this way, the relative position of the glass curves indicates that osmotic treatment and airdrying favored this separation, since the respective curves were more distant each from another than in the case of the freeze-dried material. The high temperature glass transition temperatures were also plasticized by water and congured practical glass curves (Slade & Levine, 1991) tending to an asymptotic value other than Tgw. The Kwei model [Eq. (4)] is then the most appropriated to represent the experimental data. Tg Xs Tgs k0 Xw Tgw qXs Xw Xs k0 Xw 4

Acknowledgements Authors acknowledge the nancial support received from FAPESP (Sa o Paulo State Research Fund), Proc. 98/05130-8.

References
Aguilera, J. M., Levi, G., & Karel, M. (1994). Eect of water content on the glass transition and caking of sh protein hydrolyzates. Biotechnology Progress, 9, 651654. Anglea, S. A., Karathanos, V., & Karel, M. (1993). Low-temperature transitions in fresh and osmotically dehydrated plant materials. Biotechnology Progress, 9, 204209. Baroni, A. F. & Hubinger, M. D. (2000). Physical and state properties of tomato during dehydration. Proceedings of the 12th International Drying Symposium (IDS2000), Paper No.114 (CD ROM). Bhandari, B. R., & Howes, T. (1999). Implication of glass transition for the drying and stability of dried foods. Journal of Food Engineering, 40(1), 7179. Camargo Filho, W. P., & Mazzei, A. R. (1996). Necessidade de reconversa a o o da produc o de tomate em Sa o Paulo: ac es na cadeia micas, SP, 26(6), 105116. produtiva. Informac o es Econo Cocero, A. M., & Kokini, J. L. (1991). The study of the glass transition of glutenin using small amplitude oscillatory rheological measurements and dierential scanning calorimetry. Journal of Rheology, 35(2), 257270. Del Valle, J. M., Cuadros, T. R. M., & Aguilera, J. M. (1998). Glass transitions and shrinkage during drying and storage of osmosed apple pieces. Food Research International, 31(3), 191204. Fan, J., Mitchell, J. R., & Blanshard, J. M. V. (1996). The eect of sugars on the extrusion of maize grits: I. The role of the glass transition in determining product density and shape. International Journal of Food Science and Technology, 31(1), 5565. Gontard, N., & Ring, S. (1996). Edible wheat gluten lm: inuence of water content on glass transition temperature. Journal of Agricultural and Food Chemistry, 44, 34743478. Inoue, C., & Ishikawa, M. (1997). Glass transition of Tuna Flesh at low temperature and eects of salt and moisture. Journal of Food Science, 62(3), 496499. Karel, M. (1991). Physical structure and quality of dehydrated foods. (Eds.), Drying 91 (pp. 2635). In A. S. Mujumdar, & I. Filkova Amsterdam: Elsevier Science Publishers. Karel, M., Anglea, S., Buera, P., Karmas, R., Levi, G., & Roos, Y. (1994). Stability related transitions of amorphous foods. Thermochimica Acta, 246, 249269. Levine, H., & Slade, L. (1986). A polymer physico-chemical approach to the study of commercial starch hydrolysis products (SHPs). Carbohydrate Polymers, 6, 213244. Luque, P., & Heredia, A. (1997). The glassy state in isolated cuticles: dierential scanning calorimetry of tomato fruit cuticular membranes. Plant Physiology and Biochemistry, 35(3), 251256. Murari, R. C. B. D. L., & Telis, V. R. N. (2001). Osmotic dehydration kinetics of tomatoes, Journal of Food Engineering. (submitted for publication). Nijhuis, H. H., Torringa, H. M., Muresan, S., Yuksel, D., Leguijt, C., & Kloek, K. (1998). Approaches to improving the quality of dried fruit and vegetables. Trends in Food Science and Technology, 9(1), 1320. Roos, Y., & Karel, M. (1991a). Applying state diagrams to food processing and development. Food Technology, 12, 6671,107. Roos, Y., & Karel, M. (1991b). Phase transitions of amorphous sucrose and frozen sucrose solutions. Journal of Food Science, 56(1), 266267.

Eq. (4) could be adequately tted to experimental points, with parameters calculated by non-linear regression. For freeze-dried tomato, obtained values were k0 =5.21, Tgs=380.0 K and q=413.5 K, with r=0.906, while for the osmotically treated product, k0 =83.3, Tgs=1958.7 K and q=582.9 K, with r=0.940. This model has been successfully used to represent practical glass transition curves of several products including fruits (Sobral et al., 2001; Telis & Sobral, 1999) and biopolymers (Sobral et al., 1998).

