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Non-Thermal Plasma Technologies in Food Industry (Turkish with English Abstract)

Year 2012, Volume: 37 Issue: 5, 295 - 302, 01.10.2012

Abstract

Non thermal plasma processing is an alternative technology that has been used to improve surface properties of food contacting materials in many applications. Plasma modification can lead to final products with enhanced properties characterized by desired bulk and surface properties. It is just possible to obtain regular surface characteristics by optimizing the plasma conditions such as plasma frequency and power, reactor geometry, monomer type, flow rate, pressure and exposure time. In this review, theoretical background, characteristics and feasibility of plasma technologies applied to food industry were discussed. The influence of various plasma parameters on the plasma processes was described in detail. The future trends of plasma technologies in food industry were evaluated based on the integration of this technology with various food applications.

References

  • Laroussi M. 2005. Low-temperature plasma based sterilization: Overview and state-of-the-art. Plasma Process Polym, 2(5), 391-400.
  • Şen Y, Bağcı U, Güleç HA, Mutlu M. 2012. Modification of food contacting surfaces by plasma polymerization technique: reducing the biofouling of microorganisms on stainless steel surface. Food Bioprocess Tech, 5 (1), 166-175.
  • Güleç HA, Sarıoğlu K, Mutlu M. 2006. Modification of Food Contacting Surfaces by Plasma Polymerisation Technique: Part I: Determination of Hydrophilicity, Hydrophobicity and Surface Free Energy by Contact Angle Method. J Food Eng, 75(2), 187-195.
  • Güleç HA, Topaçlı A, Topaçlı C, Albayrak N, Mutlu M. 2010. Modification of cellulose acetate membrane via low-pressure plasma polymerization for sugar separation applications Part I: Membrane development and characterization. J Membrane Sci, 350 (1-2), 310-321.
  • Çökeliler D, Mutlu M. 2002. Performance of amperometric alcohol electrodes prepared by plasma polymerization technique. Anal Chim Acta, 469, 217-223.
  • Denes FS, Manolache S. 2004. Macromolecular plasma-chemistry: en emerging field of polymer science. Prog Polym Sci, 29, 815-885.
  • Jampala SN, Manolache S, Gunasekaran S, Denes FS. 2005. Plasma-enhanced modification of xanthan gum and its effect on rheological properties. J Agr Food Chem, 53, 3618-3625.
  • Siow KS, Britcher L, Kumar S, Griesser HJ. 2006. Plasma methods for the genaration of chemically reactive surfaces for biomolecule immobilization and cell colonization-A review. Plasma Process Polym, 3, 392-418.
  • Bringmann P, Rohr O, Gammel FJ, Jansen I. 2009. Atmospheric pressure plasma deposition of adhesion promotion layers on aluminium. Plasma Process Polym, 6, 496-502.
  • Kumar V, Pulpytel J, Giudetti G, Rauscher H, Rossi F, Arefi-Khonsari F. 2011. Amphiphilic copolymer coatings via plasma polymerisation process: switching and anti-biofouling characteristics. Plasma Process Polym, 8, 373-385.
  • Friedrich J. 2011. Mechanisms of plasma polymerization – Reviewed from a chemical point of view. Plasma Process Polym, 8, 783-802. 12. Yasuda HK. 2005. Some important aspects of plasma polymerization. Plasma Process Polym, 2, 293-304.
  • Meidanshahi FS, Madanipour K, Shokri B. 2012. Investigation of first and second ionization on optical properties of atmospheric plasmas. Opt Commun, 285, 453-458.
  • Biederman H, Kylian O. 2011. Some remarks to macroscopic kinetics of plasma polymerizaton. Plasma Process Polym, 8, 475-477.
  • Kim Y, Kim KJ, Lee Y. 2009. Surface analysis of flourine-containing thin films fabricated by various plasma polymerization methods. Surf Coat Tech, 203, 3129-3135.
  • Lee HJ, Jung H, Choe W, Ham JS, Lee JH, Jo C. 2011. Inactivation of Listeria monocytogenes on agar and processed meat surfaces by atmospheric pressure plasma jets. Food Microbiol, 28, 1468-1471.
  • Chen KS, Chen SC, Lin HR, Yan TR, Tseng CC. 2007. A novel technique to immobilize DNA on surface of a quartz crystal microbalance by plasma treatment and graft polymerization. Mat Sci Eng C-Biomim, 27, 716-724.
  • Weibel DE, Vilani C, Habert AC, Achete CA. 2007. Surface modification of polyurethane membranes using acrylic acid vapour plasma and its effects on the pervaporation processes. J Membrane Sci, 293, 124-132.
  • Swaraj S, Oran U, Lippitz A, Friedrich JF, Unger WES. 2007. Aging of plasma-deposited films prepared from organic monomers. Plasma Process Polym, 4, 784-789.
  • Ruiz JC, St-Georges-Robillard A, Theresy C, Lerouge S, Wertheimer MR. 2010. Fabrication and characterisation of amine-rich organic thin films: focus on stability. Plasma Process Polym, 7, 737-753.
  • Morent R, De Geyter N, Beaurain A, Van Vli- erberghe S, Dubruel P, Payen E. 2011. Influence of operating parameters on plasma polymerization of acrylic acid in a mesh-to-plate dielectric barrier discharge. Prog Org Coat, 70, 336-341.
