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A method for the measurement of the oxygen permeability of edible films

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Food Chemistry 80 (2003) 423–431 www.elsevier.com/locate/foodchem Analytical, Nutritional and Clinical Methods Section A method for the measurement of the oxygen permeability and the development of edible films to reduce the rate of oxidative reactions in fresh foods Erol Ayranci*, Sibel Tunc Department of Chemistry, Akdeniz University, PO Box 510, Antalya, Turkey Received 22 January 2002; received in revised form 14 October 2002; accepted 14 October 2002 Abstract A method involving the flow of
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  Analytical, Nutritional and Clinical Methods Section A method for the measurement of the oxygen permeability andthe development of edible films to reduce the rate of oxidative reactions in fresh foods Erol Ayranci*, Sibel Tunc Department of Chemistry, Akdeniz University, PO Box 510, Antalya, Turkey Received 22 January 2002; received in revised form 14 October 2002; accepted 14 October 2002 Abstract A method involving the flow of O 2 and N 2 gasses from the two sides of an edible film coupled with a simple wet chemical analysisat the end, was developed to measure the oxygen permeability of edible films. The proposed method was employed to determine theoxygen permeability of methyl cellulose (MC)-based edible films of various composition with the aim of finding the optimumcomposition for minimising oxidative degradation of foods. The effects of the presence of stearic acid (SA), ascorbic acid (AA) andcitric acid (CA), in varying amounts in the film composition, on the oxygen permeability (OP) of MC based edible films wereexamined. The OP increased with increasing SA content of the film and decreased with the inclusion of AA or CA in the filmcomposition. The films, with various compositions and with the measured oxygen permeabilities, were then applied to mushrooms( Agaricus bisporus ) and cauliflower ( Brassica botrytis ). It was found, from the analysis of these coated foods, that the coatingscontaining antioxidants slowed the browning reactions and reduced the vitamin C loss in both foods, the effects being greater incauliflower. Moreover, the moisture loss of coated foods was less than that of uncoated. # 2002 Elsevier Science Ltd. All rights reserved. Keywords: Edible film; Oxygen permeability; Vitamin C; Enzyme activity; Oxidative reactions 1. Introduction The development of edible films to reduce the mois-ture transfer, the oxidation or the respiration in foodsystems is important to prolong the shelf-lives of foods.The measurements of permeabilities of stand-alone filmsto water vapour, oxygen and carbon dioxide areimportant tools for the development of edible films.Oxygen is involved in many degradation reactions infoods, such as fat and oil rancidity, micro-organismgrowth, enzymatic browning and vitamin loss. Thus,many packaging strategies seek to exclude oxygen toprotect the food product (Gontard, Thibault, Cuq, &Guilbert, 1996). On the other hand, the permeability tooxygen and carbon dioxide is essential for respiration inliving tissues such as fresh fruits and vegetables. So,moderate barrier coatings are more appropriate. If acoating with the appropriate permeability is chosen, acontrolled respiratory exchange can be established andthus the preservation of fresh fruits and vegetables canbe prolonged.The main characteristics to consider in the selection of coating materials are their oxygen, carbon dioxide andwater vapour permeabilities. The water vapour per-meability (WVP) is the most extensively studied prop-erty of edible films (Ayranci, Buyuktas, & Cetin, 1997;Ayranci & Cetin, 1995; Gontard, Marchesseau, Cuq, &Guilbert, 1995; Kamper & Fennema, 1984; McHugh,Aujard, & Krochta, 1994) mainly because of theimportance of the role of water in deteriorative reac-tions and partly because the ease of measurement. Thecorrelation between moisture sorption isotherm andWVP of cellulose-based edible films was also sought(Ayranci, 1996). The measurement of oxygen and car-bon dioxide permeabilities requires instruments whichmay not be easily available. Measurements are mostlybased on the standard method described inASTM(1988)for oxygen gas transmission through films. These 0308-8146/03/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.PII: S0308-8146(02)00485-5Food Chemistry 80 (2003) 423–431www.elsevier.com/locate/foodchem* Corresponding author. Tel.: +90-242-310-2315; fax: +90-242-227-8911. E-mail address: ayranci1@pascal.sci.akdeniz.edu.tr(E. Ayranci).  