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Mogućnost Iskorišćenja Semenki Jabuka Kao Nusproizvoda Prehrambene Industrije

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Mogućnost Iskorišćenja Semenki Jabuka Kao Nusproizvoda Prehrambene Industrije UNIVERZITET U BEOGRADU POLJOPRIVREDNI FAKULTET Miloš P. Purić MOGUĆNOST ISKORIŠĆENJA SEMENKI JABUKA KAO NUSPROIZVODA PREHRAMBENE INDUSTRIJE doktorska disertacija Beograd, 2021. UNIVERSITY OF BELGRADE FACULTY OF AGRICULTURE Miloš P. Purić POSSIBILITY OF UTILIZING APPLE SEEDS AS BY-PRODUCT OF FOOD INDUSTRY Doctoral Dissertation Belgrade, 2021. Komisija za ocenu i odbranu: Mentor 1: __________________________________ Dr Biljana Rabrenović, vanredni profesor Univerzitet u Beogradu - Poljoprivredni fakultet Mentor 2: __________________________________ Dr Vladislav Rac, vanredni profesor Univerzitet u Beogradu - Poljoprivredni fakultet Članovi komisije: ___________________________________ Dr Steva Lević, docent, Univerzitet u Beogradu - Poljoprivredni fakultet ___________________________________ Dr Marko Malićanin, docent, Univerzitet u Nišu – Poljoprivredni fakultet u Kruševcu ___________________________________ Dr Mirjana Demin, redovni profesor, Univerzitet u Beogradu - Poljoprivredni fakultet Datum odbrane:________________________ Koristim ovu priliku da se najsrdačnije zahvalim svom prvom mentoru, prof. dr. Biljani Rabrenović na neizmernoj i svesrdnoj pomoći, savetima i podršci tokom kompletnih doktorskih studija i u svim fazama izrade ove doktorske disertacije, počev od izbora sirovine za dobijanje ulja, pa do pomoći oko tumačenja rezultata fizičko-hemijskih parametara kvaliteta i nutritivnih karakteristika ispitivanih hladno ceđenih ulja. Naravno, veliko hvala i na razumevanju u najtežim trenucima. Najsrdačnije se zahvaljujem i svom drugom mentoru, prof. dr. Vladislavu Racu, na svesrdnoj podršci, sugestijama tokom izrade doktorske disertacije i razumevanju u najtežim trenucima. Posebno sam mu zahvalan na pomoći oko osmišljavanja i realizacije metoda za ispitivanje sadržaja polifenola, antioksidativnih i karakteristika koje se odnose na oksidativnu stabilnost hladno ceđenih ulja, kao i na velikoj pomoći u toku postupka inkapsulacije ulja i tumačenju kompletnih rezultata. Zahvaljujem se prof. dr. Mirjani Demin na velikoj pomoći i podršci u osmišljavanju i realizaciji izrade i kompletne analize obogaćenih hlebova sa dodatkom obezmašćene pogače od isceđenih semenki jabuka. Zahvaljujem se prof. dr. Stevi Leviću na pomoći i korisnim sugestijama i savetima u vezi sa postupkom inkapsulacije ulja i ispitivanja morfoloških karakteristika dobijenih inkapsulata, kao i na pomoći u tumačenju dobijenih rezultata inkapsulacije. Zahvaljujem se dr. Latu Pezu sa Instituta za opštu i fizičku hemiju na svesrdnoj pomoći i korisnim sugestijama u toku statističke obrade dobijenih rezultata u disertaciji. I na kraju beskrajno se zahvaljujem svojoj porodici, supruzi Jasni, majci Dušanki, bratu Ratku, tašti Nadi i tastu Srbi, kao i svim svojim kolegama i prijateljima, koji su mi pružali podršku i podsticaj sve vreme tokom izrade disertacije. MOGUĆNOST ISKORIŠĆENJA SEMENKI JABUKA KAO NUSPROIZVODA PREHRAMBENE INDUSTRIJE SAŽETAK Nakon industrijske prerade jabuka ostaje oko 25 % otpada, jabučnog tropa, koji predstavlja