  • Hegemann D, Körner E, Albrecht K, Schütz U, Guimond S. 2010. Growth mechanism of oxygen containing functional plasma polymers. Plasma Process Polym, 7, 889-898.
  • De Geyter N, Morent R, Van Vlieberghe S, Frere-Trentesaux M, Dubruel P, Payen E. 2011. Effect of electrode geometry on the uniformity of plasma-polymerized methyl methacrylate coatings. Prog Org Coat, 70, 293-299.
  • Tatoulian M, Arefi-Khonsari F, Borra JP. 2007. Deposition of organic coatings at atmospheric pressure from liquid precursors. Plasma Process Polym, 4, 360-369.
  • Morent R, De Geyter N, Jacobs T, Van Vlierberghe S, Dubruel P, Leys C, Schacht E. 2009. Plasma-polymerization of HMDSO using an atmospheric pressure dielectric barrier discharge. Plasma Process Polym, 6, 537-542.
  • Hiratsuka A, Karube I. 2000. Plasma polymerized films for sensor devices. Electroanal, 12(9), 695-702. 27 .Shenton MJ, Stevens GC, Wright NP, Duan X. 2002. Chemical-surface modification of polymers using atmospheric pressure nonequilibrium plasmas and comparisons with vacuum plasmas. J Polym Sci A1, 40, 95-109.
  • Ledernez L, Yasuda H, Olcaytug F, Gemetz F, Urban G. 2007. Pressure dependence of plasma polymerization of methane at constant W/FM. Plasma Process Polym, 4, 794-796.
  • Awaja F, Gilbert M, Kelly G, Fox B, Pigram PJ. 2009. Adhesion of polymers. Prog Polym Sci, 34, 948-968.
  • Assis OBG, Hotchkiss JH. 2007. Surface hydrophobic modification of chitosan thin films by hexamethyldisilazane plasma deposition: effects on water vapour, CO2 and O2 permeabilities. Packag Technol Sci, 20, 293-297.
  • Topala I, Asandelusa M, Spridon D, Dumitrascu N. 2009. Hydrophobic coatings obtained in atmospheric pressure plasma. IEEE T Plasma Sci, 37(6), 946-950.
  • Kim B, Yun H, Jung S, Jung Y, Jung H, Choe W, Jo C. 2011. Effect of atmospheric plasma on inactivation of pathogens inoculated onto bacon using two different gas compositions. Food Microbiol, 28, 9-13.
  • Vasilev K, Griesser SS, Griesser HJ. 2011. Antibacterial surfaces and coatings produced by plasma techniques. Plasma Process Polym, 8, 1010-1023.
  • Moisan M, Barbeau J, Crevier MC, Pelletier J, Philip N, Saoudi B. 2002. Plasma sterilization: methods and mechanisms. Pure Appl Chem, 74(3), 349-358.
  • Leipold F, Kusano Y, Hansen F, Jacobsen T. 2010. Decontamination of a rotating cutting tool during operation by means of atmospheric pressure plasmas. Food Control, 21, 1194-1198.
  • Noriega E, Shama G, Laca A, Diaz M, Kong MG. 2011. Cold atmospheric gas plasma disinfection of chicken meat and chichen skin contaminated with Listeria innocua. Food Microbiol, 28, 1293-1300.
  • Sanghini S, Paulussen S, Terryn H. 2011. Atmospheric pressure plasma technology: a straightforward deposition of antibacterial coatings. Plasma Process Polym, 8, 59-69.
  • Chen J, Li J, Zhao ZP, Wang D, Chen CX. 2007. Nanofiltration membrane prepared from polyacrylonitrile ultrafiltration membrane by low-temperature plasma: 5. Grafting of styrene in vapor phase and its application. Surf Coat Tech, 201, 6789-6792.
  • Bartolo L, Morelli S, Piscioneri A, Lopez LC, Favia P, d’Agostino R, Driolli E. 2007. Novel membranes and surface modification able to activate spesific cellular responses. Biomol Eng, 24, 23-26.
  • Ulbricht M. 2006. Advanced functional polymer membranes. Polymer, 47, 2217-2262.
  • Rios GM, Belleville MP, Jeanjean DP. 2007. Membrane engineering in biotechnology: quo vamus? Trends Biotechnol, 25(6), 242-246.
  • Zhou C, Wang Z, Liang Y, Yao J. 2008. Study on the control of pore sizes of membranes using chemical methods Part II. Optimization factors for preparation of membranes. Desalination, 225, 123-138.
  • Bryjak M, Gancarz I, Smolinska K. 2010. Plasma nanostructuring of porous polymer membranes. Adv Colloid Interfac, 161, 2-9.
  • Güleç HA, Gürdaş S, Albayrak N, Mutlu M. 2010. Immobilization of Aspergıllus oryzae β- galactosidase on low pressure plasma modified cellulose acetate membrane by polyethyleneimine for production of galactooligosaccharide. Biotechnol Bioproc E, 15 (6), 1006-1015.
  • Alp B, Mutlu S, Mutlu M. 2000. Glow-discharge -treated cellulose acetate (CA) membrane for a high linearity single-layer glucose electrode in the food industry. Food Res Int, 33, 107-112.
  • Tran TD, Mori S, Suzuki M. 2007. Plasma modification of polyacrilonitrile ultrafiltration membrane. Thin Solid Films, 515, 4148-4152.
  • Chu LQ, Knoll W, Förch R. 2009. Plasma-polymerized non-fouling thin films for DNA immobilization. Biosens Bioelectron, 25, 519-522. 48. Guermat N, Bellel A, Sahli S, Segui Y, Raynaud P. 2009. Thin plasma-polymerized layers of hexamethyldisiloxane for humidity sensor development. Thin Solid Films, 517, 4455-4460.
  • Karamollaoğlu I, Öktem H, Mutlu M. 2009. QCM-based DNA biosensor for detection of genetically modified organisms (GMOs). Biochem Eng J, 44, 142-150.
  • Mutlu S, Çökeliler D, Shard A, Goktas H, Ozansoy B, Mutlu M. 2008. Preparation and characterization of ethylenediamine and cysteamine plasma polymerized films on piezoelectric quartz crystal surfaces for a biosensor. Thin Solid Films, 516, 1249-1255.

Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri

Year 2012, Volume: 37 Issue: 5, 295 - 302, 01.10.2012

Abstract

Isıl olmayan plazma süreçleri gıda ile temas eden yüzeylerin özelliklerini çok geniş bir yelpazede geliştirmek için kullanılan alternatif bir teknolojidir. Plazma ile yüzey özellikleri değiştirilen materyal hedeflenen doğrultuda yığın ve yüzey özelliklerine sahip olmaktadır. Plazmanın karmaşık doğal yapısı gereği, bir materyal yüzeyinde hedeflenen amaca yönelik homojen bir modifikasyonun gerçekleştirilebilmesi ancak plazma frekansı, reaktör geometrisi, kullanılan monomerin kimyasal yapısı, basınç, monomer akış hızı, plazma gücü ve uygulama süresi gibi plazma koşullarının kontrol edilmesiyle mümkün olmaktadır. Bu araştırmada plazma teknolojilerinin temel prensipleri, özellikleri ve gıda endüstrisinde kullanım potansiyelleri irdelenmiştir. Farklı plazma ölçütlerinin uygulamaya etkileri ayrıntılı bir şekilde tanımlanmıştır. Plazma teknolojilerinin farklı gıda uygulamalarıyla bütünleştirilmesi için araştırmaların ne yönde gelişime ihtiyaç duyduğu araştırmada ayrıca vurgulanmıştır.

