KOREAN J. FOOD COOKERY SCI. Vol. 29, No. 2 April, 2013 ISSN 2287-1780(Print) ISSN 2287-1772(Online) http://dx.doi.org/10.9724/kfcs.2013.29.2.147 포장재의종류에따른저장중카레분말의향안정성변화 최준봉수원대학교호텔관광대학원 Effect of Packaging on Aroma Stability of Curry Powder during Storage Jun-Bong Choi Graduate School of Hotel & Tourism, The University of Suwon Abstract The objective of this study was to evaluate the effects of packaging on the aroma stability of curry powder during storage. The Volatile flavor compounds from curry powders packed with or were analyzed by the solid phase microextraction and gas chromatography-mass spectrometry during in storage at 25 for 13 weeks. Forty-eight compounds, comprising 36 terpenes, 5 alcohols, 4 benzenes, 2 carbonyl compounds, and 1 ester, were identified from the curry powders. The main volatile compounds were cuminaldehyde, anethole, and eugenol. The Volatile compounds of curry powder packed with were maintained unchanged during in the storage, whereas those packed in were decreased during the storage. The amounts of p-cymene, cuminaldehyde, anethole, and (E)-caryophyllene from curry powder packed with were maintained during storage, while those packed with decreased gradually. The aroma stability of eugenol was unaffected by packaging. The results indicates that curry powder is best packaged in with to maintain the aroma stability during storage. Key words : curry powder, aroma stability, volatile flavor compound, solid phase microextraction 1) I. 서론 카레분말은심황 (tumeric) 을비롯하여 15 20 여종의천연향신료를혼합하여향신료의풋내제거와향의조화를이루기위하여 30 40 에서 3 6 개월간숙성시켜향신료특유의맛과향을내는천연향신혼합분말로서시판분말, 고형및레토르트카레의주원료로사용된다 (Park WK 등 1991). 카레분말은매운맛이있어위장을적당히자극하여식욕을돋우며소화액의분비를도와준다. 카레특유의노란색은강황또는울금이라는식물의뿌리에서나오는 tumeric 으로 curcumin, demethoxycurcumin, bisdemethoxycurcumin 3 종류의 curcuminoids 혼합물인페놀화합물로이중 curcumin 이 77% Corresponding author : Jun-Bong Choi, Graduate School of Hotel & Tourism, The University of Suwon, Hwaseong 445-743, Korea Tel: +82-031-229-8378 Fax: +82-031-220-2458 E-mail: junbongchoi@hanmail.net 정도로함유되어있다. 카레의황색색소인 curcumin 은강한항산화제로항암성, 항염증성, 향균성, 항변이성등을갖고있는것으로알려지고있다 (Woo IA 등 2003). Kim HW 등 (1989) 은카레분에사용되는향신료 11 종 ( 육두구, 쿠민, 카다몬, 심황, 고수, 정향, 올스파이스, 카시아, 회향, 셀러리시드및검정후추 ) 의주요향기성분조성을밝힌바있으며, Park WK 등 (1991) 과 Park WK 등 (1993) 은미분쇄및배전처리가카레분말및숙성카레분말의휘발성향기성분의변화에미치는영향에서카레분말의숙성효과를향상시키기위해서숙성전의카레분말에대해서미분쇄및배전처리를하는것이효과적이라고하였다. 카레분말의장점을이용하기위해서카레분말을식빵이나떡에첨가하여그품질특성에대한연구결과가보고된바있다 (Woo IA 등 2003, Ahn JW 2009). 지금까지카레의휘발성향기성분, 생리활성효과및카레분말첨가에의한식품의품질특성에대한연구는이루어졌으나카레분말의저장조건이휘발성향기성분의변화에미치는영향에대한연구는아직이루어지지않은실정이다. 따라서본연구에서는포장재종류에따른카레분말의향안정성에대하여검토하고자한다.
