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Spray drying-microencapsulation of cinnamon infusions (Cinnamomum zeylanicum) with maltodextrin
Accepted Manuscript Spray drying-microencapsulation of cinnamon infusions (Cinnamomum zeylanicum) with maltodextrin R. Santiago-Adame, Dr. L. Medina-Torres, J.A. Gallegos-Infante, F. Calderas, R.F. González-Laredo, N.E. Rocha-Guzmán, L.A. Ochoa-Martínez, M.J. Bernad Bernad PII:
S0023-6438(15)00447-8
DOI:
10.1016/j.lwt.2015.06.020
Reference:
YFSTL 4740
To appear in:
LWT - Food Science and Technology
Received Date: 4 March 2015 Revised Date:
3 June 2015
Accepted Date: 6 June 2015
Please cite this article as: Santiago-Adame, R., Medina-Torres, L., Gallegos-Infante, J.A., Calderas, F., González-Laredo, R.F., Rocha-Guzmán, N.E., Ochoa-Martínez, L.A., Bernad Bernad, M.J., Spray drying-microencapsulation of cinnamon infusions (Cinnamomum zeylanicum) with maltodextrin, LWT Food Science and Technology (2015), doi: 10.1016/j.lwt.2015.06.020. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Spray drying-microencapsulation of cinnamon infusions (Cinnamomum zeylanicum)
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with maltodextrin
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R. Santiago-Adame a, L. Medina-Torres b*, J. A. Gallegos-Infante a , F. Calderas c, R. F.
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González-Laredo a, N. E. Rocha-Guzmán a, L.A. Ochoa-Martínez a, M. J. Bernad Bernad b
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Departamento de Ing. Química y Bioquímica, Instituto Tecnológico de Durango.,
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Blvd. Felipe Pescador 1830 Ote., 34080, Durango, Dgo., México.
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b*
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Facultad de Química, Departamento de Ingeniería Química, Universidad Nacional Autónoma de México (UNAM), México, D.F., 04510, México.
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CIATEC, A.C. Omega 201, Fracc. Industrial Delta, CP 37545, León, Gto., México.
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*
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Facultad de Química, Departamento de Ingeniería Química,
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Universidad Nacional Autónoma de México, México, D.F., 04510, México.
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e-mail address: [email protected]
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Tel. (52)-55-56225360 & (52)-55-59703815,
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Fax (52)-55-56225329
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Corresponding author: Dr. Luis Medina-Torres.
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ABSTRACT
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The effect of temperature and feed rate on spray dried cinnamon infusions (SDCInf) using
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maltodextrin as an encapsulating agent was studied (inlet temperature: 140, 160, and
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180°C; feed rate: 8 and 10 mL/min). Total phenolic content (TPC), antioxidant capacity
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(DPPH*), morphology (SEM), chemical (FTIR) and rheological properties, and releasing
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profiles were assessed in SDCInf. Cinnamon infusions (CInf) resulted in 29.32 (±0.70) mg
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of GAE/g of cinnamon. As for DPPH* inhibition, EC50 was 0.291 (±0.09) mg of cinnamon/
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mL. Microparticles showed a deflated-balloon like shape, encapsulating up to ~85% of the
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cinnamon infusion, and a simple shear-thinning behavior (n<1). Results show that
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powdered SDCInf obtained at 160 and 180 °C and 10 mL/min yielded the best protection
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for cinnamon infusions.
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Keywords: Microencapsulation, cinnamon infusions (Cinnamomum zeylanicum), spray-
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drying, rheological properties and release profile.
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1.
Introduction Spices are commonly used food additives. They provide flavor, aroma, color, and
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food preservative capabilities. Cinnamon is the second most important spice (just behind
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black pepper) in the USA and Europe (Jayaprakasha et al., 2007). Its consumption is
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related to health benefits, such as: antimicrobial activity, inhibition of cancer cells
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proliferation, protection against common flu, and glucose control in diabetes (Anderson et
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al., 2004). Among the compounds related to these effects are polyphenols. Polyphenols
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possess characteristic properties, such as free-radical scavenging and inhibition of oxidizing
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processes in the body. Phenolic compounds are important because they provide cinnamon
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with natural antioxidant capacity (i.e. scavenging of free radicals). However, they are
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extremely sensitive to environmental conditions (e.g. UV radiation, temperature, oxygen,
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digestion, etc.). Microencapsulation processes, such as spray drying, have proved to be an
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effective technology for protecting this sort of compounds. This technology turns
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suspensions into powdered microparticles, comprised of a wall material and a core.
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Carbohydrates, such as maltodextrins, are among major wall materials; they are used as
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encapsulating materials that protect the core (Desai & Park, 2005; Jafari et al., 2008).
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Maltodextrins are obtained from starch hydrolysis. They are cheap, highly water soluble
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(>75%), and aqueous solutions containing them have commonly low viscosity. This
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material has the ability to form a cover for the core, encapsulating aromas and flavors,
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minimizing exposure to oxygen (Pourashouri et al., 2014). Microparticles obtained by
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spray drying are able to protect cores for long periods and release them under digestive
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conditions. Therefore, this process is suitable for increasing polyphenols stability during
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long-term storage while preserving their biological activity (Mahadavi et al., 2014; Khazaei
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et al., 2014). Thus, this type of microparticles are studied in relation to their total phenolic
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content, chemical configuration (FTIR-analysis), morphology (Scanning Electron
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Microscopy), particle size homogeneity (Particle Size Distribution, PSD), rheological
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properties, and release profile. There are several studies on the non-polar fraction of
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cinnamon, yet only a few for the aqueous fraction. The aim of this study was to assess the
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effect of temperature and feed rate on the properties of SDCInf encapsulated with
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maltodextrin in order to find the best spray drying conditions to achieve the highest total
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phenolic content and antioxidant capacity.
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Materials and methods
2.1. Materials
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In 2013, bulk cinnamon was obtained in Durango, Mexico. It was then milled and
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sieved (#40 sieve) before processing. DE10 maltodextrin (MD) was also obtained from a
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domestic supplier (NIFRA Comerciales, S.A. Mexico City, Mexico).
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2.2.
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Cinnamon infusion, (CInf)
Infusions were prepared by adding 50 g of cinnamon into 500 mL of hot water at 80
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ºC, and continuously stirring for 10 minutes. Infusions were then filtered and lyophilized
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(Edwards Freeze-dryer modulo, Crowley, Sussex, UK), and stored until analysis.
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Extraction percent yield (%, E.Y) was calculated (Equation 1):
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%, E.Y= {[Total solids after lyophylization CInf (g)] / [Total weight of raw cinnamon used to prepare infusion (g)]} X 100
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2.3. Preparation of dispersions
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Dispersions were prepared by adding maltodextrin (100 g/L) into freshly prepared
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cinnamon infusions, and homogenized on a magnetic-stirrer at 300 rpm for 1 hour at 25 ºC.
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Dispersions were then spray dried using a Mini Spray Dryer B-290 Büchi (Flawil,
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Switzerland). Cinnamon infusions added with maltodextrin were feed into the spray dryer
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and process conditions were varied according to a 32 factorial experiment. Factors under
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study were feed rate at two levels 8 and10 mL/min, and inlet temperature at three levels
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140, 160, and 180 ºC. Pressure was held constant at 6.5 bar. These levels were chosen
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according to a number of studies regarding spray drying using maltodextrin as a wall
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material (Tonon et al., 2011; Janiszewska & Witrowa-Rajchert, 2009; Gallegos-Infante et
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al., 2013). Percent-yields were calculated using the ratio of the final weight of the powder
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obtained after spray drying to the total weight of solids in the solution fed to the spray dryer
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(Equation 2):
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%, SD.Y = [(Weight of microcapsules obtained after spray drying) / (Total weight of initial wall material and CInf)] X 100
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2.4
Moisture
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(2)
Water content was quantified by means of the AOAC 925.10 gravimetric method: a
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sample of 2 g was dried in a hot air oven at 103 ºC for 1 h, and moisture loss was
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determined by weighting and comparing the sample weight prior and after drying (AOAC
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International, 2000).
