Superficie de Respuestas
Superficie de Respuestas
Superficie de Respuestas
a r t i c l e i n f o a b s t r a c t
Article history: The objective of this work was to study the influence of spray drying conditions on the physicochemical
Received 7 December 2007 properties of acßai powder. The process was carried out on a mini spray dryer and maltodextrin 10DE was
Received in revised form 27 February 2008 used as carrier agent. Seventeen tests were made, according to a central composite design. Independent
Accepted 28 February 2008
variables were: inlet air temperature (138–202 °C), feed flow rate (5–25 g/min) and maltodextrin concen-
Available online 8 March 2008
tration (10–30%). Moisture content, hygroscopicity, process yield and anthocyanin retention were ana-
lysed as responses. Powder moisture content and process yield were positively affected by inlet air
Keywords:
temperature and negatively affected by feed flow rate, which are directly related to heat and mass trans-
Spray drying
Acßai
fer. Process yield was also negatively influenced by maltodextrin concentration, due to the increase on
Physicochemical properties mixture viscosity. Powders hygroscopicity decreased with increasing maltodextrin concentration,
Morphology decreasing temperature and increasing feed flow rate. Powders with lower moisture content were more
Anthocyanins hygroscopic, which is related to the greater water concentration gradient between the product and the
surrounding air. Anthocyanin retention was only affected by temperature, due to its high sensitivity.
In respect to morphology, the particles produced at higher temperature were larger and a great number
of them showed smooth surface.
Ó 2008 Elsevier Ltd. All rights reserved.
0260-8774/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2008.02.029
412 R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418
Nomenclature
Some authors have used carrier agents in order to protect sen- pump and the feed flow rate was controlled by the pump rotation
sitive components like vitamin C in fruits such as camu–camu (Dib speed. Drying air flow rate was 73 m3/h and compressor air pres-
Taxi et al., 2003) and to increase product stability in acerola pow- sure was 0.06 MPa. Inlet air temperature varied from 138 °C to
der (Righetto and Netto, 2005). In the case of acßai juice, spray dry- 202 °C and feed flow rate varied from 5 to 25 g/min, according to
ing with carrier agents represents an interesting process, which an experimental design, described at the item 2.5.
can promote the protection of anthocyanins against adverse condi- Process yield was calculated as the relationship between total
tions like heat, light and oxygen, besides resulting in less hygro- solids content in the resulting powder and total solids content in
scopic powders. the feed mixture.
The objective of this work was to study the influence of inlet air
temperature, feed flow rate and maltodextrin concentration on 2.4. Analytical methods
process yield, powder moisture content, powder hygroscopicity
and anthocyanin retention, during the microencapsulation of acßai Feed mixtures were analysed for moisture and anthocyanin con-
pulp by spray drying. The effect of inlet air temperature and mal- tent, as well as for viscosity. Spray-dried powders were analysed for
todextrin concentration on powders morphology and particle size moisture content, hygroscopicity and anthocyanin content. More-
distribution was also evaluated. over, the powders produced with different maltodextrin concentra-
tions and at different inlet air temperatures were analysed in respect
2. Materials and methods to their morphology, by means of scanning electron microscopy and
particles size distribution.
2.1. Materials
2.4.1. Mixture viscosity
Frozen acßai pulp was purchased from Palamaz Ind. e Com. Ltda. Feed mixtures viscosity was analysed through the determina-
(Belém, Brazil). The pulp was stored in a freezing chamber at – tion of steady-shear flow curves (shear stress shear rate), using
18 °C and thawed according to the quantity required for each test. a controlled stress Carri-Med CSL2 500 rheometer (TA Instruments,
Table 1 shows its physicochemical composition. Crawley, England) with acrylic concentric cylinders geometry.