148 최준봉 Ⅱ. 재료및방법 Ⅲ. 결과및고찰 1. 시료 본실험에사용한카레분말은 ( 주 ) CJ 로부터제공받았다. 카레분말은 20 g 씩각각 및 로포장하여저장하였다. 포장재재질구성은 은 PET12/PE20/AL7/PE20/LLDPE50 이며, 은 LDPE200 이었다. 2. 저장방법 포장재종류에따른카레분말의향안정성을알아보기위하여 및 로포장한카레분말을 25 ( 실온 ) 에서 13 주동안저장하면서휘발성향기성분을 1 주일간격으로분석하였다. 3. 휘발성향기성분의추출및분석 (1) Solid phase microextraction (SPME) 카레분말의휘발성향기성분추출은 solid phase microextraction(spme) 을이용하였다. SPME fiber 는 50/30 μm dibenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) 을사용하였다. 카레분말 1 g, deodorized distilled water 12 ml, 내부표준물질로서 3-heptanol 38.9 μg을 20 ml headspace vial 에넣고 teflon cap 으로밀봉하였다. 4 0 에서 30 분간방치하여평형상태에도달시킨후, SPME fiber 를 1 cm 노출시켜 30 분동안카레분말의휘발성향기성분을흡착시켰다. Injector port (200 ) 에 fiber 를노출시키고 1 분동안탈착시켜 gas chromatograph-mass spectrometer 에 injection 하였다. 분석은 duplicate 로실시하였다. (2) Gas chromatography-mass spectrometry (GC-MS) SPME로추출한카레분말의휘발성향기성분은 Agilent 6890N GC/Agilent 5973 mass selective detector(msd)(agilent Co., Palo Alto, CA, USA) 를사용하여동정하였다. Column은 DB-5ms(60 m length x 0.25 mm i.d. x 0.25 μm film thickness : J & W Scientific, Folsom, CA, USA) 를사용하였고, oven 온도는 40 에서 5분간유지한후 90 까지 10 /min, 210 까지 3 /min의속도로승온시킨후다시 250 까지 10 /min의속도로승온시켜 10분간유지하였다. Injector 온도는 200, detector 온도는 250 이었으며 carrier gas로는 helium을사용하였고유속은 1 ml/min 이었다. Ionization voltage는 70 ev 그리고분석할분자량의범위 (m/z) 는 33 350으로하여분석하였다. 분석은 2회반복실시하였다. (3) 휘발성향기성분동정 휘발성향기성분의동정은 retention indices(ri) 와 Wiley/7n mass spectral database (Hewlett-Packard Co., Palo Alto, CA, USA) 를이용하였다. 또한문헌상의 retention index 와 spectrum 을비교하여휘발성향기성분을확인하였다. 1. 카레분말의휘발성향기성분 포장재종류에따른카레분말의향안정성을알아보기위하여 및 로포장한카레분말을 25 에서 13 주동안저장하면서휘발성향기성분을 1 주일간격으로분석하였다. SPME 를이용하여카레분말의휘발성향기성분을추출하고 GC-MS 로분석한결과모두 48 종의휘발성향기성분이동정되었고그결과는 Table 1 과같았다. Table 1. Volatile flavor compounds of curry powder by SPME No a RI b Compound name Concentration (ppm) 1 926 α-thejene 25.2±6.8 c 2 935 α-pinene 98.5±2.5 3 975 sabinene 177.3±5.6 4 983 β-pinene 239.0±0.6 5 987 β-myrcene 50.8±3.5 6 1010 α-phellandrene 165.8±4.5 7 1012 δ-3-carene 32.8±3.0 8 1019 α-terpinene 30.6±4.9 9 1028 p-cymene 428.6±5.5 10 1033 limonene 244.9±6.6 11 1035 β-phellandrene 47.0±7.2 12 1037 eucalyptol 71.5±2.6 13 1061 γ-terpinene 424.9±7.3 14 1073 (E )-sabinene hydrate 24.4±3.3 15 1088 α-terpinolene 29.3±7.6 16 1095 1,3,3-trimethyl bicyclo[2.1.1]heptane-2-one 17.3±2.8 17 1100 linalool 123.4±3.7 18 1106 (Z)-sabinene hydrate 18.7±6.5 19 1187 4-terpineol 107.4±1.8 20 1202 p-allylanisole 229.6±0.7 21 1259 cuminaldehyde 2,447.3±3.8 22 1287 cinnamaldehyde 274.3±19.9 23 1299 anethole 1,485.3±10.6 24 1302 1-phenyl-1-butanol 336.3±0.6 25 1303 1-phenyl-1,2-ethanediol 198.7±4.6 26 1340 δ-elenene 18.2±2.2 27 1350 camphene 185.1±4.7 28 1352 α-cubebene 21.6±3.6 29 1361 eugenol 1,072.6±3.4 30 1375 geranyl acetate 51.0±2.9 31 1383 α-copaene 81.5±8.7 32 1399 methyl eugenol 109.2±1.2 33 1432 (E)-caryophyllene 641.7±1.6 34 1451 (E)-β-farnesene 38.1±3.2 35 1465 α-humulene 77.0±1.2 36 1484 α-curcumene 101.4±0.2 37 1489 γ-himachalene 34.5±1.4 ( 계속 ) 한국식품조리과학회지제 29 권제 2 호 (2013)