4. Conclusions Dierential scanning calorimetry allowed obtaining a state diagram for freeze-dried tomato, with GordonTaylor model adequately representing the matrix glass transition curve. For the osmotically treated, air-dried tomatoes, measured glass transition temperatures were lower than those of the freeze-dried product due to incorporation of low molecular weight solutes (sucrose and NaCl). No dierences were observed between glass transition temperatures of samples dried at dierent air temperatures. Additional high temperature glass transitions, attributed to the presence of natural macromolecules behaving like a separated phase, were detected in samples with moisture content less than 40% (w.b.) and the Kwei model resulted in a good t to these transitions. Devitrication peaks were observed in an intermediate moisture range (aw=0.80 and 0.84), which disappeared after annealing for a period of 30 min. In the high moisture range, samples exhibited a constant glass transition value of 59.0  C, which corresponds to the maximally concentrated solid matrix glass transition Tg0 .

V.R.N. Telis, P.J.A. Sobral / Food Research International 35 (2002) 435443 Roos, Y., & Karel, M. (1991c). Plasticizing eect of water on thermal behavior and crystallization of amorphous food models. Journal of Food Science, 56(1), 3843. Roos, Y. (1995). Characterization of food polymers using state diagrams. Journal of Food Engineering, 24(3), 339360. Roos, Y. H. (1987). Eect of moisture on the thermal behavior of strawberries studied using dierential scanning calorimetry. Journal of Food Science, 52(1), 146214. , M. M., Figueiredo, A. M., & Sereno, A. M. (1999). Glass transiSa tions and state diagrams for fresh and processed apple. Themochimica Acta, 329, 3138. , M. M., & Sereno, A. M. (1994). Glass transitions and state diaSa grams for typical natural fruits and vegetables. Thermochimica Acta, 246, 285297. , M. M., & Figueiredo, A. M. (1998). Glass transitions Sereno, A. M., Sa and state diagrams for freeze-dried and osmotically dehydrated apple. In C. B. Akritids, D. Marinos-Kouris, & G. D. Saravacos (Eds.), Drying98 (pp. 12141220). Thessaloniki: Ziti Editions. Shi, J., Le Maguer, M., Kakuda, Y., Liptay, A., & Niekamp, F. (1999). Lycopene degradation and isomerization in tomato dehydration. Food Research International, 32(1), 1521. Slade, L., & Levine, H. (1991). Beyond water activity: recent advances based on an alternative approach to the assessment of food quality and safety. Critical Reviews in Food Science and Nutrition, 30(2), 115360. Sobral, P. J. A., Menegalli, F. C., & Guilbert, S. (1998). Phase transitions of bovine hide gelatin plasticized by water. In P. Colonna, & S. Guilbert (Eds.), Biopolymer science: food and non food applications, Les Colloques, (No. 91) (pp. 111123). Paris: INRA.

443

Sobral, P. J. A., Telis, V. R. N., Habitante, A. M. Q. B., & Sereno, A. (2001). Phase diagram for freeze-dried persimmon. Thermochimica Acta. 376(1), 8389. Souza, S. M. A., Sobral, P. J. A., & Menegalli, F. C. (1998). Glass transition of a meat myobrillar protein based edible lm. In P. Colonna, & S. Guilbert (Eds.), Biopolymer science: food and non food applications, Les Colloques No 91 (pp. 183188). Paris: INRA. Spiess, W. E. L., & Wolf, W. R. (1983). The results of the COST 90 project on water activity. In F. Escher, B. Hallstrom, H. S. Meert, W. E. L. Spiess, & G. Voss (Eds.), Physical properties of foods (pp. 6587). New York: Applied Science Publishers. Tavares, C. A., & Rodriguez-Amaya, D. B. (1994). Carotenoid composition of Brazilian tomatoes and tomato products. LebensmittelWissenschaft und-Technologie, 27(3), 219224. Telis, V. R. N., & Sobral, P. J. A. (1999). Glass transitions of freezedried pineapple. Brazilian Journal of Food Technology, 21(1), 181 184. Telis, V. R. N., & Sobral, P. J. A. (2001). Glass transitions and state diagram for freeze-dried pineapple. Lebensmittel-Wissenschaft undTechnologie, 34(4), 199205. Verghoogt, H., Ramsay, B. A., & Favis, B. D. (1994). Polymer blends containing poly(3-hydroxyalkanoate)s. Polymer Reviews, 35(24), 51555169. Zanoni, B., Peri, C., Nani, R., & Lavelli, V. (1999). Oxidative heat damage of tomato halves as aected by drying. Food Research International, 31(5), 395401. Zeleznak, K. J., & Hoseney, R. C. (1987). The glass transition in starch. Cereal Chemistry, 64(2), 121124.