methods involve a flowing an oxygen gas stream on oneside of the film and a nitrogen stream, to carry thetransmitted oxygen gas to the analyzer, on the otherside. A coulometric sensor, an infrared sensor, a gaschromatograph or a dedicated oxygen analyser may beused for monitoring.Park, Weller, Wergano, and Testin (1993)measuredthe oxygen permeabilities of methyl cellulose (MC) andhydroxypropyl methyl cellulose (HPC)-based ediblefilms by the OX-TRAN 1000 system, operated accor-ding to theASTM (1988)standard method. They foundthat the oxygen permeability (OP) of the films increasedwith the molecular weight of MC and HPC. In anotherwork byGennadios, Weller, and Testin (1993), the OPof corn zein, wheat gluten and wheat gluten/soy proteinisolate films was measured at 7, 15, 25 and 35  C by amethod again based onASTM (1988). The OP of allfilms was found to increase with temperature. It wasalso noted that the OP values of wheat gluten/soy pro-tein isolate films were lower than those of other films.The degree of resistance of various lipid films to theoxygen transmission was measured with the aim of determining the influences of polymorphic forms of thelipid and of tempering, using the method of ASTM byKester and Fennema (1989a, 1989b, 1989c).Greenerand Fennema (1989)reported oxygen permeabilities of bilayer films prepared from methyl cellulose and bees-wax measured by the same method. Another work onthe oxygen transmission of a methyl cellulose-palmiticacid film was reported byRico-Pena and Torres (1990).In a recent work from our laboratory, a simplemethod was proposed for the measurement of CO 2 per-meability (Ayranci, Tunc, & Etci, 1999) and appliedsuccessfully to various cellulose-based edible films(Ayranci & Tunc, 2001).In the present work, we introduce a method tomeasure the OP of edible films. The proposed methodwas applied to measure the OP of films of various com-position with the aim of finding the optimum compo-sition to minimise oxidative degradation of foods.Application of film solutions to fresh foods, such asmushrooms and cauliflower, and analysis of these foodsfor oxidative degradation, are also investigated. 2. Materials and methods 2.1. Materials MC with an average molecular weight of 41000,polyethylene glycol (PEG) with an average molecularweight of 400 and stearic acid (SA) were purchasedfrom Sigma. Citric acid (CA), manganese(II) sulphatemonohydrate, potassium iodide, sodium thiosulphateand sodium hydroxide were obtained from Merck.Oxygen gas was obtained from a local gas supplier,HABAS. Ethanol was reagent grade and water wasdistilled.Gallic acid, Folin and Ciocalteu phenol reagent,obtained from Sigma, and Na 2 CO 3 , obtained fromMerck, were used for the analysis of phenol. (+) Cat-echin, purchased from Sigma, and phosphate buffer,obtained from Merck, were used in the polyphenoloxidase (PPO) activity measurements. Ascorbic acid(AA), purchased from Sigma, CuSO 4 .5H 2 O andH 2 C 2 O 4 , obtained from Merck, were used for the ana-lysis of vitamin C.Mushrooms were obtained from ANT-BUZ Gıda veTarım U¨ru¨nleri San. Tic. A.S¸. and cauliflower was froma local bazaar. 2.2. Preparation of films MC (3 g) was dissolved in a solvent mixture of 66 mlethanol and 33 ml water. After the addition of 1 mlPEG, the solution was homogenised with an homo-geniser at 24 000 rev min À 1 for 5 min. It was re-homo-genised after the addition of fatty acid and otheradditives. The final solution was kept in a vacuum ovenat 80  C for about 5 h in order to remove air bubbles ordissolved air. It was then spread on 20 Â 20 cm glassplates by adjusting the hand-operated thin layer chroma-tography plate coater to 0.5 mm thickness. The spreadfilms were dried at 60  C in an oven for 25 min and thenat room temperature for 1 day. 2.3. Measurement of the OP An edible film was sealed between two speciallydesigned glass cups, each having a diameter of 4 cm anda depth of 5 cm (Fig. 1). Both cups have two channels.Oxygen enters to the cup on one side of the film fromone channel and leaves from the other with a controlledflow rate to keep the oxygen pressure constant in thatcompartment. The cup on the other side of the film waspurged by a stream of nitrogen