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1 Korean J Food Cook Sci Vol. 32, No. 1, pp. 16~26 (2016) pissn eissn 흑마늘의첨가량을달리한식초의품질특성 심혜진 서원택 1 최명효 김경화 신정혜 강민정 ( 재 ) 남해마늘연구소, 1 경남과학기술대학교 Quality Characteristics of Vinegar Added with Different Levels of Black Garlic Hye Jin Sim Weon Taek Seo 1 Myoung Hyo Choi Kyoung Hwa Kim Jung Hye Shin Min Jung Kang Namhae Garlic Research Institute, Namhae, 52430, Korea 1 Department of Food Technology, Gyeongnam National University of Science and Technology, Jinju, 52725, Korea Abstract In this study, we aimed to develop functional vinegar with different levels of black garlic through two stages of fermentation. Black garlic vinegars were prepared from black garlic and water (w/w) mixed with 1:2 (BG3), 1:5 (BG6), 1:9 (BG9) and 1:11 (BG12), and adding the sugar by adjusting the soluble solids content to 14 Brix. The alcohol content of black garlic vinegar was % after 7 days of alcohol fermentation at 25 C. Acetic acid fermented was at 30 C for 25 days and samples were taken at 3, 6, 9, 12, 15, 20 and 25 days. The ph of black garlic vinegar was not significantly different among the samples, but acidity was increased during fermentation. Total polyphenol contents showed irregular changes with the fermentation periods and were higher by black garlic content. At 25 days fermentation, total polyphenol contents were mg/100 ml. Acetic acid content of black garlic vinegars was higher than other organic acids. S-allyl cysteine (SAC) contents of BG3 and BG6 were and mg/l, respectively. However SAC was not detected in BG9 and BG12. In 25 days fermented black garlic vinegar, the major mineral was K with a content ratio of 61-68% of total minerals. The DPPH and ABTS radical scavenging activity of 25 days fermented black garlic vinegar were stronger at higher black garlic content. Key words: vinegar, black garlic, fermentation, acetobacter, S-allyl cysteine Ⅰ. 서론 식초는동서양의대표적인발효식품으로미생물을이용하여당류나전분질을함유하고있는여러원료들을알코올및초산발효시켜제조된다 (Hong SM 등 2012a). 식초의종류는초산을희석하고각종감미료를첨가하여만드는합성식초와곡류, 사과, 감등을이용하여발효시키는양조식초로대별되며 (Yi MR 등 2014), 양조식초는과즙을 30% 이상함유하는과실식초와곡물을 4% 이상함유하는곡물식초로분류되고있다 (Beak CH 등 2013). 