KOREAN J. FOOD COOKERY SCI. Vol. 29, No. 2 April, 2013 38 1497 zingiberene 61.8±4.2 39 1499 β-selinene 90.1±2.5 40 1505 thujopsene-13 49.3±1.9 41 1510 β-bisabolene 37.5±2.7 42 1515 acetyl eugenol 75.5±10.9 43 1525 4-methoxy-6-(2-propenyl)-1,3-benzodioxole 197.4±2.5 44 1528 β-sesquiphellandrene 79.0±1.8 45 1543 1,2,3-trimethoxy-5-(2-propenyl)benzene 26.4±9.3 46 1667 β-tumerone 219.2±0.2 47 1672 ar-tumerone 129.2±0.4 48 1705 α-tumerone 92.2±2.2 a Numbers correspond to those in Figure 1. b Retention indices were determined on DB-5ms using C6 C22 as external reference. c Mean ± standard deviation. 카레분말의휘발성향기성분을작용기별로보면, terpene 류가 36 종으로카레분말의주요휘발성향기성분으로확인되었으며 alcohol 류가 5 종, benzene 류가 4 종, carbonyl 화합물이 2 종, ester 류가 1 종이었다. 이중 cuminaldehyde(no. 21) 가 2,447.3 ppm 으로가장높은함량을나타내었으며, anethole(no. 23) 과 eugenol(no. 29) 도 1,000 ppm 이상의높은함량을나타내었다. 그외 p-cymene(no. 9), γ-terpinene(no. 13), 1-phenyl-1-butanol(no. 24) 및 (E)-caryophyllene(no. 33) 등이카레분말에높은함량으로존재하는휘발성향기성분이었다. Park WK 등 (1991) 은카레분의주요휘발성성분은 eugenol, cuminaldehyde, myristicin, anethole, cinnamaldehyde, linalool 및 limonene 이라하였으며본연구에서도비슷한경향을보여주었다. Cuminaldehyde 는 p-isopropylbenzaldehyde 이며향신료쿠민 (cumin) 의주요향기성분으로쿠민에 37.68% 함유되어있으며쿠민특유의향특성은나타낸다고알려져있다 (Kim HW 등 1989). 최근엔 cuminaldehyde 의건강기능성에대해많은연구가이루어지고있다 (Sowbhagya HB 2013). Anethole 은회향 (fennel) 의주요향기성분으로아니스향특성을가지고있으며 Streptococcus mutans 에대한항균작용이있다고알려져있다 (Park JS 등 2004). Eugenol 은정향 (clove) 에 63.63% 함유되어있는주요향기성분으로정향특유의 spicy 한향특성을가지고있다 (Kim HW 등 1989). 2. 포장재종류에따른카레분말의휘발성향기성분변화 Laminated film 및 로포장하여 25 에서저장한카레분말의휘발성향기성분을저장초기와 13 주째에측정한 total ion chromatogram (TIC) 은 Fig 1 과같았다. Laminated film 으로포장하여저장한카레분말의휘발성향기성분은 13 주저장한후에도변화가거의없었음을알수있다. Vinyl 로포장하여 13 주저장한카레분말의 TIC 를보면피크면적이초기에비해크게감소하여카레분말의휘발성향기성분이많이손실되었음을알수있다. 즉, 은카레분말을 2 5 에서 13 주동안저장하여도향손실이거의없어카레분말의향안정성에효과가있으나 포장은휘발성향기성분의손실이많이발생하여카레분말의향안정성에효과가 없음을알수있었다. Abundance 2.1e+07 2e+07 1.9e+07 1.8e+07 1.7e+07 1.6e+07 1.5e+07 1.4e+07 1.3e+07 1.2e+07 1.1e+07 1e+07 9000000 8000000 7000000 6000000 5000000 4000000 3000000 2000000 1000000 Time--> Abundance 9000000 8000000 7000000 6000000 5000000 4000000 3000000 2000000 1000000 Time--> 2.1e+07 2e+07 1.9e+07 1.8e+07 1.7e+07 1.6e+07 1.5e+07 1.4e+07 1.3e+07 1.2e+07 1.1e+07 1e+07 Abundance 9000000 8000000 7000000 6000000 5000000 4000000 3000000 2000000 1000000 Time--> 2.1e+07 2e+07 1.9e+07 1.8e+07 1.7e+07 1.6e+07 1.5e+07 1.4e+07 1.3e+07 1.2e+07 1.1e+07 1e+07 IS 9 TIC: C-OD1.D 21 10 15.00 20 25.00 30 35.00 40 45.00 IS 9 23 29 33 TIC: CNPR13-2.D 21 0 day 10 15.00 20 25.00 30 35.00 40 45.00 IS 9 23 29 33 TIC: CPR13-2.D 21 23 Laminated film 10 15.00 20 25.00 30 35.00 40 45.00 29 33 Vinyl Fig 1. Total ion chromatograms of curry powder packed with or after storage at 25 for 13 weeks (IS: internal standard, 9: p-cymene, 21: cuminaldehyde 23: anethole, 29: eugenol, 33: (E)-caryophyllene). 