entering from onechannel and leaving from the other. This nitrogen actedas a carrier for oxygen permeated from the other side of the film to the wet analysis system (Fig. 1). Up to thewet analysis system, the design was mainly based on theASTM standard (1988). A modification was made tothe O 2 analysis and a classical wet analysis, based on thewell-known method of iodimetry was applied for thedetermination of the amount of permeated O 2 , insteadof using an oxygen analyser as in the ASTM standard,which uses a coulometric sensor.The mixture of N 2 and permeated O 2 was passed fromthe wet system for a known period of time. Then the wetsystem, which srcinally contained aqueous mangane-se(II) sulphate and alkaline iodide solution, was ana-lysed for O 2 (Vogel, 1989). It is well known thatmanganese(II) hydroxide is rapidly and quantitatively 424 E. Ayranci, S. Tunc/Food Chemistry 80 (2003) 423–431  converted to manganese(III) hydroxide with oxygen bythe following reaction:4 Mn OH ð Þ 2 þ O 2 þ 2 H 2 O ! 4 Mn OH ð Þ 3 # The brown precipitate formed was dissolved on acid-ification and allowed to oxidise iodide ions present inthe system quantitatively to iodine ; Mn OH ð Þ 3 þ I À þ 3 H þ ! Mn 2 þ þ 1 = 2 I 2 þ 3 H 2 O The liberated iodine could then be titrated with astandard thiosulphate solution;2 S 2 O 2 À 3 þ I 2 ! S 4 O 2 À 6 þ 2 I À A blank titration was carried out to determine anyoxygen pre-dissolved in the wet system. The stoichio-metry indicated that 1 mol of dissolved oxygen required4 mol of thiosulphate.The OP of the film was then calculated byEq. (1); OP ¼ m Á d A Á t Á Á P ð 1 Þ where m is the mass of O 2 permeated through the filmwith a thickness of  d  and an area of  A over the mea-sured time interval t . Á P is the difference in O 2 pressurebetween the two sides of the film. The pressure on theO 2 side of the film (Fig. 1) was kept at 1 atm by con-trolling the flow of pure O 2 purged to this compartmentand by measuring its pressure with a Hg manometer(Fig. 1). The O 2 pressure on the N 2 side of the film wasassumed to be zero, since any O 2 permeated through thefilm was continuously swept to the wet system for ana-lysis at the end. So, Á P was taken as 1 atm.The OP of various edible films were determinedaccording to the method described above at 25 Æ 1  Cand 0% relative humidity. Both O 2 and N 2 gases weredried by passing through a gas drying column containinganhydrous calcium chloride before entering the system(Fig. 1). Prior to the permeability measurements, filmswere also conditioned in a desiccator over anhydrouscalcium chloride for 1 day. 2.4. Measurement of the film thickness The film thickness was measured with a hand-heldmicrometer having a sensitivity of 0.001 mm. Thismeasurement was carried out at the end of the perme-ability test to avoid the effect of mechanical damagethat could be caused on the film during the thicknessmeasurement. The thickness was measured at variouslocations (at least five) of the film and then an averagevalue was calculated. 2.5. Comparison of the OP results obtained by thepresent method with those reported in literature The data on OP, determined by ASTM methods inthe literature, are reported at varying conditions of temperature, film thickness, film composition and rela-tive humidity. It should be recognised that it is verydifficult to match all these conditions exactly for OPmeasurements in different laboratories to compare ortest the results obtained by a new method. However, areasonable comparison can be made between the repor-ted OP data and the data obtained in this work, underslightly different conditions, in order to seek support forthe validity of the method.Rico-Pena and Torres’ (1990)OP data, reported for afilm with a composition of PA:MC:PEG in 3:9:1 ratio, Fig. 1. Schematic of the apparatus used to measure oxygen permeability of edible films. E. Ayranci, S. Tunc/Food Chemistry 80 (2003) 423–431 425  was taken as the first reference to compare with theresults obtained in the present method. The film used inthe reference work had a thickness of 54 m m and its OPwas measured at 24  C and 0% relative humidity as0.52 Â 10 À 9 g d À 1 Pa À 1 m À 1 . The film prepared in thepresent work, for comparison purposes, had the samecomposition. Its OP was measured at the same tem-perature and relative humidity. However, the thicknessof the film could only be adjusted to 42 m m which is 12 m m thinner than