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2.5
Volumetric density
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Volumetric density was measured as proposed by Papadakis et al., (2006): 100 g of sample
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powder was transferred to a 250 mL graduated cylinder and the cylinder was tapped by hand on a
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bench 100 times from a height of 10 cm. Then the bulk density was calculated by dividing the mass
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of the powder by the final volume occupied by the powder in the cylinder.
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2.6
Total phenolic content
Both CInf and SDCInf were assessed for Total Phenolic Content (TPC) using the
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Folin-Ciocalteau method modified by Heimler et al., (2005). A calibration curve for Gallic
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acid in concentrations from 10 to 120 µg/mL (R2 = 0.99) was used to interpolate results of the TPC.
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2.7
Total flavonoid content
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Total flavonoid content (TFC) was assessed following Heimler et al., (2005). A
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calibration curve from catechin in concentrations from 10 to 120 µg/mL (R2 = 0.99) was
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used to interpolate the results of the TFC.
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Radical scavenging activity, (DPPH method) Antioxidant capacity was assessed by means of the DDPH assay (Brand-Williams et
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al., 1995) with minor modifications. A solution of CInf (10 mg/mL) in methanol was
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prepared in a range of concentrations (from 100 to 500 µg/mL). Then, 3.9 mL of a solution
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of DPPH* in methanol (6x10-5M) was added to the former solution. After 30 min,
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absorbance was measured at 515nm and 20 ºC. Methanol alone was used as a blank.
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Antioxidant capacity was calculated as EC50, i.e. the concentration of antioxidant required
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to achieve 50% of inhibition, (Equation 3): 6
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%, Inhibition = [(Conc. Of DPPH* t=30’) / (Conc. of DPPH* t=0)] X 100
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(3)
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2.9
IR spectrometry analysis, (FTIR)
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An analysis for CInf, MD, and SDCInf was carried out. Analysis was performed on
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an FTIR Nicolet 6700 (Thermo Fisher Scientific, USA) using the potassium bromide disc
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method. 100 scans were performed from 4000 to 400 cm-1 with a resolution of 1 cm-1.
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2.10 Scanning electron microscopy, (SEM)
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It was carried out according to the method reported by Quiñones-Muñoz et al.,
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(2011). SDCInf samples were placed on a piece of copper with conductive tape and coated
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with gold at 10 mbar for 90 seconds (model Desk II, Denton Vacuum, NJ, USA). They
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were then observed in a scanning electron microscope (JEOL Mod. JSM6300 Jeol, Japan)
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at an accelerating voltage of 20 Kv and magnified up to 1000X.
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2.11 Particle size distribution, (PSD)
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PSD of SDCInf dispersions were quantified in a Master-Sizer 2000 laser diffraction
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particle analyzer (Malvern Instrument Ltd, UK). Powdered SDCInf was dispersed using
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deionized water as dispersing agent (SDCInf, R. I. =1.582; dispersant agent R. I. =1.330).
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2.12 Rheological behavior of spray dried cinnamon infusions
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Rheological characterization of SDCInf aqueous dispersions (3 g/100 mL) was
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performed by means of both simple and oscillatory shear tests. A controlled stress
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rheometer (AR-G2, TA Instruments) attached to a concentric cylinder geometry (21.96mm
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outer diameter, 20.38mm inner diameter, 59.50mm height, and 500µm gap) was used.
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Temperature was held constant at 25 ºC using a circulating water bath (Cole Parmer
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Polystat and Peltier AR-G2). Powdered SDCInf were dispersed in deionized water using a
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magnetic-stirrer at 300 rpm for 1 hour at 25 ºC. Aqueous dispersions were assessed for both
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viscosity, [η ( γ& )] (simple shear rates from 0.1 to 200 s-1), and viscoelastic properties
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[storage G’, and loss G” moduli] (oscillatory shear frequencies from 0.1 to 200 rad/s),
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within the linear viscoelastic range. Each rheological test was performed by duplicate. Data
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from tests were acquired and analyzed directly from the TA Rheology Advance Data
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Analysis software V.5.7.0 (TA Instrument Ltd., Crawley, UK).
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2.13 Controlled release analysis of SDCInf
Release analysis of CInf from powdered SDCInf (microcapsules) was carried out
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following Desai & Park, (2005) using a dissolution device (Franz cell) equipped with a
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permeable membrane of 0.45 µm (Nylon HV, Millipore) and a water bath at 37 ºC under
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constant stirring (300 rpm). SDCInf aqueous dispersions at a concentration of 0.2 g/mL and
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pH ~6.0 (simulated medium) were prepared trying to mimic the release under digestive
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tract conditions.
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2.14 Statistical analysis
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This study was carried out according to a 32 factorial design (Temperature: 140, 160,
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and 180 ºC; Feed rate: 8 and 10 mL/min and pressure was held constant at 6.5 bar.
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ANOVA and Tukey test (α=0.05) were performed to the data using Statistica 7.0 (Statsoft,
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Tulsa, Oklahoma, EUA).
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Results and discussion
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3.1
Percent-yield from extraction and drying processes, moisture content, and density.
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The highest percent-yield was obtained at a high feed rate (10 mL/min) (Table 1). A
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similar behavior, yet with lower percent-yields (~25%), was reported for Quercus resinosa
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infusions (Gallegos-Infante et al., 2013) using maltodextrin as an encapsulating agent.
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Moisture content ranged from 1.34% (±0.07) to 1.99% (±0.14). The lowest moisture
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content was obtained at a temperature of 180 ºC and a feed rate of 8 mL/min. This result
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was lower than those reported in studies on watermelon extracts and mixtures of
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pomegranate with apple (Quek et al., 2007; Ochoa-Martinez et al., 2011). These
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differences could be attributed to the content of sugar in the sample, as well as to the degree
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of dextrinization of the maltodextrin used as encapsulating material. As for density, results
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ranged from 0.536 to 0.554 g/cm3, similar to those reported in other studies (Papadakis et
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al., 2006; Ochoa-Martínez et al., 2011).
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3.2
Total phenolic content, flavonoids and antioxidant activity
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TPC in the CInf was 29.32 (±0.70) mg of GAE/g of cinnamon. As for SDCInf, the highest
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TPC values were achieved in samples SDCInf 18010 and SDCInf 18008 at 8 and 10
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mL/min respectively (both at 180 °C), and in sample SDCInf 14010 at 10 ml/min feed rate
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and 140 °C temperature (Table 1). These conditions reduced heat degradation of phenols
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during the spray drying process, thus preserving from 55.9 to 68.79% of the original TPC
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in the SDCInf. TPC in cinnamon was higher than that reported by Cai et al., (2004) and
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Muchuweti et al., (2007) (18.7 mg and 15.5 mg of GAE/g of cinnamon, respectively). On
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the other hand, it was lower than that reported by Shan et al., (2005) (63.4 mg of GAE/g of
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cinnamon). This trend was also observed on the TFC for CInf, 51.34 (±3.41) mg of CE/g of
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cinnamon. The highest TFC in SDCInf was 35.76 (±1.51) mg of CE/g of cinnamon; it was
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obtained at a temperature of 140 ºC and a feed rate of 10 mL/min. The spray drying process
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preserved from 29.02 to 35.76 (±1.51) mg of CE/g of cinnamon (i.e., 56.53 - 69.65%) from
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the flavonoids originally present in raw cinnamon. These results were from 9.63 to 46.40
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mg of CE (i.e., 18.75 - 90.37 %) higher than those observed on 5 varieties of cinnamon in
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China (Prasad et al., 2009).
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There is a significant reduction of TPC and TFC when the temperature was increased from
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140 to 160 °C (Table 1), a reverse effect is observed when the temperature varies from 160
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to 180 °C. This reverse trend may be explained by the occurrence of synthesis and
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polymerization of phenols and flavonoids which influences the total content of these
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compounds (Mishra et al., 2014). However, other factor may be affecting the results such
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as the outflow spray drying conditions which were not controlled nor evaluated here.