향신료저장시적합한포장재선택의기준은저장시향기성분의유지와산화작용의지연에있다 (Mizani M 등 2009). 고분자물질로제조된포장재는향기성분과같이분자량이작은물질에투과성이있으므로적합한포장재의선택은식품의바람직한향을오랫동안유지하여저장기간을연장시키는데필수적이다 (Zhou Q 등 2004). 일반적으로향신료저장시 이많이사용되나일부에서는포장재선택에부주의하여 포장을사용하는경우도있는데이경우에는장기간저장시카레분말의향기성분을유지하기어려울것으로판단되며이는최종카레제품의품질에도영향을미칠것이다. Korean J. Food Cookery Sci. Vol. 29, No. 2(2013)
150 최준봉 포장재에따른식품의품질변화에대한연구로는나물 (Jo IH 등 2012), 양파 (Hong SI 등 2003), 부추 (Kim CB 등 1999) 및상추 (Lee JS 등 2008) 에서행해진바있는데포장재및포장방법이식품의품질에많은영향을준다는사실이일반적으로잘알려져있다. Park HW 등 (1989) 과 Han JG 등 (1996) 은 으로포장한비엔나소세지와현미의품질에대해연구한바있다. 3. 저장기간에따른카레분말의총휘발성향기성분변화 Fig 2 는카레분말을 13 주저장하는동안휘발성향기성분의총피크면적의변화를살펴본것으로 으로포장한카레분말의휘발성향기성분은저장기간중변화가거의없음을알수있고 로포장한카레분말의휘발성향기성분은저장 3 주동안은완만하게감소하다가저장 4 주째부터휘발성향기성분의감소가크게일어나저장기간중에계속해서향기성분이손실됨을알수있다. 3.0e+10 이포장재종류에큰영향을받지않아서 과 로포장한카레분말은저장기간동안 eugenol 의감소가거의일어나지않았다 (Fig 7). 1.5e+9 5.0e+8 Fig 3. Changes in peak area of p-cymene in curry powders packed with or 2.5e+10 8.0e+9 2.0e+10 1.5e+10 1.0e+10 7.0e+9 6.0e+9 4.0e+9 3.0e+9 Fig 2. Changes in total peak area of volatile flavor compounds in curry powders packed with or 4. 저장기간중카레분말의주요휘발성향기성분변화 카레분말에높은함량으로존재하는휘발성향기성분인 p-cymene, cuminaldehyde, anethole, eugenol 및 (E)-caryophyllene 의저장중변화를살펴보았다 (Fig 3-7). Laminated film 으로포장하였을때 13 주저장기간중 p-cymene 의변화가거의없었으나, 로포장하였을때에는감소가두드러져 1 주후부터지속적으로감소하였다 (Fig 3). Cuminaldehyde 는 으로포장하였을때 13 주저장기간중변화가거의없었으나, 로포장하였을때에는 3 주까지는향이유지되었으나 4 주부터감소하기시작하여저장기간동안지속적으로감소하였다 (Fig 4). Anethole 과 (E)-caryophyllene 의저장중변화도 cuminaldehyde 과비슷한경향을보여주었다 (Fig 5 와 6). 휘발성향기성분의종류에따라포장재종류에따른향안정성에차이가있었는데 eugenol 은저장기간중향안정성 Fig 4. Changes in peak area of cuminaldehyde in curry powders packed with or 4.0e+9 3.0e+9 Fig 5. Changes in peak area of anethole in curry powders packed with and 한국식품조리과학회지제 29 권제 2 호 (2013)
KOREAN J. FOOD COOKERY SCI. Vol. 29, No. 2 April, 2013 해서는 으로포장하여저장하는것이바람직하다고생각한다. 참고문헌 Fig 6. Changes in peak area of (E )-caryophyllene in curry powders packed with and 4.0e+9 3.0e+9 Fig 7. Changes in peak area of eugenol in curry powders packed with or Ⅳ. 결론 포장재종류에따른카레분말의향안정성을알아보기위하여카레분말을 또는 로포장하여 25 에서 13 주동안저장하면서휘발성향기성분의변화를측정하였다. 포장재종류에따른카레분말의휘발성향기성분은 으로포장한경우저장기간 (13 주 ) 동안향이유지되는경향을나타냈다. 반면, 로포장한경우는휘발성향기성분의손실이많았다. p-cymene, cuminaldehyde, anethole 및 (E)-caryophyllene 은 으로포장하였을때 13 주저장기간동안향기성분의변화가적었으나, 로포장하였을때에는향기성분이지속적으로감소하였다. Eugenol 의향안정성은포장재종류의영향을받지않아저장기간중휘발성향기성분의감소가적게일어났다. 