Maltodextrin MOR-REXÒ 1910 (Corn Products, Mogi-Guacßu, Three flow ramps were obtained in a range of shear stress corre-
Brazil), with 9.0 6 DE 6 12.0, was used as carrier agent. sponding to shear rates from 0 to 300 s1. The first one with
increasing shear rate, the second one with decreasing shear rate
2.2. Sample preparation and the third one also with increasing shear rate. This assured that
the viscosity time-dependency was eliminated, once the second
Before entering the spray dryer, acßai pulp was filtered through a and the third curves matched. Trials were performed in triplicate,
qualitative filter paper, in order to reduce fat content, thus reduc- using a new sample for each repetition. Rheograms were analysed
ing the risk of lipid oxidation (lipids content was reduced from according to empirical models and apparent viscosity was calcu-
6.83 ± 0.03% to 0.21 ± 0.01%) and increasing anthocyanin content lated as the relationship between shear stress (r) and shear rate (_c).
per g of dried mass (from 234 ± 4 to 766 ± 5 mg/g of dried mass).
Maltodextrin was added to the filtered pulp under magnetic agita- 2.4.2. Moisture content
tion, until complete dissolution. Powders and mixtures moisture contents were determined
gravimetrically by drying in a vacuum oven at 70 °C until constant
2.3. Spray drying weight (A.O.A.C., 1990).
Spray drying process was performed in a laboratory scale spray 2.4.3. Hygroscopicity
dryer LabPlant SD-05 (Huddersfield, England), with a 1.5 mm Hygroscopicity was determined according to the method pro-
diameter nozzle and main spray chamber of 500 mm 215 mm. posed by Cai and Corke (2000), with some modifications. Samples
The mixture was fed into the main chamber through a peristaltic of each powder (approximately 1 g) were placed at 25 °C in a con-
tainer with NaCl saturated solution (75.29%RH). After one week,
samples were weighed and hygroscopicity was expressed as g of
adsorbed moisture per 100 g dry solids (g/100 g).
Table 1
Composition of acßai (Euterpe oleraceae Mart.)
2.4.4. Anthocyanin content
Analyzed item Mean value Analysis method Anthocyanins were extracted with 95% ethanol/1.5 N HCl
Moisture (wet basis) 85.96 ± 0.11 A.O.A.C. (1990) (85:15, v:v), according to the procedure described by Francis
Proteins 1.43 ± 0.04 A.O.A.C. (1990) (1982). Absorbance was measured in a UV–vis spectrophotometer
Lipids 6.83 ± 0.03 Bligh and Dyer (1959)
at a kmax of 535 nm, and the total anthocyanin content was calcu-
Fibers 4.52 ± 0.22 A.O.A.C. (1990)
Total sugars 0.48 ± 0.05 A.O.A.C. (1990) lated by using the absorption coefficient of 982, corresponding to
Ash 0.44 ± 0.01 A.O.A.C. (1990) cyanidin-3-glucoside in ethanol/1.5 N HCl (Zanatta et al., 2005).
Acidity (% citric acid) 0.34 ± 0.02 A.O.A.C. (1990) For determination of anthocyanin retention, total anthocyanin con-
Anthocyanins (mg/100 g) 32.81 ± 0.57 Francis (1982) tent was calculated as mg/100 g of dry matter, in the mixture be-
pH 5.18 ± 0.02 pH meter
fore entering the spray dryer as well as in the resulting powder.
R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418 413
Table 2 tween 0.909 and 0.961) for all the maltodextrin concentrations.
Experimental design for the spray drying tests Thus, the mixture ‘‘filtered acßai pulp + maltodextrin” could be
Tests Inlet air temperature Feed flow rate Maltodextrin characterized as a fluid with shear-thinning behavior, which is typ-
(°C) (g/min) concentration (%) ical for most of the food materials, specially fruit pulps (Dak et al.,
1 150 (1) 9 (1) 14 (1) 2006; Nindo et al., 2007).
2 190 (+1) 9 (1) 14 (1) The apparent viscosity was calculated as the relationship
3 150 (1) 21 (+1) 14 (1) between shear stress and shear rate. In order to evaluate this
4 190 (+1) 21 (+1) 14 (1)
5 150 (1) 9 (1) 26 (+1)
property as a function of maltodextrin concentration, experimental
6 190 (+1) 9 (1) 26 (+1) data for a shear rate of 100 s1 were considered. The mixtures
7 150 (1) 21 (+1) 26 (+1) apparent viscosity varied from 3.88 103 to 23.70 103 Pa s
8 190 (+1) 21 (+1) 26 (+1) and showed an exponential increase with maltodextrin concentra-
9 138 (1.68) 15 (0) 20 (0)
tion, as shown in Fig. 1.