식초는제조시원료의종류, 제조방법, 발효방법및함유성분들의함량에따라독특한풍미를나타내며, 품질은초산의함량, 휘발성향기성분, 미량의각종유기산및아미노산, 당류, 염류등의다양한요인에의해결정된다 (Jeoung YJ & Lee MH 2000). 식초의주요성분인유기산중약 50% 는초산이며, 이 외에도 citric acid, succinic acid, lactic acid, tartaric acid 등당분해과정인 TCA cycle 에서볼수있는대부분의유기산이함유되어있어생체조직내에서호기적으로쉽게분해가능하며, 생리적상태에따라필요한물질로쉽게전환될수있다. 또한식초는생체의균형을유지하는데도움이되는장점이있어건강식품으로인식되면서 (Son SM 1992), 단순조미료기능에서마시는건강음료로서마케팅되어소비량이급속하게증가되고있다 (Park HJ 등 2014). 식초의소재또한향이나풍미가독특하거나유효성분을함유하고있는무화과 (Kim DH 1999), 매실 (Ko YJ 등 2007), 감 (Park MH 등 2005), 사과 (Kang BH 등 2011) 등의과실류식초와함초 (Kim HC 2011), 다시마 (Kim KE 등 2001), 죽순 (Jang HJ 등 2013), 야콘 (Lee MK 등 2012), 인삼 (Ann YG 등 1999) 등의다양한재료들을이용한식초가활발히연구개발되고있고, 이러한식초들은소화액분비촉진, 젖산분해에따른피로 Corresponding author: Min Jung Kang, Namhae Garlic Research Institute, Namhae-daero , Idong-myeon, Namhae-gun, Gyeongsangnam-do, 52430, Korea ORCID: Tel: , Fax: , jung-75@hanmail.net 2016 Korean Society of Food and Cookery Science This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License ( nses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

2 Korean J Food Cook Sci 흑마늘의첨가량을달리한식초의품질특성 17 회복과숙취해소, 동맥경화와고혈압등의성인병예방, 콜레스테롤저하, 체지방감소와같은다양한생리활성 (Jeong YJ 2009, Hong SM 등 2012b, Sung NH & Jeong YJ 2013) 을지니는것으로보고되고있다. 마늘의냄새와맛을조절하기위해열처리공정을활용한가공마늘인흑마늘은마늘자체성분에의한 aminocarbonyl 반응에의해갈변물질이생성되어점차검게변하게되고, 단맛이증가하며마늘의매운맛이나향은감소하게된다 (Shin JH 등 2010a). 따라서생마늘에비해섭취가용이하므로추출물이나분말의형태로여러가공식품유형에첨가하여재가공이이루어지고있는데, 흑마늘을첨가한소시지 (Shin JH 등 2011), 양갱 (Park CH 등 2014), 떡 (Shin JH 등 2010b), 잼 (Kim MH 등 2008) 및요구르트 (Shin JH 등 2010b) 등이개발되어있다. 흑마늘은숙성되는과정을거치면서폴리페놀류의함량이증가하며, S-allyl cysteine(sac) 과같은수용성유황아미노산과 diallyl sulfide(das), triallyl sulfide, diallyl disulfide(dads), diallyl polysulfides 등의지용성물질이유리됨으로서 (Lee JO 등 2009, Kim AJ & Rho JO 2011) 생리활성이증가한다. 이러한성분들과더불어새로이생성된갈변물질에의해생마늘보다높은항산화활성을나타내며암예방, 콜레스테롤저하, 동맥경화개선, 심장질환예방, 산화스트레스와관련된증상의예방및항염증활성등의효과가보고되어있다 (Shin JH 등 2008, Tak HM 등 2014a). 본연구에서는흑마늘첨가량을달리하여식초를제조함에있어초기고형분함량을동일하게조절하기위하여설탕으로보당하고알코올발효한다음초산발효기간에따른흑마늘식초의품질특성을조사하여자연발효를통한흑마늘식초의개발가능성을확인하고자하였다. 1. 흑마늘식초제조 Ⅱ. 재료및방법 식초제조를위한흑마늘은남해보물섬마늘영농조합법인에서시판중인것을제공받아사용하였다. 