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Table 1
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At 180 °C and 160 °C, both runs (8 and 10 mL/min) showed the highest antioxidant
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capacity (lowest EC50 values in Table 1). However, sample at 180 °C and 10 mL/min
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(SDCInf 18010) resulted with the highest percent yield of all samples. Antioxidant capacity
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analysis estimates the median effective concentration (EC50). EC50 is the concentration than 10
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inhibits 50 % of the DPPH* radicals in solution; the lower the EC50, the higher the
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antioxidant capacity. In this study, an EC50 of 0.29 mg/mL (R2= 0.99) was estimated for
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CInf. This estimate is somehow lower than that reported for alcoholic extracts of Cinnamon
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cassia (Jang et al., 2012). However, spray drying conditions had an effect on the
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antioxidant capacity of powdered SDCInf. As for EC50, results ranged from 3.36 (±0.14) to
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5.96 (±0.11) mg/mL in powdered SDCInf. The highest antioxidant capacity and % yield
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were obtained at a temperature of 180 ºC and a feed rate of 10 mL/min. This behavior is
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commonly observed on processes for encapsulating compounds with antioxidant activity at
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spray drying temperatures higher than 65 ºC (Krishnaiah et al., 2012; Gallegos-Infante et
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al., 2013). As for TPC, TFC, and free radical scavenging (DPPH), the effect of the feed rate
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was significant (p-value<0.05), i.e., the time the material remains in contact with the air
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inside the chamber of the spray dryer is relevant. Although more energy is required to
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remove water from the dispersion (CInf-MD) at a feed rate of 10 mL/min, this seems to be
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beneficial for the antioxidant capacity of CInf, thus minimizing polyphenol degradation and
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protecting its antioxidant capacity. In general, the best results were found in samples at a
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feed rate of 10 mL/min, analyses were performed only at this condition for particle size
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distribution (PSD) and release profiles.
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3.3
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FTIR spectrometry analysis
FTIR spectrometry analysis was carried out to elucidate the sort of molecules
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comprising the compound of interest. Both CInf-MD (raw material) and SDCInf (dry
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product) samples were analyzed in solid state. Air contact was minimized in order to avoid
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water absorption (aw = 0.1). All FTIR-spectra (Figure 1) showed an absorption band at a 11
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wave length (λ) of 3300 cm-1, which is characteristic of hydroxyl (-OH) groups; this band
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decreased in SDCInf samples though. CInf FTIR-spectra showed absorption bands that
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could be regarded as its molecular fingerprint because these bands are not present in MD
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FTIR-spectrum. Furthermore, these bands can be helpful to set criteria for the cover-up
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effect of MD on CInf when analyzing SDCInf FTIR-spectra. Figure 1.
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Figure 1 shows characteristic wave lengths. Wave lengths at 1020 cm-1 (C-O; C-O-
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C), 1440 cm-1 (=CH2, -C-H, =C-H), 1519 cm-1 (R-CO-NH-R), 1600 cm-1 (C-C, C=C, H-O-
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H), and 2387 cm-1 (CH2, nCH3) are closely related to aromatic compounds with phenyl
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bonds similar to those in polyphenolic compounds, such as flavonoids (Schulz & Baranska,
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2007; Heneczkowski et al., 2001). MD cover-up effect on CInf was ~85%. From these
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results, encapsulation of CInf with MD can be assumed. Moreover, results from TPC in
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SDCInf support this assumption, see Section 3.2 above.
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3.4
Scanning electron microscopy, (SEM)
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Interactions between CInf and MD could be explained by microparticles morphology.
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Figure 2 shows micrographs of powdered SDCInf obtained at different temperatures and
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feed rates. In these micrographs, semi-spherical microparticles are the most commonly
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observed morphology. Microparticles showed rough surfaces with cavities and some
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structural cracks. Morphological irregularities could be due to water evaporation rates
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during spray drying process. The higher the temperature (faster evaporation) the smoother
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and more defined the surfaces. This result is similar to that reported by Alamilla-Beltran et
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al., (2005), who found that lower air inlet temperatures resulted in irregularly shaped
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microparticles with creased surfaces, while higher air inlet temperatures resulted in more
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rigid microparticles and porous surfaces. Spray drying process both at 160 and 180 ºC and
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at a feed rate of 10 mL/min produced microparticles morphologically more defined, semi-
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spherical, without evident cracks or particle agglomerations. Microparticles obtained at a
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feed rate of 8 mL/min showed irregular surfaces and particle agglomerations for all three
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temperatures. A similar result was reported by Tonon et al., (2009) for açai juice
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encapsulated with maltodextrin. They obtained both smooth spherical and irregular semi-
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spherical microparticles. Figure 2
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Particle size distribution of SDCInf
Particle size distribution of microparticles was also studied. Figure 3 shows PSD of
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powdered SDCInf obtained at a Feed rate of 10 mL/min for all three temperatures (140, 160
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and 180 ºC). Microparticles size ranged from 6 to 30 microns. Particle size results show a
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quasi-modal distribution with a single mode and wide base (heavy tails) for some
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treatments. This result is particularly interesting because small particles tend to form
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uniform arrays in solution with minimal gaps among particles. On the other hand, large
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particles can fill surrounding gaps, mostly producing homogeneous solutions that are stable
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under mechanical flow. Large particles, if present, could probably be produced by particle
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agglomeration processes due to particle-particle interactions and continuous aggregation.
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This situation was observed at low feed rate (Figure 3). Volumetric diameter d [4, 3] ranged
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from 10.01 to 12.51 microns. There was a very small difference, yet statistically significant,
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among treatments (p-value < 0.05).
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On the other hand, both samples at 160 ºC and 180 ºC temperatures showed similar
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results (10.53 and 10.01 microns, respectively). This can indeed be attributed to
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temperature. This result is in accordance to those reported by Reineccius (2001). They
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reported that high drying temperatures produce a particle structure, and minimize creasing
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and flexing of microparticles. Similar particle sizes were reported using polyphenolic
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compounds from Orthosiphon stamineus extracts (Pang et al., 2014) encapsulated with
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maltodextrins, and rosemary oil encapsulated both with maltodextrins and arabic gum in a
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range of proportions (Janiszewska & Witrowa‐Rajchert, 2009). Note that this analysis is
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important to determine the dimensional space occupied by microparticles in aqueous
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dispersions. This information is essential to shed light on the mechanical response
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(dynamic spectrum and viscosity of dispersions).
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Rheological behavior of spray dried cinnamon infusions All treatments produced powdered SDCInf with shear-thinning behaviors (n<1) in
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solution (Figure 4). However, powdered SDCInf obtained at a temperature of 160 ºC
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showed a more stable mechanical response (regardless of the Feed rate), i.e., Temperature
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had a significant effect (p-value < 0.05) on shear-flow stability. This could be due to
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thermal degradation and/or oxidation of microparticles during the spray drying process
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(Tuyen et al., 2010).
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Figure 4
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Powdered SDCInf remained stable even when obtained at a temperature as high as
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180 ºC. Flow curves showed the same shear-thinning trend around γ& =10 s-1, where
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samples from all treatments overlapped. Similar results were reported in studies on spray
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drying (Grabowski et al., 2008; Medina-Torres, et al., 2000 and 2013). Results from
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SDCInf obtained at a temperature of 160 ºC and a feed rate of 10 mL/min showed the
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highest viscosity. This could be related to particle size distribution (quasi-modal), since
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viscosity increases are related to small and uniform particle sizes, like those obtained in this
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study, where particle-particle interactions possibly increase along with flow resistance,
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specifically at high shear rates like those reported in similar studies (Hill & Carrington,
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2006). The effect of temperature and feed rate on both the storage (G’) and loss (G”)
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moduli, as a function of oscillatory shear frequency (ω), of SDCInf dispersions are shown
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in Figure 5.