10 202 (+1.68) 15 (0) 20 (0)
11 170 (0) 5 (1.68) 20 (0)
12 170 (0) 25 (+1.68) 20 (0) 3.2. Response surface analysis
13 170 (0) 15 (0) 10 (1.68)
14 170 (0) 15 (0) 30 (+1.68) The values of process yield, powders moisture content, hygro-
15 170 (0) 15 (0) 20 (0)
scopicity and anthocyanin retention, as well as the outlet air tem-
16 170 (0) 15 (0) 20 (0)
17 170 (0) 15 (0) 20 (0) perature, are shown in Table 3.
Table 4 shows the regression coefficients for the coded second-
order polynomial equation, the F and p values and the determina-
tion coefficients (R2). Some non-significant terms were eliminated
2.4.5. Particles morphology and the resulting equations were tested for adequacy and fitness
Particles morphology was evaluated by scanning electron by the analysis of variance (ANOVA). The fitted models were suit-
microscopy (SEM). Powders were attached to a double-sided adhe- able, showing significant regression, low residual values, no lack of
sive tape mounted on SEM stubs, coated with 3–5 mA gold/palla- fit and satisfactory determination coefficients.
dium under vacuum and examined with a LEO440i scanning
electron microscope (LEICA Electron Microscopy Ltd., Cambridge,
England). SEM was operated at 5 kV with magnifications of
2000 and 7000. 25
Apparent viscosity (s-1)
y ¼ b0 þ b1 x1 þ b2 x2 þ b3 x3 þ b11 x21 þ b22 x22 þ b33 x23 þ b12 x1 x2 Tests Process Moisture Hygroscopicity Anthocyanin Outlet air
yield (%) content (%) (g/100 g) retention (%) temperature (°C)
þ b13 x1 x3 þ b23 x2 x3 ð1Þ
1 50.33 1.23 ± 0.07 14.73 ± 0.20 84.86 ± 1.74 89 ± 2
The analysis of variance (ANOVA), test for the lack of fit, deter- 2 52.47 0.69 ± 0.08 15.42 ± 0.20 81.40 ± 2.04 111 ± 3
mination of the regression coefficients and the generation of three- 3 42.53 2.89 ± 0.10 15.17 ± 0.06 86.01 ± 2.86 82 ± 2
4 49.32 0.86 ± 0.04 15.10 ± 0.29 79.09 ± 2.78 106 ± 2
dimensional graphs were carried out using the Statistica 5.5 soft- 5 45.74 1.92 ± 0.27 13.83 ± 0.09 84.08 ± 2.31 90 ± 2
ware (StatSoft, Tulsa, USA). 6 48.17 0.64 ± 0.02 14.77 ± 0.10 79.38 ± 1.05 114 ± 2
7 34.39 2.34 ± 0.06 12.54 ± 0.20 83.99 ± 1.23 86 ± 2
8 38.38 1.05 ± 0.07 14.30 ± 0.20 79.29 ± 1.66 106 ± 2
3. Results and discussion 9 46.01 2.56 ± 0.17 12.98 ± 0.11 84.62 ± 1.58 83 ± 2
10 55.66 0.66 ± 0.18 15.13 ± 0.15 77.21 ± 1.10 112 ± 3
11 50.27 0.95 ± 0.24 14.31 ± 0.04 80.05 ± 1.15 111 ± 2
3.1. Mixtures viscosity
12 39.02 1.88 ± 0.02 13.62 ± 0.20 80.82 ± 1.37 94 ± 2
13 50.83 1.78 ± 0.06 15.79 ± 0.29 83.13 ± 1.28 96 ± 2
As stated before, feed mixtures viscosity was determined 14 41.40 1.68 ± 0.40 12.48 ± 0.10 84.06 ± 3.15 99±3
through steady-shear flow curves. The most appropriate mathe- 15 46.04 1.29 ± 0.05 13.71 ± 0.05 84.65 ± 1.44 97 ± 2
16 48.85 1.45 ± 0.10 13.68 ± 0.14 82.42 ± 2.33 100 ± 2
matical model for describing the flow characteristics was the
17 47.21 1.30 ± 0.11 13.34 ± 0.30 79.76 ± 1.43 97 ± 2
Power Law, with flow behavior index values (n) inferior to 1 (be-
414 R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418
Fig. 2. Response surface for process yield, for (a) 20% maltodextrin, (b) feed flow rate of 15 g/min and (c) inlet air temperature of 170 °C.