References

  • Laroussi M. 2005. Low-temperature plasma based sterilization: Overview and state-of-the-art. Plasma Process Polym, 2(5), 391-400.
  • Şen Y, Bağcı U, Güleç HA, Mutlu M. 2012. Modification of food contacting surfaces by plasma polymerization technique: reducing the biofouling of microorganisms on stainless steel surface. Food Bioprocess Tech, 5 (1), 166-175.
  • Güleç HA, Sarıoğlu K, Mutlu M. 2006. Modification of Food Contacting Surfaces by Plasma Polymerisation Technique: Part I: Determination of Hydrophilicity, Hydrophobicity and Surface Free Energy by Contact Angle Method. J Food Eng, 75(2), 187-195.
  • Güleç HA, Topaçlı A, Topaçlı C, Albayrak N, Mutlu M. 2010. Modification of cellulose acetate membrane via low-pressure plasma polymerization for sugar separation applications Part I: Membrane development and characterization. J Membrane Sci, 350 (1-2), 310-321.
  • Çökeliler D, Mutlu M. 2002. Performance of amperometric alcohol electrodes prepared by plasma polymerization technique. Anal Chim Acta, 469, 217-223.
  • Denes FS, Manolache S. 2004. Macromolecular plasma-chemistry: en emerging field of polymer science. Prog Polym Sci, 29, 815-885.
  • Jampala SN, Manolache S, Gunasekaran S, Denes FS. 2005. Plasma-enhanced modification of xanthan gum and its effect on rheological properties. J Agr Food Chem, 53, 3618-3625.
  • Siow KS, Britcher L, Kumar S, Griesser HJ. 2006. Plasma methods for the genaration of chemically reactive surfaces for biomolecule immobilization and cell colonization-A review. Plasma Process Polym, 3, 392-418.
  • Bringmann P, Rohr O, Gammel FJ, Jansen I. 2009. Atmospheric pressure plasma deposition of adhesion promotion layers on aluminium. Plasma Process Polym, 6, 496-502.
  • Kumar V, Pulpytel J, Giudetti G, Rauscher H, Rossi F, Arefi-Khonsari F. 2011. Amphiphilic copolymer coatings via plasma polymerisation process: switching and anti-biofouling characteristics. Plasma Process Polym, 8, 373-385.
  • Friedrich J. 2011. Mechanisms of plasma polymerization – Reviewed from a chemical point of view. Plasma Process Polym, 8, 783-802. 12. Yasuda HK. 2005. Some important aspects of plasma polymerization. Plasma Process Polym, 2, 293-304.
  • Meidanshahi FS, Madanipour K, Shokri B. 2012. Investigation of first and second ionization on optical properties of atmospheric plasmas. Opt Commun, 285, 453-458.
  • Biederman H, Kylian O. 2011. Some remarks to macroscopic kinetics of plasma polymerizaton. Plasma Process Polym, 8, 475-477.
  • Kim Y, Kim KJ, Lee Y. 2009. Surface analysis of flourine-containing thin films fabricated by various plasma polymerization methods. Surf Coat Tech, 203, 3129-3135.
  • Lee HJ, Jung H, Choe W, Ham JS, Lee JH, Jo C. 2011. Inactivation of Listeria monocytogenes on agar and processed meat surfaces by atmospheric pressure plasma jets. Food Microbiol, 28, 1468-1471.
  • Chen KS, Chen SC, Lin HR, Yan TR, Tseng CC. 2007. A novel technique to immobilize DNA on surface of a quartz crystal microbalance by plasma treatment and graft polymerization. Mat Sci Eng C-Biomim, 27, 716-724.
  • Weibel DE, Vilani C, Habert AC, Achete CA. 2007. Surface modification of polyurethane membranes using acrylic acid vapour plasma and its effects on the pervaporation processes. J Membrane Sci, 293, 124-132.
  • Swaraj S, Oran U, Lippitz A, Friedrich JF, Unger WES. 2007. Aging of plasma-deposited films prepared from organic monomers. Plasma Process Polym, 4, 784-789.