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Figure 5.
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Microparticles showed a pseudo solid-like behavior, with a plateau zone formation at
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low frequencies yet with dominant viscous behavior (G'' > G'). This evidences phase
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interactions between MD and CInf at short times due to encapsulation. Moduli dissociation
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is found at oscillatory shear frequencies (ω) lower than 100 rad/s. However, SDCInf
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obtained at a temperature of 160 ºC showed mechanical stability to flow (regardless of the
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feed rate). Similar trends were reported in studies using carbohydrates as an encapsulating
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agent (Medina-Torres et al., 2013; León-Martinez et al., 2011).
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3.7
Controlled release analysis of SDCInf 15
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Releasing profiles of microcapsules are very important in order to estimate the
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storage time that microcapsules can achieve, as well as the releasing profile of the core. In
3
this study, we had no problems when preparing SDCInf dispersions in water. In fact,
4
SDCInf-water dispersions were homogeneous and no precipitates were observed (electric
5
potential, p Z > 30mV). However, feed rate had a significant effect (p-value < 0.05), i.e.,
6
high feed rates yielded concentrations of CInf ~10% higher inside the microcapsule and
7
core release lasted around 36 hours. This difference is partially due to mechanical stability
8
to flow (see Figure 4 and 5).
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The study of the release profile of microcapsules of SDCInf was performed in a Franz
10
cell equipped with a 0.45 micron membrane. SDCInf samples were double processed at a
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concentration of 3 g/100 mL in order to mimic digestive tract conditions. These results
12
were analyzed at a wavelength of 281.2 nm (Spectro-photometer UV-Vis, Analytical
13
Instruments Co. USA). SDCInf controlled release is designed for the conditions inside the
14
small bowel, because it is there where polyphenols from CInf are released. SDCInf samples
15
were continuously monitored until no signal was registered in the spectrum. However, after
16
60 hours there was still an increase in the signal spectrum due to MD, but not due to CInf.
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Figure 6 shows the controlled release of SDCInf, where ~80.5% of CInf was released
18
within 48 hours. Liberation profiles reach a steady state after approximately 5 hours when
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~70% of the encapsulated compounds have been released. This will ensure optimum
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absorption of the polyphenols in the small intestine.
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Microcapsules showed high efficiency of encapsulation (>70%) using maltodextrin.
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This can be attributed to microencapsulation conditions, which showed a quasi-modal
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particle size and are in principle more stable. Sample at 160 °C and 10 mL/min (SDCaSA
24
16010) showed the highest percent release of the three samples investigated. This is 16
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attributed to the quasi-modal particle size distribution together with stability to flow (high
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viscosity) of this sample due to the enhanced particle-particle interactions promoted by
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agitation and shear.
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Figure 6.
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These results can shed light on the expected behavior when SDCInf dispersions are
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prepared and ingested, mimicking conditions similar to those inside the digestive tract,
9
where release occurs for a longer time, and allowing the antioxidant capacity of this spice
10
to last longer in the body. The co-existence of two microstructures was confirmed by FTIR,
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rheological behavior and controlled release of SDCInf. This can be attributed to
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microencapsulation conditions (Medina et al., 2013).
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4.
Conclusions
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Spray drying of cinnamon infusions using maltodextrin as a wall material under the
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temperature and feed rate conditions developed in this study showed that encapsulation and
18
interactions are both possible. Spray drying at a feed rate of 10 mL/min and temperatures of
19
160 and 180 ºC are both ideal for encapsulating this sort of cinnamon infusions.
20
Microcapsules obtained under these conditions protect both phenolic content and
21
antioxidant capacity, and produced similar particle size distributions for all treatments.
22
However, at 160 °C percent-yield of dried product was lower than at 180 °C.
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SDCInf obtained at 10 mL/min and a
temperature of 160 ºC showed the best
mechanical response to shear (high viscosity), and this combined with a narrower particle 17
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size distribution resulted in a more rapid and higher percent release of encapsulated
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polyphenols. This study conditions may shed some light on the properties and stability of
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microencapsulated water infusions of spices. It sets a precedent for further research in an
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area that has been barely explored.
Nomenclature List:
7
SDCInf:
Spray drying cinnamon infusions
8
TPC:
Total phenolic content
9
TFC:
Total flavonoids content
10
DPPH*:
1,1-diphenyl-2picrylhydrazil radical
11
SEM:
Scanning electron microscopy
12
FTIR:
Fourier transform infrared spectroscopy
13
CInf:
Cinnamon infusion
14
PSD:
Particle size distribution
15
GAE:
Gallic acid equivalents
16
CE:
Catechin equivalents
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EC50:
Efficient concentration
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Figure and table captions
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Table 1.
Results of spray drying yield, moisture, density, total phenols content (TPC), total flavonoid content (TFC) and DPPH* EC50.
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Figure 1. FTIR spectrum of (—) Maltodextrin (···), Cinnamon Infusion and (- - -) SDCInf 16010.
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Figure 2. Micrographs of SDCInf, a)SDCInf 14008, b)SDCInf 16008 and c) SDCInf 18008, d) SDCInf 14010, e) SDCInf 16010 and f) SDCInf 18010.
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Figure 3. PSD of SDCInf feeding at 10 mL/min.
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Figure 4. Viscosity curves of SDCInf: SDCInf 14008, SDCInf 16008
and
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SDCInf 18008 and b) SDCInf 14010, SDCInf 16010 and SDCInf
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18010. Figure 5.
Effect of spray drying conditions on curve of storage (G’) and loss (G”)
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modulus a): SDCInf 14008, SDCInf 16008 and SDCInf 18008 and b):
15
SDCInf 14010, SDCInf 16010 and SDCInf 18010. (Filled symbols are
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G’, blank symbols represent G”).
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Figure 6. Release profiles of SDCInf: SDCInf 14010, SDCInf 16010 and SDCInf 18010.
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Table 1. Results of spray drying yield, moisture, density, total phenols content (TPC), total flavonoid content (TFC) and DPPH* EC50. Yield %
Moisturea
CInf
4.75 (+0.33)
--
SDCInf 14008
27.48 (+ 0.10)
SDCInf 16008
36.92 (+ 0.74)
SDCInf 18008
39.19 (+ 0.80)
SDCInf 14010
40.28 (+ 0.14)
SDCInf 16010 SDCInf 18010
TPCc
TFC d
DPPH* EC50 e
--
29.32 (+ 0.70)
51.34 (+3.41)
0.29 (+0.95)
1.89 (+ 0.01)
0.544 (+ 0.003)
18.33 (+ 0.29)
31.13 (+1.51)
4.74 (+0.46)
1.54 (+ 0.07)
0.554 (+ 0.005)
18.43 (+ 0.04)
30.41 (+4.12)
3.60 (+0.12)
1.34 (+ 0.07)
0.550 (+ 0.003)
18.77 (+ 0.80)
33.33 (+2.07)
3.50 (+0.19)
1.99 (+ 0.14)
0.540 (+ 0.004)
19.60 (+ 0.07)
35.76 (+1.51)
5.96 (+0.11)
40.82 (+ 0.73)
1.75 (+ 0.07)
0.540 (+ 0.004)
16.39 (+ 0.83)
29.02 (+0.79)
3.65 (+0.22)
49.60 (+ 0.15)
1.58 (+ 0.13)
0.536 (+ 0.007)
20.17 (+ 0.81)
34.70 (+4.06)
3.36 (+0.14)
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Highlights • Cinnamon infusions with antioxidant capacity were spray dried • Optimum conditions were found to produce stable and well-formed microcapsules
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• Produced microcapsules preserve both phenolic content and antioxidant capacity • The rheological characterization evidenced strong particle-particle interactions
• Encapsulated systems may be optimum delivery systems according to release
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S0023-6438(15)00447-8
DOI:
10.1016/j.lwt.2015.06.020
Reference:
YFSTL 4740
To appear in:
LWT - Food Science and Technology
Received Date: 4 March 2015 Revised Date:
3 June 2015
Accepted Date: 6 June 2015
Please cite this article as: Santiago-Adame, R., Medina-Torres, L., Gallegos-Infante, J.A., Calderas, F., González-Laredo, R.F., Rocha-Guzmán, N.E., Ochoa-Martínez, L.A., Bernad Bernad, M.J., Spray drying-microencapsulation of cinnamon infusions (Cinnamomum zeylanicum) with maltodextrin, LWT Food Science and Technology (2015), doi: 10.1016/j.lwt.2015.06.020. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
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Spray drying-microencapsulation of cinnamon infusions (Cinnamomum zeylanicum)
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with maltodextrin
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R. Santiago-Adame a, L. Medina-Torres b*, J. A. Gallegos-Infante a , F. Calderas c, R. F.