R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418 415
Fig. 3. Response surface for powder moisture content, for (a) 20% maltodextrin, (b) feed flow rate of 15 g/min and (c) inlet air temperature of 170 °C.
Fig. 4. Response surface for powder hygroscopicity, for (a) 20% maltodextrin, (b) feed flow rate of 15 g/min and (c) inlet air temperature of 170 °C.
the greater water concentration gradient between the product and tion (20%). As inlet air temperature was the only variable affecting
the surrounding air. These results are in agreement with those anthocyanin retention (Table 3), the response surface relating inlet
published by Goula et al. (2004), in their work about spray drying air temperature and maltodextrin concentration is identical to the
of tomato pulp. Varying the compressed air flow rate, the drying air one showed at Fig. 5, while the surface relating feed flow rate and
flow rate and the inlet air temperature, the authors verified that maltodextrin concentration is a flat surface without inclination,
powders hygroscopicity inversely increased with powders mois- once none of these variables showed significant effect on this
ture content. response.
Increasing inlet air temperatures led to an increase on anthocy-
3.2.4. Anthocyanin retention anins loss, which is due to the high sensitivity of these pigments to
Fig. 5 shows the surface response obtained for anthocyanin high temperatures. Moreover, according to Quek et al. (2007),
retention, considering the middle point of maltodextrin concentra- powders produced at lower temperatures have a tendency to
agglomerate, because of their higher moisture content. This
agglomeration reduces the powder exposition to oxygen, protect-
ing the pigments against oxidation. Working with spray drying of
watermelon juice, these authors also verified a decrease of lyco-
pene and b-carotene content in the final powder, when increasing
the drying air temperature.
Ersus and Yurdagel (2007) studied the microencapsulation by
spray drying of anthocyanins extracted from black carrot, using
three drying temperatures (160, 180 and 200 °C) and three types
of maltodextrin (10, 20 and 30DE). The authors verified that for
the maltodextrins with higher DE, the powders produced at
160 °C showed higher pigments retention than the ones produced
at higher temperatures. On the other hand, for maltodextrin 10DE,
the drying temperature did not show significant effect on the
retention of anthocyanins.
Cai and Corke (2000) also verified a greater pigment loss with
Fig. 5. Response surface for anthocyanin retention, for 20% maltodextrin. increasing air temperatures in the spray drying of Amaranthus
416 R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418
betacyanin pigments and concluded that temperatures higher than obtained at different temperatures may also arise from the physi-
180 °C are not suitable for spray drying of betacyanins. The pow- cal characteristics of the crust, which may be pliable and collapsed
ders produced at lower temperatures showed better storage stabil- (when low and intermediate temperatures are used) or rigid and
ity (better retention of betacyanins) after 16 weeks, at 25 °C and porous (when high temperatures are used).
32%RH. Nijdam and Langrish (2006) also verified the formation of more
rigid particles when using higher temperatures in the spray drying
3.3. Powders morphology of milk. According to the authors, a vacuole forms within the par-
ticle soon after a skin develops on the surface, and it inflates once
Fig. 6 shows the SEM microphotographs of powders produced the particle temperature exceeds the local ambient boiling point
with feed flow rate of 15 g/min and 20% of maltodextrin, at three and the vapour pressure within the vacuole rises above the local
different temperatures. The particles produced with different mal- ambient pressure. When the drying temperature is sufficiently
todextrin concentrations (at 170 °C and feed flow rate of 15 g/min) high, moisture is evaporated very quickly and the skin becomes
were similar to those at Fig. 6c and d and are not shown here. dry and hard, so that the hollow particle cannot deflate when va-
The particles showed spherical shape and various sizes, which is pour condenses within the vacuole as the particle moves into cool-
typical of materials produced by spray drying. When the inlet air er regions of the dryer. However, when the drying temperature is
temperature was low, most of the particles showed a shriveled sur- lower, the skin remains moist and supple for longer, so that the
face, while increasing drying temperatures resulted in a larger hollow particle can deflate and shrivel as it cools.