  • Ruiz JC, St-Georges-Robillard A, Theresy C, Lerouge S, Wertheimer MR. 2010. Fabrication and characterisation of amine-rich organic thin films: focus on stability. Plasma Process Polym, 7, 737-753.
  • Morent R, De Geyter N, Beaurain A, Van Vli- erberghe S, Dubruel P, Payen E. 2011. Influence of operating parameters on plasma polymerization of acrylic acid in a mesh-to-plate dielectric barrier discharge. Prog Org Coat, 70, 336-341.
  • Hegemann D, Körner E, Albrecht K, Schütz U, Guimond S. 2010. Growth mechanism of oxygen containing functional plasma polymers. Plasma Process Polym, 7, 889-898.
  • De Geyter N, Morent R, Van Vlieberghe S, Frere-Trentesaux M, Dubruel P, Payen E. 2011. Effect of electrode geometry on the uniformity of plasma-polymerized methyl methacrylate coatings. Prog Org Coat, 70, 293-299.
  • Tatoulian M, Arefi-Khonsari F, Borra JP. 2007. Deposition of organic coatings at atmospheric pressure from liquid precursors. Plasma Process Polym, 4, 360-369.
  • Morent R, De Geyter N, Jacobs T, Van Vlierberghe S, Dubruel P, Leys C, Schacht E. 2009. Plasma-polymerization of HMDSO using an atmospheric pressure dielectric barrier discharge. Plasma Process Polym, 6, 537-542.
  • Hiratsuka A, Karube I. 2000. Plasma polymerized films for sensor devices. Electroanal, 12(9), 695-702. 27 .Shenton MJ, Stevens GC, Wright NP, Duan X. 2002. Chemical-surface modification of polymers using atmospheric pressure nonequilibrium plasmas and comparisons with vacuum plasmas. J Polym Sci A1, 40, 95-109.
  • Ledernez L, Yasuda H, Olcaytug F, Gemetz F, Urban G. 2007. Pressure dependence of plasma polymerization of methane at constant W/FM. Plasma Process Polym, 4, 794-796.
  • Awaja F, Gilbert M, Kelly G, Fox B, Pigram PJ. 2009. Adhesion of polymers. Prog Polym Sci, 34, 948-968.
  • Assis OBG, Hotchkiss JH. 2007. Surface hydrophobic modification of chitosan thin films by hexamethyldisilazane plasma deposition: effects on water vapour, CO2 and O2 permeabilities. Packag Technol Sci, 20, 293-297.
  • Topala I, Asandelusa M, Spridon D, Dumitrascu N. 2009. Hydrophobic coatings obtained in atmospheric pressure plasma. IEEE T Plasma Sci, 37(6), 946-950.
  • Kim B, Yun H, Jung S, Jung Y, Jung H, Choe W, Jo C. 2011. Effect of atmospheric plasma on inactivation of pathogens inoculated onto bacon using two different gas compositions. Food Microbiol, 28, 9-13.
  • Vasilev K, Griesser SS, Griesser HJ. 2011. Antibacterial surfaces and coatings produced by plasma techniques. Plasma Process Polym, 8, 1010-1023.
  • Moisan M, Barbeau J, Crevier MC, Pelletier J, Philip N, Saoudi B. 2002. Plasma sterilization: methods and mechanisms. Pure Appl Chem, 74(3), 349-358.
  • Leipold F, Kusano Y, Hansen F, Jacobsen T. 2010. Decontamination of a rotating cutting tool during operation by means of atmospheric pressure plasmas. Food Control, 21, 1194-1198.
  • Noriega E, Shama G, Laca A, Diaz M, Kong MG. 2011. Cold atmospheric gas plasma disinfection of chicken meat and chichen skin contaminated with Listeria innocua. Food Microbiol, 28, 1293-1300.
  • Sanghini S, Paulussen S, Terryn H. 2011. Atmospheric pressure plasma technology: a straightforward deposition of antibacterial coatings. Plasma Process Polym, 8, 59-69.
  • Chen J, Li J, Zhao ZP, Wang D, Chen CX. 2007. Nanofiltration membrane prepared from polyacrylonitrile ultrafiltration membrane by low-temperature plasma: 5. Grafting of styrene in vapor phase and its application. Surf Coat Tech, 201, 6789-6792.