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González-Laredo a, N. E. Rocha-Guzmán a, L.A. Ochoa-Martínez a, M. J. Bernad Bernad b
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Departamento de Ing. Química y Bioquímica, Instituto Tecnológico de Durango.,
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Blvd. Felipe Pescador 1830 Ote., 34080, Durango, Dgo., México.
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b*
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Facultad de Química, Departamento de Ingeniería Química, Universidad Nacional Autónoma de México (UNAM), México, D.F., 04510, México.
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CIATEC, A.C. Omega 201, Fracc. Industrial Delta, CP 37545, León, Gto., México.
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*
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Facultad de Química, Departamento de Ingeniería Química,
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Universidad Nacional Autónoma de México, México, D.F., 04510, México.
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e-mail address: [email protected]
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Tel. (52)-55-56225360 & (52)-55-59703815,
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Fax (52)-55-56225329
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Corresponding author: Dr. Luis Medina-Torres.
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ABSTRACT
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The effect of temperature and feed rate on spray dried cinnamon infusions (SDCInf) using
3
maltodextrin as an encapsulating agent was studied (inlet temperature: 140, 160, and
4
180°C; feed rate: 8 and 10 mL/min). Total phenolic content (TPC), antioxidant capacity
5
(DPPH*), morphology (SEM), chemical (FTIR) and rheological properties, and releasing
6
profiles were assessed in SDCInf. Cinnamon infusions (CInf) resulted in 29.32 (±0.70) mg
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of GAE/g of cinnamon. As for DPPH* inhibition, EC50 was 0.291 (±0.09) mg of cinnamon/
8
mL. Microparticles showed a deflated-balloon like shape, encapsulating up to ~85% of the
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cinnamon infusion, and a simple shear-thinning behavior (n<1). Results show that
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powdered SDCInf obtained at 160 and 180 °C and 10 mL/min yielded the best protection
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for cinnamon infusions.
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Keywords: Microencapsulation, cinnamon infusions (Cinnamomum zeylanicum), spray-
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drying, rheological properties and release profile.
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1.
Introduction Spices are commonly used food additives. They provide flavor, aroma, color, and
3
food preservative capabilities. Cinnamon is the second most important spice (just behind
4
black pepper) in the USA and Europe (Jayaprakasha et al., 2007). Its consumption is
5
related to health benefits, such as: antimicrobial activity, inhibition of cancer cells
6
proliferation, protection against common flu, and glucose control in diabetes (Anderson et
7
al., 2004). Among the compounds related to these effects are polyphenols. Polyphenols
8
possess characteristic properties, such as free-radical scavenging and inhibition of oxidizing
9
processes in the body. Phenolic compounds are important because they provide cinnamon
10
with natural antioxidant capacity (i.e. scavenging of free radicals). However, they are
11
extremely sensitive to environmental conditions (e.g. UV radiation, temperature, oxygen,
12
digestion, etc.). Microencapsulation processes, such as spray drying, have proved to be an
13
effective technology for protecting this sort of compounds. This technology turns
14
suspensions into powdered microparticles, comprised of a wall material and a core.
15
Carbohydrates, such as maltodextrins, are among major wall materials; they are used as
16
encapsulating materials that protect the core (Desai & Park, 2005; Jafari et al., 2008).
17
Maltodextrins are obtained from starch hydrolysis. They are cheap, highly water soluble
18
(>75%), and aqueous solutions containing them have commonly low viscosity. This
19
material has the ability to form a cover for the core, encapsulating aromas and flavors,
20
minimizing exposure to oxygen (Pourashouri et al., 2014). Microparticles obtained by
21
spray drying are able to protect cores for long periods and release them under digestive
22
conditions. Therefore, this process is suitable for increasing polyphenols stability during
23
long-term storage while preserving their biological activity (Mahadavi et al., 2014; Khazaei
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et al., 2014). Thus, this type of microparticles are studied in relation to their total phenolic
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content, chemical configuration (FTIR-analysis), morphology (Scanning Electron
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Microscopy), particle size homogeneity (Particle Size Distribution, PSD), rheological
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properties, and release profile. There are several studies on the non-polar fraction of
4
cinnamon, yet only a few for the aqueous fraction. The aim of this study was to assess the
5
effect of temperature and feed rate on the properties of SDCInf encapsulated with
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maltodextrin in order to find the best spray drying conditions to achieve the highest total
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phenolic content and antioxidant capacity.
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Materials and methods
2.1. Materials
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In 2013, bulk cinnamon was obtained in Durango, Mexico. It was then milled and
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sieved (#40 sieve) before processing. DE10 maltodextrin (MD) was also obtained from a
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domestic supplier (NIFRA Comerciales, S.A. Mexico City, Mexico).
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2.2.
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Cinnamon infusion, (CInf)
Infusions were prepared by adding 50 g of cinnamon into 500 mL of hot water at 80
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ºC, and continuously stirring for 10 minutes. Infusions were then filtered and lyophilized
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(Edwards Freeze-dryer modulo, Crowley, Sussex, UK), and stored until analysis.
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Extraction percent yield (%, E.Y) was calculated (Equation 1):
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%, E.Y= {[Total solids after lyophylization CInf (g)] / [Total weight of raw cinnamon used to prepare infusion (g)]} X 100
(1)
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2.3. Preparation of dispersions
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Dispersions were prepared by adding maltodextrin (100 g/L) into freshly prepared
2
cinnamon infusions, and homogenized on a magnetic-stirrer at 300 rpm for 1 hour at 25 ºC.
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Dispersions were then spray dried using a Mini Spray Dryer B-290 Büchi (Flawil,
4
Switzerland). Cinnamon infusions added with maltodextrin were feed into the spray dryer
5
and process conditions were varied according to a 32 factorial experiment. Factors under
6
study were feed rate at two levels 8 and10 mL/min, and inlet temperature at three levels
7
140, 160, and 180 ºC. Pressure was held constant at 6.5 bar. These levels were chosen
8
according to a number of studies regarding spray drying using maltodextrin as a wall
9
material (Tonon et al., 2011; Janiszewska & Witrowa-Rajchert, 2009; Gallegos-Infante et
10
al., 2013). Percent-yields were calculated using the ratio of the final weight of the powder
11
obtained after spray drying to the total weight of solids in the solution fed to the spray dryer
12
(Equation 2):
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%, SD.Y = [(Weight of microcapsules obtained after spray drying) / (Total weight of initial wall material and CInf)] X 100
15
17
2.4
Moisture
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(2)
Water content was quantified by means of the AOAC 925.10 gravimetric method: a
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sample of 2 g was dried in a hot air oven at 103 ºC for 1 h, and moisture loss was
20
determined by weighting and comparing the sample weight prior and after drying (AOAC
21
International, 2000).
22 23
2.5
Volumetric density
5
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Volumetric density was measured as proposed by Papadakis et al., (2006): 100 g of sample
2
powder was transferred to a 250 mL graduated cylinder and the cylinder was tapped by hand on a
3
bench 100 times from a height of 10 cm. Then the bulk density was calculated by dividing the mass
4
of the powder by the final volume occupied by the powder in the cylinder.