껍질을제거한흑마늘과미리멸균처리한음용수를 1:2(BG3), 1:5 (BG6), 1:8(BG9) 및 1:11(BG12) 의비율 (w/w) 로혼합하여균질화하였다. 균질화된흑마늘분쇄물의고형분함량은각각 14, 6.8, 5 및 4.6 Brix 였으며 (data not shown), 가용성고형분함량이가장높았던 BG3 와여타실험군의가용성고형분함량을동일하게조절하기위하여설탕을가해 14 Brix 로조절하였다. 이것을각각 4 kg 씩 5 L 광구병에담아 99 C 에서 10 분간살균하고흑마늘혼합물에효모 (Saccharomyces cerevisiae) 를 5% 접종하여 25 C 에서알코올발효하였다. 7 일간의알코올발효후알코올 함량이 % 인발효물을얻었다. 여기에 1% 알코올을함유하는맥아추출액배지에서 Acetobacter pasterianus 균을 3 일간배양한종초를 2.5% 접종한것을 0 일차로하여 30 C 에서발효시키면서발효 15 일까지는 3 일간격으로, 그이후는 5 일간격으로시료를채취하여발효기간에따른차이를분석하였다. 2. ph, 산도및당도측정 시료 5 g 에증류수를가해 50 ml 로만든다음잘혼합한후여과지 (No. 2, Advantec, Tokyo, Japan) 로여과한여액을시료로하여 ph 와적정산도를자동적정기 (G20 compact titrator, Mettler Toledo, Greifensee, Switzerland) 를이용하여동시에측정하였다. 적정산도는 0.1 N NaOH 용액 (Daejung, Siheung, Korea) 으로시료액의 ph 가 8.4 가될때까지적정하여초산양으로환산하였다. 당도는시료액을일정량취하여자동굴절당도계 (PR-201α, Atago, Tokyo, Japan) 로 3 회반복측정하였다. 3. 총폴리페놀화합물의정량 총폴리페놀화합물의함량은폴리페놀성물질인 phosphomolybdic acid 와반응하여청색을나타내는원리로 Folin-Denis 법 (Ragazzi E & Veronese G 1973) 에따라시료액 1 ml 에 2 M Folin-Ciocalteau 시약 (Sigma Co., St. Louis, MO, USA) 0.5 ml 를넣고 3 분후 10% Na 2 CO 3 용액 (Daejung, Siheung, Korea) 0.5 ml 씩을혼합하여실온의암실에서 1 시간정치한다음분광광도계 (Libra S 35, Biochrom, Cambridge, England) 를이용하여 760 nm 에서흡광도를측정하였다. 표준물질로 gallic acid(sigma Co., St. Louis, MO, USA) 를사용하여시료와동일한방법으로분석하여얻은검량선으로부터총폴리페놀함량을계산하였다. 4. S-allyl-L-cysteine(SAC) 함량분석각각의시료를 filter paper로여과한후여액을 0.22 μm membrane filter로재여과하여 HPLC-PDA-MS/MS(TSQ Quantum LC-MS/MS, Thermo scientific, Waltham, MA, USA) 로분석하였다. Analytical column은 Agilent Zorbax SB-C18( mm, 5 μm, Agilent Technologies, Santa Clara, CA, USA) 를사용하였고, 이동상용매는 positive mode에서 0.1% formic acid containing water와 0.1% formic acid containing acetonitrile을시간에따라 gradient 로조절하였다. 이동상의속도는 0.7 ml/min, 시료주입량은 10 μl, scan type은 SRM mode에서분석을실시하였다. SAC 표준물질을시료와동일한조건에서분석하여머무름시간을비교해확인하였으며, 농도별검량곡선으로부터그함량을산출하였다 ; 32(1):16-26