  • Bartolo L, Morelli S, Piscioneri A, Lopez LC, Favia P, d’Agostino R, Driolli E. 2007. Novel membranes and surface modification able to activate spesific cellular responses. Biomol Eng, 24, 23-26.
  • Ulbricht M. 2006. Advanced functional polymer membranes. Polymer, 47, 2217-2262.
  • Rios GM, Belleville MP, Jeanjean DP. 2007. Membrane engineering in biotechnology: quo vamus? Trends Biotechnol, 25(6), 242-246.
  • Zhou C, Wang Z, Liang Y, Yao J. 2008. Study on the control of pore sizes of membranes using chemical methods Part II. Optimization factors for preparation of membranes. Desalination, 225, 123-138.
  • Bryjak M, Gancarz I, Smolinska K. 2010. Plasma nanostructuring of porous polymer membranes. Adv Colloid Interfac, 161, 2-9.
  • Güleç HA, Gürdaş S, Albayrak N, Mutlu M. 2010. Immobilization of Aspergıllus oryzae β- galactosidase on low pressure plasma modified cellulose acetate membrane by polyethyleneimine for production of galactooligosaccharide. Biotechnol Bioproc E, 15 (6), 1006-1015.
  • Alp B, Mutlu S, Mutlu M. 2000. Glow-discharge -treated cellulose acetate (CA) membrane for a high linearity single-layer glucose electrode in the food industry. Food Res Int, 33, 107-112.
  • Tran TD, Mori S, Suzuki M. 2007. Plasma modification of polyacrilonitrile ultrafiltration membrane. Thin Solid Films, 515, 4148-4152.
  • Chu LQ, Knoll W, Förch R. 2009. Plasma-polymerized non-fouling thin films for DNA immobilization. Biosens Bioelectron, 25, 519-522. 48. Guermat N, Bellel A, Sahli S, Segui Y, Raynaud P. 2009. Thin plasma-polymerized layers of hexamethyldisiloxane for humidity sensor development. Thin Solid Films, 517, 4455-4460.
  • Karamollaoğlu I, Öktem H, Mutlu M. 2009. QCM-based DNA biosensor for detection of genetically modified organisms (GMOs). Biochem Eng J, 44, 142-150.
  • Mutlu S, Çökeliler D, Shard A, Goktas H, Ozansoy B, Mutlu M. 2008. Preparation and characterization of ethylenediamine and cysteamine plasma polymerized films on piezoelectric quartz crystal surfaces for a biosensor. Thin Solid Films, 516, 1249-1255.
There are 47 citations in total.

Details

Primary Language Turkish
Journal Section Articles
Authors

Hacı Ali Güleç This is me

Publication Date October 1, 2012
Published in Issue Year 2012 Volume: 37 Issue: 5

Cite

APA Güleç, H. A. . (2012). Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri. Gıda, 37(5), 295-302.
AMA Güleç HA. Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri. The Journal of Food. October 2012;37(5):295-302.
Chicago Güleç, Hacı Ali. “Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri”. Gıda 37, no. 5 (October 2012): 295-302.
EndNote Güleç HA (October 1, 2012) Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri. Gıda 37 5 295–302.
IEEE H. A. . Güleç, “Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri”, The Journal of Food, vol. 37, no. 5, pp. 295–302, 2012.
ISNAD Güleç, Hacı Ali. “Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri”. Gıda 37/5 (October 2012), 295-302.
JAMA Güleç HA. Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri. The Journal of Food. 2012;37:295–302.
MLA Güleç, Hacı Ali. “Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri”. Gıda, vol. 37, no. 5, 2012, pp. 295-02.
Vancouver Güleç HA. Gıda Endüstrisinde Isıl Olmayan Plazma Teknolojileri. The Journal of Food. 2012;37(5):295-302.

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