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2.6
Total phenolic content
Both CInf and SDCInf were assessed for Total Phenolic Content (TPC) using the
8
Folin-Ciocalteau method modified by Heimler et al., (2005). A calibration curve for Gallic
9
acid in concentrations from 10 to 120 µg/mL (R2 = 0.99) was used to interpolate results of the TPC.
11 12
2.7
Total flavonoid content
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Total flavonoid content (TFC) was assessed following Heimler et al., (2005). A
14
calibration curve from catechin in concentrations from 10 to 120 µg/mL (R2 = 0.99) was
15
used to interpolate the results of the TFC.
16
18
2.8
Radical scavenging activity, (DPPH method) Antioxidant capacity was assessed by means of the DDPH assay (Brand-Williams et
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al., 1995) with minor modifications. A solution of CInf (10 mg/mL) in methanol was
20
prepared in a range of concentrations (from 100 to 500 µg/mL). Then, 3.9 mL of a solution
21
of DPPH* in methanol (6x10-5M) was added to the former solution. After 30 min,
22
absorbance was measured at 515nm and 20 ºC. Methanol alone was used as a blank.
23
Antioxidant capacity was calculated as EC50, i.e. the concentration of antioxidant required
24
to achieve 50% of inhibition, (Equation 3): 6
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%, Inhibition = [(Conc. Of DPPH* t=30’) / (Conc. of DPPH* t=0)] X 100
2
(3)
3
2.9
IR spectrometry analysis, (FTIR)
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An analysis for CInf, MD, and SDCInf was carried out. Analysis was performed on
6
an FTIR Nicolet 6700 (Thermo Fisher Scientific, USA) using the potassium bromide disc
7
method. 100 scans were performed from 4000 to 400 cm-1 with a resolution of 1 cm-1.
8
2.10 Scanning electron microscopy, (SEM)
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It was carried out according to the method reported by Quiñones-Muñoz et al.,
11
(2011). SDCInf samples were placed on a piece of copper with conductive tape and coated
12
with gold at 10 mbar for 90 seconds (model Desk II, Denton Vacuum, NJ, USA). They
13
were then observed in a scanning electron microscope (JEOL Mod. JSM6300 Jeol, Japan)
14
at an accelerating voltage of 20 Kv and magnified up to 1000X.
16
2.11 Particle size distribution, (PSD)
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PSD of SDCInf dispersions were quantified in a Master-Sizer 2000 laser diffraction
18
particle analyzer (Malvern Instrument Ltd, UK). Powdered SDCInf was dispersed using
19
deionized water as dispersing agent (SDCInf, R. I. =1.582; dispersant agent R. I. =1.330).
20 21
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2.12 Rheological behavior of spray dried cinnamon infusions
22
Rheological characterization of SDCInf aqueous dispersions (3 g/100 mL) was
23
performed by means of both simple and oscillatory shear tests. A controlled stress
7
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rheometer (AR-G2, TA Instruments) attached to a concentric cylinder geometry (21.96mm
2
outer diameter, 20.38mm inner diameter, 59.50mm height, and 500µm gap) was used.
3
Temperature was held constant at 25 ºC using a circulating water bath (Cole Parmer
4
Polystat and Peltier AR-G2). Powdered SDCInf were dispersed in deionized water using a
5
magnetic-stirrer at 300 rpm for 1 hour at 25 ºC. Aqueous dispersions were assessed for both
6
viscosity, [η ( γ& )] (simple shear rates from 0.1 to 200 s-1), and viscoelastic properties
7
[storage G’, and loss G” moduli] (oscillatory shear frequencies from 0.1 to 200 rad/s),
8
within the linear viscoelastic range. Each rheological test was performed by duplicate. Data
9
from tests were acquired and analyzed directly from the TA Rheology Advance Data
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Analysis software V.5.7.0 (TA Instrument Ltd., Crawley, UK).
11 12
2.13 Controlled release analysis of SDCInf
Release analysis of CInf from powdered SDCInf (microcapsules) was carried out
14
following Desai & Park, (2005) using a dissolution device (Franz cell) equipped with a
15
permeable membrane of 0.45 µm (Nylon HV, Millipore) and a water bath at 37 ºC under
16
constant stirring (300 rpm). SDCInf aqueous dispersions at a concentration of 0.2 g/mL and
17
pH ~6.0 (simulated medium) were prepared trying to mimic the release under digestive
18
tract conditions.
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2.14 Statistical analysis
21
This study was carried out according to a 32 factorial design (Temperature: 140, 160,
22
and 180 ºC; Feed rate: 8 and 10 mL/min and pressure was held constant at 6.5 bar.
8
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ANOVA and Tukey test (α=0.05) were performed to the data using Statistica 7.0 (Statsoft,
2
Tulsa, Oklahoma, EUA).
3
3.
Results and discussion
5
3.1
Percent-yield from extraction and drying processes, moisture content, and density.
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The highest percent-yield was obtained at a high feed rate (10 mL/min) (Table 1). A
7
similar behavior, yet with lower percent-yields (~25%), was reported for Quercus resinosa
8
infusions (Gallegos-Infante et al., 2013) using maltodextrin as an encapsulating agent.
9
Moisture content ranged from 1.34% (±0.07) to 1.99% (±0.14). The lowest moisture
10
content was obtained at a temperature of 180 ºC and a feed rate of 8 mL/min. This result
11
was lower than those reported in studies on watermelon extracts and mixtures of
12
pomegranate with apple (Quek et al., 2007; Ochoa-Martinez et al., 2011). These
13
differences could be attributed to the content of sugar in the sample, as well as to the degree
14
of dextrinization of the maltodextrin used as encapsulating material. As for density, results
15
ranged from 0.536 to 0.554 g/cm3, similar to those reported in other studies (Papadakis et
16
al., 2006; Ochoa-Martínez et al., 2011).
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3.2
Total phenolic content, flavonoids and antioxidant activity
19
TPC in the CInf was 29.32 (±0.70) mg of GAE/g of cinnamon. As for SDCInf, the highest
20
TPC values were achieved in samples SDCInf 18010 and SDCInf 18008 at 8 and 10
21
mL/min respectively (both at 180 °C), and in sample SDCInf 14010 at 10 ml/min feed rate
22
and 140 °C temperature (Table 1). These conditions reduced heat degradation of phenols
23
during the spray drying process, thus preserving from 55.9 to 68.79% of the original TPC
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in the SDCInf. TPC in cinnamon was higher than that reported by Cai et al., (2004) and
2
Muchuweti et al., (2007) (18.7 mg and 15.5 mg of GAE/g of cinnamon, respectively). On
3
the other hand, it was lower than that reported by Shan et al., (2005) (63.4 mg of GAE/g of
4
cinnamon). This trend was also observed on the TFC for CInf, 51.34 (±3.41) mg of CE/g of
5
cinnamon. The highest TFC in SDCInf was 35.76 (±1.51) mg of CE/g of cinnamon; it was
6
obtained at a temperature of 140 ºC and a feed rate of 10 mL/min. The spray drying process
7
preserved from 29.02 to 35.76 (±1.51) mg of CE/g of cinnamon (i.e., 56.53 - 69.65%) from
8
the flavonoids originally present in raw cinnamon. These results were from 9.63 to 46.40
9
mg of CE (i.e., 18.75 - 90.37 %) higher than those observed on 5 varieties of cinnamon in
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China (Prasad et al., 2009).
11
There is a significant reduction of TPC and TFC when the temperature was increased from
12
140 to 160 °C (Table 1), a reverse effect is observed when the temperature varies from 160
13
to 180 °C. This reverse trend may be explained by the occurrence of synthesis and
14
polymerization of phenols and flavonoids which influences the total content of these
15
compounds (Mishra et al., 2014). However, other factor may be affecting the results such
16
as the outflow spray drying conditions which were not controlled nor evaluated here.