3 18 심혜진 서원택 최명효 김경화 신정혜 강민정 Korean J Food Cook Sci 5. 유기산함량분석 각각의시료를 filter paper 로여과한후 0.45 μm membrane filter 로재여과하여 HPLC-DAD(Agilent 1260 infinity, Agilent, Santa Clara, CA, USA) 로분석하였다. Analytical column 은 Watchers 120 ODS-BP( mm, 5 μm, Daiso Chemical Co., Tokyo, Japan) 를사용하였고, 0.1% H 3PO 4 수용액을이동상으로하여 30 C 에서 30 분간분석하였다. 이동상의속도는 0.5 ml/min, 시료주입량은 10 μl 로하였으며 DAD(Diode Array Detector) 로 210 nm 에서검출하였다. 총 11 종의유기산 (citric acid, oxalic acid, tartaric acid, formic acid, malic acid, glutaric acid, lactic acid, acetic acid, fumaric acid, succinic acid, propionic acid) 표준물질을시료와동일한조건에서분석하여머무름시간을비교해확인하였으며, 각각의검량곡선으로부터그함량을산출하였다. 6. 무기물함량분석 무기물은 Lee SJ 등 (2010) 의방법에따라분해용플라스크에시료 1 g 을취하여진한황산 (Duksan, Ansan, Korea) 과진한질산 (Duksan, Ansan, Korea) 을각각 10 ml 씩차례로가한다음 heating block 에서무색으로변할때까지분해하였다. 분해하고남은여액에증류수를가해 50 ml 로정용한것을여과한후 ICP(Inductively Coupled Plasma, Optima 7300DV, Perkin-Elmer Co., Norwalk, CO, USA) 로분석하였다. 이때, RF generator 는 MHz, RF power 는 1300 W, plasma argon 15 L/min, auxiliary argon flow rate 0.5 L/min, nebulizer argon flow rate 는 0.8 L/min, sample up take 는 1.5 ml/min 으로하였다. 7. 항산화활성측정 숙성이완료된 25 일차시료를여과지 (Advantec) 로여과한여액을희석하여 mg/ml 의농도가되도록조정하여항산화활성측정용시료액으로사용하였다. DPPH(1,1-Diphenyl-2-picrylhydrazyl) 라디칼소거활성은 DPPH 에대한전자공여활성으로나타낸것으로시료액과 DPPH 용액 (5 mg/100 ml methanol) 을동량으로혼합한다음실온에서 20 분간반응시킨후분광광도계 (Libra S 35, Biochrom, Cambridge, England) 를이용하여 525 nm 에서흡광도를측정하였다 (Blois MS 1958). ABTS(2,2-azinobis-3-ethylbenzo-thiazoline-6-sulphonate) 라디칼소거활성은 7 mm 의 ABTS 용액에 potassium persulfate 를 2.4 mm 이되도록용해시킨다음암실에서 시간동안반응시킨후 415 nm 에서흡광도가 1.5 가되도록증류수로조정한 ABTS 용액을사용하였다. ABTS 용액에동량의시료액을혼합하고실온에서 1 분간반응시킨다음분광광도계 (Biochrom) 를이용하여 415 nm 에서흡광도를측정하였다 (Re R 등 1999). DPPH 및 ABTS 라디칼소거활성은시료무첨가구에대한시료첨가구의흡광도비로계산하여 % 로나타내었다. 8. 통계처리 모든실험은 3 회이상반복하여실시하였으며실험으로부터얻은결과는 SPSS 12.0(IBM, Armonk, NY, USA) 을사용하여분석하였다. 결과치는실험군당평균 ± 표준편차로표시하였고, 통계적유의성검정은일원배치분산분석 (one-way analysis of variance) 을한후 p<0.05 수준에서 Duncan's multiple range test 를시행하였다. 동일한농도내에시료간의유의차는 Student t-test 를통해 p< 0.05 수준에서검증하였다. Ⅲ. 결과및고찰 1. ph의변화흑마늘의첨가량을달리하여제조한흑마늘식초의발효중 ph 변화는 Table 1과같다. 