number of particles with smooth surface. This is related to the dif-
ferences in the drying rate, which is higher for higher tempera- 3.4. Particle size distribution
tures, causing faster water evaporation and leading to the
formation of a smooth and hard crust. According to Allamilla-Belt- Figs. 7 and 8 show the particle size distribution for the powders
rán et al. (2005), the morphological differences between powders produced at different temperatures (with feed flow rate of 15 g/min
Fig. 6. Micrographs of particles at different temperatures and in different magnifications, with feed flow rate of 15 g/min and 20% maltodextrin: (a) 138 °C, 2000; (b) 138 °C,
7000; (c) 170 °C, 2000; (d) 170 °C, 7000; (e) 202 °C, 2000; (f) 202 °C, 7000.
R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418 417
Table 6
10
138ºC Mean diameter D[4,3] of powders produced at different temperatures, with feed flow
rate of 15 g/min and 20% maltodextrin
170ºC
8 202ºC Maltodextrin concentration (%) Mean diameter (lm)
10 13.27
Volume (%)
20 16.12
6 30 21.35
Table 5 References
Mean diameter D[4,3] of powders produced at different temperatures, with feed flow
rate of 15 g/min and 20% maltodextrin Abadio, F.D.B., Domingues, A.M., Borges, S.V., Oliveira, V.M., 2004. Physical
properties of powdered pineapple (Ananás comosus) juice – effect of malt
Temperature (°C) Mean diameter (lm)
dextrin concentration and atomization speed. Journal of Food Engineering 64
138 13.38 (3), 285–287.
170 16.12 Allamilla-Beltrán, L., Chanona-Pérez, J.J., Jiménez-Aparicio, A.R., Gutiérrez-López,
202 20.11 G.F., 2005. Description of morphological changes of particles along spray drying.
Journal of Food Engineering 67 (1–2), 179–184.
418 R.V. Tonon et al. / Journal of Food Engineering 88 (2008) 411–418
A.O.A.C., 1990. Official Methods of Analysis, 14th ed. Association of Official Khuri, A.J., Cornell, F.A., 1996. Response Surfaces: Design and Analyses, second ed.
Analytical Chemists, Washington, D.C. Marcel Dekker, NY.
Bhandari, B.R., Senoussi, A., Dumoulin, E.D., Lebert, A., 1993. Spray drying of Masters, K., 1991. Spray Drying Handbook, fifth ed. Longman Scientific and
concentrated fruit juices. Drying Technology 11 (5), 1081–1092. Technical, London.
Bligh, E.G., Dyer, W.J., 1959. A rapid method of total lipid extraction and Nijdam, J.J., Langrish, T.A.J., 2006. The effect of surface composition on the
purification. Canadian Journal of Biochemistry and Physiology 37 (8), 911–917. functional properties of milk powders. Journal of Food Engineering 77 (4),
Cai, Y.Z., Corke, H., 2000. Production and properties of spray-dried Amaranthus 919–925.
betacyanin pigments. Journal of Food Science 65 (6), 1248–1252. Nindo, C.I., Tang, J., Powers, J.R., Takhar, P.S., 2007. Rheological properties of
Cano-Chauca, M., Stringheta, P.C., Ramos, A.M., Cal-Vidal, J., 2005. Effect of the blueberry puree for processing applications. LWT – Food Science and
carriers on the microstructure of mango powder obtained by spray drying and Technology 40 (2), 292–299.
its functional characterization. Innovative Food Science and Emerging Papadakis, S.E., Gardeli, C., Tzia, C., 2006. Spray drying of raisin juice concentrate.
Technologies 5 (4), 420–428. Drying Technology 24 (2), 173–180.
Coisson, J.D., Travaglia, F., Piana, G., Capasso, M., Arlorio, M., 2005. Euterpe oleracea Quek, S.Y., Chok, N.K., Swedlund, P., 2007. The physicochemical properties of spray-
juice as a functional pigment for yogurt. Food Research International 38 (8–9), dried watermelon powder. Chemical Engineering and Processing 46 (5), 386–
893–897. 392.