18 19
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Table 1
20
At 180 °C and 160 °C, both runs (8 and 10 mL/min) showed the highest antioxidant
21
capacity (lowest EC50 values in Table 1). However, sample at 180 °C and 10 mL/min
22
(SDCInf 18010) resulted with the highest percent yield of all samples. Antioxidant capacity
23
analysis estimates the median effective concentration (EC50). EC50 is the concentration than 10
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inhibits 50 % of the DPPH* radicals in solution; the lower the EC50, the higher the
2
antioxidant capacity. In this study, an EC50 of 0.29 mg/mL (R2= 0.99) was estimated for
3
CInf. This estimate is somehow lower than that reported for alcoholic extracts of Cinnamon
4
cassia (Jang et al., 2012). However, spray drying conditions had an effect on the
5
antioxidant capacity of powdered SDCInf. As for EC50, results ranged from 3.36 (±0.14) to
6
5.96 (±0.11) mg/mL in powdered SDCInf. The highest antioxidant capacity and % yield
7
were obtained at a temperature of 180 ºC and a feed rate of 10 mL/min. This behavior is
8
commonly observed on processes for encapsulating compounds with antioxidant activity at
9
spray drying temperatures higher than 65 ºC (Krishnaiah et al., 2012; Gallegos-Infante et
10
al., 2013). As for TPC, TFC, and free radical scavenging (DPPH), the effect of the feed rate
11
was significant (p-value<0.05), i.e., the time the material remains in contact with the air
12
inside the chamber of the spray dryer is relevant. Although more energy is required to
13
remove water from the dispersion (CInf-MD) at a feed rate of 10 mL/min, this seems to be
14
beneficial for the antioxidant capacity of CInf, thus minimizing polyphenol degradation and
15
protecting its antioxidant capacity. In general, the best results were found in samples at a
16
feed rate of 10 mL/min, analyses were performed only at this condition for particle size
17
distribution (PSD) and release profiles.
18 19 20
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FTIR spectrometry analysis
FTIR spectrometry analysis was carried out to elucidate the sort of molecules
21
comprising the compound of interest. Both CInf-MD (raw material) and SDCInf (dry
22
product) samples were analyzed in solid state. Air contact was minimized in order to avoid
23
water absorption (aw = 0.1). All FTIR-spectra (Figure 1) showed an absorption band at a 11
ACCEPTED MANUSCRIPT
wave length (λ) of 3300 cm-1, which is characteristic of hydroxyl (-OH) groups; this band
2
decreased in SDCInf samples though. CInf FTIR-spectra showed absorption bands that
3
could be regarded as its molecular fingerprint because these bands are not present in MD
4
FTIR-spectrum. Furthermore, these bands can be helpful to set criteria for the cover-up
5
effect of MD on CInf when analyzing SDCInf FTIR-spectra. Figure 1.
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Figure 1 shows characteristic wave lengths. Wave lengths at 1020 cm-1 (C-O; C-O-
9
C), 1440 cm-1 (=CH2, -C-H, =C-H), 1519 cm-1 (R-CO-NH-R), 1600 cm-1 (C-C, C=C, H-O-
10
H), and 2387 cm-1 (CH2, nCH3) are closely related to aromatic compounds with phenyl
11
bonds similar to those in polyphenolic compounds, such as flavonoids (Schulz & Baranska,
12
2007; Heneczkowski et al., 2001). MD cover-up effect on CInf was ~85%. From these
13
results, encapsulation of CInf with MD can be assumed. Moreover, results from TPC in
14
SDCInf support this assumption, see Section 3.2 above.
15
3.4
Scanning electron microscopy, (SEM)
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Interactions between CInf and MD could be explained by microparticles morphology.
18
Figure 2 shows micrographs of powdered SDCInf obtained at different temperatures and
19
feed rates. In these micrographs, semi-spherical microparticles are the most commonly
20
observed morphology. Microparticles showed rough surfaces with cavities and some
21
structural cracks. Morphological irregularities could be due to water evaporation rates
22
during spray drying process. The higher the temperature (faster evaporation) the smoother
23
and more defined the surfaces. This result is similar to that reported by Alamilla-Beltran et
24
al., (2005), who found that lower air inlet temperatures resulted in irregularly shaped
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microparticles with creased surfaces, while higher air inlet temperatures resulted in more
2
rigid microparticles and porous surfaces. Spray drying process both at 160 and 180 ºC and
3
at a feed rate of 10 mL/min produced microparticles morphologically more defined, semi-
4
spherical, without evident cracks or particle agglomerations. Microparticles obtained at a
5
feed rate of 8 mL/min showed irregular surfaces and particle agglomerations for all three
6
temperatures. A similar result was reported by Tonon et al., (2009) for açai juice
7
encapsulated with maltodextrin. They obtained both smooth spherical and irregular semi-
8
spherical microparticles. Figure 2
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Particle size distribution of SDCInf
Particle size distribution of microparticles was also studied. Figure 3 shows PSD of
13
powdered SDCInf obtained at a Feed rate of 10 mL/min for all three temperatures (140, 160
14
and 180 ºC). Microparticles size ranged from 6 to 30 microns. Particle size results show a
15
quasi-modal distribution with a single mode and wide base (heavy tails) for some
16
treatments. This result is particularly interesting because small particles tend to form
17
uniform arrays in solution with minimal gaps among particles. On the other hand, large
18
particles can fill surrounding gaps, mostly producing homogeneous solutions that are stable
19
under mechanical flow. Large particles, if present, could probably be produced by particle
20
agglomeration processes due to particle-particle interactions and continuous aggregation.
21
This situation was observed at low feed rate (Figure 3). Volumetric diameter d [4, 3] ranged
22
from 10.01 to 12.51 microns. There was a very small difference, yet statistically significant,
23
among treatments (p-value < 0.05).
24
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Figure 3. 13
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On the other hand, both samples at 160 ºC and 180 ºC temperatures showed similar
3
results (10.53 and 10.01 microns, respectively). This can indeed be attributed to
4
temperature. This result is in accordance to those reported by Reineccius (2001). They
5
reported that high drying temperatures produce a particle structure, and minimize creasing
6
and flexing of microparticles. Similar particle sizes were reported using polyphenolic
7
compounds from Orthosiphon stamineus extracts (Pang et al., 2014) encapsulated with
8
maltodextrins, and rosemary oil encapsulated both with maltodextrins and arabic gum in a
9
range of proportions (Janiszewska & Witrowa‐Rajchert, 2009). Note that this analysis is
10
important to determine the dimensional space occupied by microparticles in aqueous
11
dispersions. This information is essential to shed light on the mechanical response
12
(dynamic spectrum and viscosity of dispersions).
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Rheological behavior of spray dried cinnamon infusions All treatments produced powdered SDCInf with shear-thinning behaviors (n<1) in
16
solution (Figure 4). However, powdered SDCInf obtained at a temperature of 160 ºC
17
showed a more stable mechanical response (regardless of the Feed rate), i.e., Temperature
18
had a significant effect (p-value < 0.05) on shear-flow stability. This could be due to
19
thermal degradation and/or oxidation of microparticles during the spray drying process
20
(Tuyen et al., 2010).
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Figure 4
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Powdered SDCInf remained stable even when obtained at a temperature as high as
2
180 ºC. Flow curves showed the same shear-thinning trend around γ& =10 s-1, where
3
samples from all treatments overlapped. Similar results were reported in studies on spray
4
drying (Grabowski et al., 2008; Medina-Torres, et al., 2000 and 2013). Results from
5
SDCInf obtained at a temperature of 160 ºC and a feed rate of 10 mL/min showed the
6
highest viscosity. This could be related to particle size distribution (quasi-modal), since
7
viscosity increases are related to small and uniform particle sizes, like those obtained in this
8
study, where particle-particle interactions possibly increase along with flow resistance,
9
specifically at high shear rates like those reported in similar studies (Hill & Carrington,
10
2006). The effect of temperature and feed rate on both the storage (G’) and loss (G”)
11
moduli, as a function of oscillatory shear frequency (ω), of SDCInf dispersions are shown
12
in Figure 5.