Rico-Pena and Torres’ film. The mea-sured OP was (0.82 Æ 0.05) Â 10 À 9 g d À 1 Pa À 1 m À 1 whichhas the same order of magnitude but is greater thanRico-Pena and Torres’ reported value. The difference isbelieved to srcinate from the difference in thickness of the two films. It was reported byPark and Chinnan(1990)that O 2 and CO 2 permeabilities of protein basedfilms increase with decreasing thickness.The second selected reference OP was reported byPark and Chinnan (1990)for a film with a compositionof MC:PEG in 9:1 ratio and with a thickness of 40 m m.The OP of this film was found to be 0.21 Â 10 À 9 g d À 1 Pa À 1 m À 1 at 30  C and 0% relative humidity. The con-trol film prepared in the present work had the samecomposition and the same thickness. Its OP was mea-sured at 29  C and 0% relative humidity as(0.52 Æ 0.03) Â 10 À 9 g d À 1 Pa À 1 m À 1 , which again has thesame order of magnitude but is greater than the repor-ted result of Park and Chinnan. This time the differencein conditions seems to be only in temperature and thatis only 1  C, which can not explain the large differenceobserved in OP values. This large difference can only beattributed to the srcin of MC used in the film prepara-tion. The MC used in the present work has an averagemolecular weight of 41 000. Unfortunately, the molecularweight of MC used by Park and Chinnan was not repor-ted. It might be different.Ayranci et al. (1997)found theeffective molecular weight of MC on WVP of MC-basededible films to be especially important above 41 000.The OP values of edible films measured with the pro-posed method, in the present work, have the same orderof magnitude as those reported in the literature. Somedifferences may arise due to the differences in conditionsof measurements and composition or thickness of thefilms. It is noteworthy that the OP values determinedwith the proposed method, for a series of films, showthe same trend even if there are some differences inabsolute values from those in literature. 2.6. Coating procedure Mushrooms and cauliflowers were selected as modelsystems for the application of coating formulations forseveral reasons. They are susceptible to browning, con-tain sufficient vitamin C, the loss of which can be stud-ied, they are easily available and coatings can easily beapplied. Whole mushrooms and cuts of cauliflowerswere used for coating. Fresh foods were dipped com-pletely into the coating solutions, whose compositionsare given inTable 1, for about 5 s at room temperature(and then taken out). This process was repeated twice.Then the coating was dried with the help of a fan.Coated and uncoated foods were kept in a SanyoMIR 152 incubator (Japan) at 25  C and 84% relativehumidity until analysis for water loss, colour, vitaminC, polyphenol oxidase activity and total phenol contentas a function of time. 2.7. Measurement of water loss The coated and uncoated fresh mushrooms and cauli-flower were weighed to the nearest 0.1 mg and kept inan incubator at 25  C for 5–8 days. Weighings of foodswere repeated every 24 h in order to determine themoisture loss as a function of time. 2.8. Colour measurement The lightness ( L value) of mushrooms was determinedusing a Minolta CR-200 colorimeter. Colour measure-ment of cauliflower was not possible with a colorimeterdue to the non-smooth surface. So, their colour changecould only be followed by eye. 2.9. Vitamin C determination TheconcentrationofvitaminCinfoodswasdeterminedby a spectrophotometric method (Sawyer, Heineman, &Beebe, 1984). Ten grams of food was homogenised inabout 100 ml, 4% H 2 C 2 O 4 solution. The mixture was fil-tered and diluted to a certain volume with 4% H 2 C 2 O 4 .For the calibration process, the standard solutionswere prepared from 100 m g ml À 1 AA solution in 4%H 2 C 2 O 4 . 1 ml of 50 m g ml À 1 CuSO 4 .5H 2 O solution(pH=6) was added to each standard solution and thentheir absorbance values were recorded at 249 nm as afunction of AA concentration. 2.10. Polyphenoloxidase activity Polyphenoloxidase (PPO) activity was determinedaccording to the procedure described byZemel, Sims, Table 1Compositions of the coating solutions applied to mushrooms andcauliflowerCoatingno.Ethanol/water(ml/ml)MC(g)PEG(ml)SA(g)Antioxidant(g)1 66/33 3 1 – – 2 66/33 3 1 0.6 – 3 66/33 3 1 0.6 0.5 AA4 66/33 3 1 0.6 0.5 CA426 E. Ayranci, S. Tunc/Food Chemistry 80 (2003) 423–431
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