ekološki i ekonomski problem. Ovaj otpad sadrži potencijalno vredne nusproizvode, kao što su semenke jabuka. U disertaciji su ispitane mogućnosti iskorišćenja semenki jabuka sorti Ajdared, Zlatni Delišes i Šumatovka. Iz semenki su, postupkom hladnog ceđenja, izdvojena ulja. Na osnovu ispitivanja fizičko- hemijskih parametara, sva tri ulja su ispunjavala uslove kvaliteta za ovu kategoriju, prema Pravilniku. Sadržaji nezasićenih masnih kiselina (89,56-90,09 %), tokoferola (23,4-45,1 mg/100g) i polifenola (2,42–3,81 mgGAE/100g), pokazali su da se radi o uljima visoke nutritivne vrednosti. Najbolju oksidativnu stabilnost na DSC testu, imalo je ulje semenki Šumatovke, a najjača antioksidativna aktivnost, ispitana DPPH i ABTS testom, utvrđena je u ulju semenki sorte Zlatni Delišes. Drugi deo istraživanja je bio posvećen inkapsulaciji ulja, u pogodne nosače, metodama elektrostatičke ekstruzije i sprej-sušenja. Obe metode su pokazale visok stepen efikasnosti (prosečno 92,6 % i 85,7 %, redom), čime je omogućena lakša manipulacija uljem. Rezultati Oven testa su pokazali da inkapsulacija, u određenoj meri, pruža zaštitu uljima od oksidacije. Zaostala obezmašćena pogača od isceđenih semenki, korišćena je kao delimična zamena (5 % i 20 %) za pšenično brašno, u proizvodnji hleba. Hlebovi obogaćeni pogačom su imali značajno veći sadržaj hranljivih vlakana, proteina, polifenola i bolju svežinu u odnosu na standardni hleb. Delovi pogače su se jasno uočavali na poprečnom preseku obogaćenih hlebova, što je doprinelo njihovom atraktivnom izgledu. Konstatovano je da ulje, inkapsulati ulja i obezmašćena pogača mogu imati upotrebnu vrednost u praksi, što semenke jabuka u potpunosti čini iskoristljivim. Ključne reči: ulje semenki jabuke, hladno ceđeno, masne kiseline, tokoferoli, polifenoli, antioksidativna aktivnost, oksidativna stabilnost, inkapsulacija, obezmašćena samlevena pogača, obogaćeni hleb. Naučna oblast: Tehnološko inženjerstvo Uža naučna oblast: Nauka o preradi ratarskih sirovina UDK broj: 631.53.01:634.10]:663/664(043.3) POSSIBILITY OF UTILIZING APPLE SEEDS AS BY-PRODUCT OF FOOD INDUSTRY ABSTRACT After the industrial processing of apples, there remains about 25 % of apple pomace, which is an environmental and economic problem. This waste contains potentially valuable by-products, such as apple seeds. In this dissertation, the possibilities of utilization of apple seeds of the varieties Ajdared, Zlatni Delišes, and Šumatovka were examined. Oils were extracted from the seeds by cold pressing. Based on their physico-chemical parameters, all three oils met the quality requirements for this category, according to the official regulations. The content of unsaturated fatty acids (89.56-90.09 %), tocopherols (23.4-45.1 mg/100g) and polyphenols (2.42-3.81 mgGAE/100g) showed that these oils had high nutritional value. Šumatovka seeds had the best oxidative stability according to the DSC test, whereas Zlatni Delišes had the strongest antioxidant activity, tested by the DPPH and ABTS tests. The encapsulation of oils by electrostatic extrusion and spray-drying methods showed high degree of efficiency (on average 92.6 % and 85.7 %, respectively), which enabled easier oil manipulation. The results of the Owen test showed that encapsulation provided partial protection