따라서카레분말을상온에서저장시향안정성을유지하기위 Ahn JW. 2009. Properties of rice cakes for topokki with curry powder. Korean J Food Cookery Sci 25(4) :467-473 Han JG, Kang KJ, Kim KK, Kim SK. 1996. Water absorption of stored brown rice in pouch. J Korean Soc Food Sci Nutr 25(4) :643-648 Hong SI, Son SM, Chung MS, Kim D. 2003. Storage quality of minimally processed onions as affected by seal-packaging methods. Korean J Food Sci Technol 35(6) :1110-1116 Jo IH, Kim HS, Kim GM, Kim JS, Kim GC. 2012. Effects of packaging method on the quality of blanched Namul during storage. Korean J Food Preserv 19(3) :328-336 Kim CB, Lee SH, Kim JS, Yoon JT, Kim T. 1999. Effects of packing materials on the keeping freshness of Chinese chives(allium tubersum Rottler) at low temperature storage. Korean J Food Preserv 6(3) :270-275 Kim HW, Huh KT, Choi CU. Studies on the volatile flavor components of spices in curry. Korean J Food Sci Technol 21(1) :127-135 Lee JS, Lee HE, Lee YS, Chun CH. 2008. Effect of packaging methods on the quality of leaf lettuce. Korean J Food Preserv 15(5) :630-634 Mizani M, Sheikh N, Ebrahimi SN, Gerami A. Tavakoli FA. 2009. Effect of gamma irradiation on physico-mechanical properties of spice packaging films. Radiat. Phys. Chem 78:806-809 Park HW, Kim BS, Park MH. 1989. Comparison of shelf-life of vienna sausage packed with polyidene chloride and nylon. Korean J Food Sci Technol 21(2) :252-257 Park JS, Baek HH, Bai DH, Oh TK, Lee CH. 2004. Antibacterial activity of fennel (Foeniculum vulgare Mill.) seed essential oil against the growth of Streptococcus mutans. Food Sci Biotechnol 13(5) :581-585 Park WK, Yoon JH, Kim HW, Choi CU. 1991. The effects of stamping and roasting treatments on volatile aromatic components in curry powder. Korean J Food Sci Technol 23(3) :276-279 Park WK, Yoon JH, Kim JH, Jung SH, Son SH. 1993. The effects of stamping and roasting treatments on change of volatile flavor components in aged curry powder. Korean J Food Sci Technol 25(5) :426-429 Korean J. Food Cookery Sci. Vol. 29, No. 2(2013)
152 최준봉 Sowbhagya HB. 2013. Chemistry, technology, and nutraceutical functions of cumin (Cuminum cyminum L): An Overview. Crit. Rev. Food Sci Nutr. 53(1) :1-10 Woo IA, Nam HW, Pyun JW. 2003. Quality characteristics of bread prepared with the addition of curry powder. Korean J Food Cookery Sci 19(4) :447-453 Zhou Q, Guthrie B, Cadwallader KR. 2004. Development of a system for measurement of permeability of aroma compounds through multilayer polymer films by coupling dynamic vapour sorption with purge-and-trap/fast gas chromatography. Packg Technol Sci 17:175-185. 2013 년 1 월 23 일접수 ; 2013 년 2 월 7 일심사 ( 수정 ); 2013 년 3 월 15 일체택 한국식품조리과학회지제 29 권제 2 호 (2013)