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Figure 5.
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Microparticles showed a pseudo solid-like behavior, with a plateau zone formation at
16
low frequencies yet with dominant viscous behavior (G'' > G'). This evidences phase
17
interactions between MD and CInf at short times due to encapsulation. Moduli dissociation
18
is found at oscillatory shear frequencies (ω) lower than 100 rad/s. However, SDCInf
19
obtained at a temperature of 160 ºC showed mechanical stability to flow (regardless of the
20
feed rate). Similar trends were reported in studies using carbohydrates as an encapsulating
21
agent (Medina-Torres et al., 2013; León-Martinez et al., 2011).
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3.7
Controlled release analysis of SDCInf 15
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Releasing profiles of microcapsules are very important in order to estimate the
2
storage time that microcapsules can achieve, as well as the releasing profile of the core. In
3
this study, we had no problems when preparing SDCInf dispersions in water. In fact,
4
SDCInf-water dispersions were homogeneous and no precipitates were observed (electric
5
potential, p Z > 30mV). However, feed rate had a significant effect (p-value < 0.05), i.e.,
6
high feed rates yielded concentrations of CInf ~10% higher inside the microcapsule and
7
core release lasted around 36 hours. This difference is partially due to mechanical stability
8
to flow (see Figure 4 and 5).
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The study of the release profile of microcapsules of SDCInf was performed in a Franz
10
cell equipped with a 0.45 micron membrane. SDCInf samples were double processed at a
11
concentration of 3 g/100 mL in order to mimic digestive tract conditions. These results
12
were analyzed at a wavelength of 281.2 nm (Spectro-photometer UV-Vis, Analytical
13
Instruments Co. USA). SDCInf controlled release is designed for the conditions inside the
14
small bowel, because it is there where polyphenols from CInf are released. SDCInf samples
15
were continuously monitored until no signal was registered in the spectrum. However, after
16
60 hours there was still an increase in the signal spectrum due to MD, but not due to CInf.
17
Figure 6 shows the controlled release of SDCInf, where ~80.5% of CInf was released
18
within 48 hours. Liberation profiles reach a steady state after approximately 5 hours when
19
~70% of the encapsulated compounds have been released. This will ensure optimum
20
absorption of the polyphenols in the small intestine.
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Microcapsules showed high efficiency of encapsulation (>70%) using maltodextrin.
22
This can be attributed to microencapsulation conditions, which showed a quasi-modal
23
particle size and are in principle more stable. Sample at 160 °C and 10 mL/min (SDCaSA
24
16010) showed the highest percent release of the three samples investigated. This is 16
ACCEPTED MANUSCRIPT
attributed to the quasi-modal particle size distribution together with stability to flow (high
2
viscosity) of this sample due to the enhanced particle-particle interactions promoted by
3
agitation and shear.
4
Figure 6.
5 6
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These results can shed light on the expected behavior when SDCInf dispersions are
8
prepared and ingested, mimicking conditions similar to those inside the digestive tract,
9
where release occurs for a longer time, and allowing the antioxidant capacity of this spice
10
to last longer in the body. The co-existence of two microstructures was confirmed by FTIR,
11
rheological behavior and controlled release of SDCInf. This can be attributed to
12
microencapsulation conditions (Medina et al., 2013).
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4.
Conclusions
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Spray drying of cinnamon infusions using maltodextrin as a wall material under the
17
temperature and feed rate conditions developed in this study showed that encapsulation and
18
interactions are both possible. Spray drying at a feed rate of 10 mL/min and temperatures of
19
160 and 180 ºC are both ideal for encapsulating this sort of cinnamon infusions.
20
Microcapsules obtained under these conditions protect both phenolic content and
21
antioxidant capacity, and produced similar particle size distributions for all treatments.
22
However, at 160 °C percent-yield of dried product was lower than at 180 °C.
23 24
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SDCInf obtained at 10 mL/min and a
temperature of 160 ºC showed the best
mechanical response to shear (high viscosity), and this combined with a narrower particle 17
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size distribution resulted in a more rapid and higher percent release of encapsulated
2
polyphenols. This study conditions may shed some light on the properties and stability of
3
microencapsulated water infusions of spices. It sets a precedent for further research in an
4
area that has been barely explored.
Nomenclature List:
7
SDCInf:
Spray drying cinnamon infusions
8
TPC:
Total phenolic content
9
TFC:
Total flavonoids content
10
DPPH*:
1,1-diphenyl-2picrylhydrazil radical
11
SEM:
Scanning electron microscopy
12
FTIR:
Fourier transform infrared spectroscopy
13
CInf:
Cinnamon infusion
14
PSD:
Particle size distribution
15
GAE:
Gallic acid equivalents
16
CE:
Catechin equivalents
17
EC50:
Efficient concentration
19
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Figure and table captions
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Table 1.
Results of spray drying yield, moisture, density, total phenols content (TPC), total flavonoid content (TFC) and DPPH* EC50.
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Figure 1. FTIR spectrum of (—) Maltodextrin (···), Cinnamon Infusion and (- - -) SDCInf 16010.
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Figure 2. Micrographs of SDCInf, a)SDCInf 14008, b)SDCInf 16008 and c) SDCInf 18008, d) SDCInf 14010, e) SDCInf 16010 and f) SDCInf 18010.
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Figure 3. PSD of SDCInf feeding at 10 mL/min.
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Figure 4. Viscosity curves of SDCInf: SDCInf 14008, SDCInf 16008
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Effect of spray drying conditions on curve of storage (G’) and loss (G”)
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modulus a): SDCInf 14008, SDCInf 16008 and SDCInf 18008 and b):
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SDCInf 14010, SDCInf 16010 and SDCInf 18010. (Filled symbols are
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G’, blank symbols represent G”).
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Figure 6. Release profiles of SDCInf: SDCInf 14010, SDCInf 16010 and SDCInf 18010.
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Table 1. Results of spray drying yield, moisture, density, total phenols content (TPC), total flavonoid content (TFC) and DPPH* EC50. Yield %
Moisturea
CInf
4.75 (+0.33)
--
SDCInf 14008
27.48 (+ 0.10)
SDCInf 16008
36.92 (+ 0.74)
SDCInf 18008
39.19 (+ 0.80)
SDCInf 14010
40.28 (+ 0.14)
SDCInf 16010 SDCInf 18010
TPCc
TFC d
DPPH* EC50 e
--
29.32 (+ 0.70)
51.34 (+3.41)
0.29 (+0.95)
1.89 (+ 0.01)
0.544 (+ 0.003)
18.33 (+ 0.29)
31.13 (+1.51)
4.74 (+0.46)
1.54 (+ 0.07)
0.554 (+ 0.005)
18.43 (+ 0.04)
30.41 (+4.12)
3.60 (+0.12)
1.34 (+ 0.07)
0.550 (+ 0.003)
18.77 (+ 0.80)
33.33 (+2.07)
3.50 (+0.19)
1.99 (+ 0.14)
0.540 (+ 0.004)
19.60 (+ 0.07)
35.76 (+1.51)
5.96 (+0.11)
40.82 (+ 0.73)
1.75 (+ 0.07)
0.540 (+ 0.004)
16.39 (+ 0.83)
29.02 (+0.79)
3.65 (+0.22)
49.60 (+ 0.15)
1.58 (+ 0.13)
0.536 (+ 0.007)
20.17 (+ 0.81)
34.70 (+4.06)
3.36 (+0.14)
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Highlights • Cinnamon infusions with antioxidant capacity were spray dried • Optimum conditions were found to produce stable and well-formed microcapsules
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• Produced microcapsules preserve both phenolic content and antioxidant capacity • The rheological characterization evidenced strong particle-particle interactions
• Encapsulated systems may be optimum delivery systems according to release
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profiles