Dak, M., Verma, R.C., Jaaffrey, S.N.A., 2006. Effect of temperature and concentration Rattes, A.L.R., Oliveira, W.P., 2007. Spray drying conditions and encapsulating
on rheological properties of ‘‘Kesar” mango juice. Journal of Food Engineering composition effects on formation and properties of sodium diclofenac
80 (4), 1011–1015. microparticles. Powder Technology 171 (1), 7–14.
Del Pozo-Insfran, D., Brenes, C.H., Talcott, S.T., 2004. Phytochemical composition Reiniccius, G.A., 2001. Multiple-core encapsulation – the spray drying of food
and pigment stability of acßai (Euterpe oleraceae Mart.). Journal of Agricultural ingredients. In: Vilstrup, P. (Ed.), Microencapsulation of Food Ingredients.
and Food Chemistry 52 (6), 1539–1545. Leatherhead Publishing, Surrey, pp. 151–185.
Dib Taxi, C.M., Menezes, H.C., Santos, A.B., Grosso, C.R., 2003. Study of the Ré, M.I., 1998. Microencapsulation by spray drying. Drying Technology 16 (6),
microencapsulation of camu–camu (Myrciaria dubia) juice. Journal of 1195–1236.
Microencapsulation 20 (4), 443–448. Righetto, A.M., Netto, F.M., 2005. Effect of encapsulating materials on water
Ersus, S., Yurdagel, U., 2007. Microencapsulation of anthocyanin pigments of black sorption, glass transition and stability of juice from immature acerola.
carrot (Daucuscarota L.) by spray dryer. Journal of Food Engineering 80 (3), 805– International Journal of Food Properties 8 (2), 337–346.
812. Rodríguez-Hernández, G.R., González-García, R., Grajales-Lagunes, A., Ruiz-Cabrera,
Francis, F.J., 1982. Analysis of anthocyanins. In: Markakis, P. (Ed.), Anthocyanins as M.A., 2005. Spray-drying of cactus pear juice (Opuntia streptacantha): effect on
Food Colors. Academic Press, NY, pp. 182–205. the physicochemical properties of powder and reconstituted product. Drying
Goula, A.M., Adamopoulos, K.G., Kazakis, N.A., 2004. Influence of spray drying Technology 23 (4), 955–973.
conditions on tomato powder properties. Drying Technology 22 (5), 1129–1151. Schauss, A.G., Wu, X., Prior, R.L., Ou, B., Huang, D., Owens, J., Agarwal, A., Jensen, G.S.,
Grabowski, J.A., Truong, V.D., Daubert, C.R., 2006. Spray-drying of amylase Hart, A.N., Shanbrom, E., 2006. Antioxidant capacity ond other bioactivities of
hydrolyzed sweet potato puree and physicochemical properties of powder. the freeze-dried amazoniam palm berry, Euterpe oleracea Mart. (Acai). Journal of
Journal of Food Science 71 (5), E209–E217. Agricultural and Food Chemistry 54 (22), 8604–8610.
Hong, J.H., Choi, Y.H., 2007. Physico-chemical properties of protein-bound Toneli, J., Park, K.J., Murr, F., Negreiros, A., 2006. Spray drying optimization to obtain
polysaccharide from Agaricus blazei Murill prepared by ultrafiltration and spray inulin powder. In: Proceedings of the 15th International Drying Symposium
drying process. International Journal of Food Science and Technology 42 (1), 1–8. (IDS 2006). Budapest, Hungary.
Jinapong, N., Suphantharika, M., Jamnong, P., 2008. Production of instant soymilk Wang, H., Cao, G., Prior, R.L., 1997. Oxygen radical absorbing capacity of
powders by ultrafiltration, spray drying and fluidized bed agglomeration. anthocyanins. Journal of Agricultural and Food Chemistry 45 (2), 304–309.
Journal of Food Engineering 84 (2), 194–205. Zanatta, C.F., Cuevas, E., Bobbio, F.O., Winterhalter, P., Mercadante, A.Z., 2005.
Keogh, M.K., Murray, C.A., O’Kennedy, B.T., 2003. Effects of ultrafiltration of whole Determination of anthocyanins from camu–camu (Myrciaria dubia) by HPLC-
milk on some properties of spray-dried milk powders. International Dairy PDA, HPLC-MS and NMR. Journal of Agricultural and Food Chemistry 53 (24),
Journal 13 (12), 995–1002. 9531–9535.