from oxidation. Residual defatted apple seed cake was used as a partial substitute (5 % and 20 %) for wheat flour in the production of bread. Breads enriched with different portions of cake had a significantly higher content of dietary fiber, proteins, polyphenols, and better freshness compared to the standard bread. In addition, the enriched breads have an attractive appearance, pleasant tactile sensation during chewing, and smell. It was concluded that oil, oil encapsulates, and enriched bread can all be used in the manufacture, which makes apple seeds completely usable. Key words: apple seed oil, cold pressed, fatty acids, tocopherols, polyphenols, antioxidant activity, oxidative stability, encapsulation, defatted ground oil cake, enriched breads. Scientific field: Technological engineering Scientific subfield: Science of field crop processing UDC number: 631.53.01:634.10]:663/664(043.3) SADRŽAJ 1. UVOD 1 2. PREGLED LITERATRURE 3 2.1. Jabuka 3 2.1.1. Klimatski i zemljišni uslovi za gajenje jabuka 3 2.1.2. Proizvodnja jabuke u svetu 3 2.1.3. Proizvodnja jabuke u Srbiji 4 2.1.4. Plod jabuke – morfologija i anatomija 4 2.1.5. Sortiment jabuka 5 2.1.5.1. Ajdared 6 2.1.5.2. Zlatni Delišes 6 2.1.5.3. Šumatovka 7 2.1.6. Zrelost, berba i skladištenje plodova jabuke 8 2.2. Fizičko-hemijski sastav jabučnog tropa 9 2.3. Semenke jabuka 10 2.3.1. Izdvajanje semenki iz jabučnog tropa i priprema za ceđenje ulja 11 2.4. Tehnološki postupak proizvodnje hladno ceđenih biljnih ulja 13 2.4.1. Faktori koji utiču na efikasnost presovanja 13 2.4.2. Presovanje – pužne prese 14 2.4.3. Odvajanje mehaničkih nečistoća – čišćenje ulja 14 2.4.4. Naknadna obrada i pakovanje ulja 15 2.5. Glavni sastojci biljnih ulja 16 2.5.1. Triacilgliceroli 16 2.5.2. Masne kiseline 17 2.5.2.1. Zasićene masne kiseline 18 2.5.2.2. Nezasićene masne kiseline 19 2.6. Minorni sastojci biljnih ulja – neosapunjive materije 20 2.6.1. Fosfolipidi 20 2.6.2. Tokoferoli i tokotrienoli 21 2.6.3. Steroli 23 2.6.4. Pigmenti 24 2.6.5. Fenolne materije 25 2.7. Kvarenje ulja i delovanje prirodnih antioksidanata 26 2.7.1. Mehanizam autooksidacije lipida 27 2.7.2. Mehanizam delovanja prirodnih antioksidanata 28 2.8. Sadržaj i hemijski sastav ulja iz semenki jabuka 29 2.8.1. Sadržaj ulja 29 2.8.2. Sadržaj i sastav triacilglicerola i masnih kiselina 30 2.8.3. Sadržaj i sastav tokoferola 31 2.9. Analitičke tehnike u analizi biljnih ulja 31 2.9.1. Kiselost ulja 32 2.9.2. Identifikacija biljnih ulja 32 2.9.2.1. Određivanje gustine i indeksa refrakcije ulja 32 2.9.2.2. Jodni broj 33 2.9.2.3. Saponifikacioni broj 34 2.9.3. Procena stepena oksidacije i održivosti ulja 35 2.9.3.1. Peroksidni broj 36 2.9.3.2. Anisidinski broj, konjugovani dieni i trieni 37 2.9.3.3. Rancimat test 37 2.9.3.4. Schaal ili Oven test 38 2.9.3.5. Diferencijalno-skenirajuća kalorimetrija (DSC) 38 2.9.4. Gasna hromatografija 39 2.9.5. Tečna hromatografija visokog stepena razdvajanja (HPLC) 41 2.9.6. Antioksidativna aktivnost biljnih ulja 41 2.9.6.1. DPPH test 42 2.9.6.2. ABTS test 42 2.10. Inkapsulacija 43 2.10.1. Definicija inkapsulacije, osnovne karakteristike i primena 43 2.10.2. Materijali za inkapsulaciju 44 2.10.3. Tehnike inkapsulacije 45 2.10.3.1. Elektrostatička ekstruzija 46 2.10.3.2.
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