알코올발효직후흑마늘식초의 ph는 의범위로흑마늘의첨가농도에따른유의차가없었는데, 흑마늘발효주의 ph도흑 Table 1. Changes in ph of vinegar added with different levels of black garlic during fermentation period Fermentation period (days) BG3 4.54±0.03 e1) 4.12±0.08 d 4.01±0.08 ca2) 3.94±0.11 bca 3.90±0.07 ba 3.81±0.02 abc 3.82±0.01 ad 3.81±0.01 ab BG6 4.52±0.03 e 4.15±0.09 d 4.02±0.07 ca 3.98±0.08 bcab 3.94±0.07 bab 3.72±0.01 aa 3.67±0.01 aa 3.66±0.01 aa BG9 4.56±0.07 f 4.25±0.09 e 4.11±0.09 dab 4.03±0.07 cab 3.99±0.05 cab 3.78±0.02 bb 3.72±0.02 abb 3.67±0.03 aa BG ±0.10 f 4.25±0.09 e 4.15±0.11 db 4.06±0.07 cdb 4.02±0.06 cb 3.84±0.03 bc 3.75±0.01 ac 3.67±0.02 aa 1) a-f Means with different superscripts within the same row are significantly different (p<0.05). 2) A-D Means with different superscripts within the same column are significantly different (p<0.05). 2016; 32(1):

4 Korean J Food Cook Sci 흑마늘의첨가량을달리한식초의품질특성 19 마늘농도와관계없이대부분 ph 4.5 이하로유지되었다는보고 (Lee HH 등 2010) 는본연구와도동일한경향이었다. 흑마늘식초의발효기간에따른 ph 는발효가진행될수록감소하는경향을보였으며발효초기 ph 의감소폭이컸는데이는으름어린잎식초 (Kwon WY 등 2014) 와아로니아식초 (Park HJ 등 2014) 의경우와동일하게초산발효가진행됨에따라초산과같은유기산의증가로 ph 가감소하였기때문으로생각된다. ph 의감소속도는흑마늘의첨가량에따라다소차이가있어발효 6 일이후부터흑마늘의첨가량이가장적은 BG12 군은흑마늘첨가량이가장많은 BG3 군에비해유의적으로 ph 가높았다. 발효가완료된 25 일에는 BG3 군만이 3.81 로유의적으로 ph 가높았고, 여타실험군에서는서로유의적인차이가없었다. Na HS 등 (2013) 은원료가다른시판발효식초의 ph 를측정한결과감식초 (3.60), 무화과및양조식초 (3.37), 쌀식초 (2.62), 사과식초 (2.54), 현미식초 (2.53), 매실식초 (2.39) 순으로서로상이하였는데, 이는식초제조에사용된원료에따른차이라고보고한바있다. 2. 산도의변화 흑마늘식초의발효기간에따른산도변화를분석한결과는 Table 2 와같으며흑마늘의첨가량이많을수록, 발효기간이경과할수록산도는유의적으로증가하는경향을보였다. 발효초기흑마늘의첨가량이많을수록산도가높았는데이는흑마늘자체가강한산성 (Yang SM 등 2011) 으로산도가높기때문으로생각된다. 발효초기산도는 % 이던것이발효 25 일에는 % 로발효기간의경과와더불어지속적으로유의차를보이면서증가하였는데, 이는초산발효과정중초산균이알코올을영양원이나발효기질로사용하여초산을포함한유기산을생성시키고초산균의증식과더불어유기산의함량이점차증가하였기때문으로 (Lee EK 등 2014) 사료된다. 흑마늘식초제조시발효기간이경과할수록산도는유의적으로증가하는경향을보였으나 ph 는발효 15 일까지는유의적으로감소하다가그이후부터는유의적인차이를확인할수없어일정기간숙성이후부터는산도의증가가 ph 변화에영향을미치지않았다. 발효기간에따른아로니아식초에서는초산생성에따라 ph 가감소하는경향이었으나비례적으로감소하지는않았으며초산생성량이더높은시료에서 ph 가더높게나타난경우도있었고 (Park HJ 등 2014), 현미식초에서는초산을분해하는과산화가일어나적정산도가감소함에도불구하고 ph 가상승하지않고유지되었다고보고되고있어 (Beak CH 등 2013) 본연구의결과와동일한경향으로식초발효에있어 ph 와산도가발효기간의경과와더불어서로상반되게증가또는감소하지않음을알수있었다. 총산은식초에있어서양조과정중초산균의작용으로생성되는초산이대부분이며이는품질판정에중요한성분의하나로 (Ko EJ 등 1998) 일반적으로국내식초의총산규격은초산으로서 w/v%( 감식초는 2.6 w/v% 이상 ) 으로규정하고있는데 (Ministry of Food and Drug Safety 2015), 본연구결과에서도 20 일이상발효하였을때산도가 % 로식초규격을충족하였다. 식초의산도차이는각식초의품질특성, 첨가하는원료의종류와양, 제조방법및희석도등에따라다양한결과를보이는데 (Jeong YJ 등 1998, Na HS 등 2013) 에탄올과재료의첨가량에따라초산농도를조절하여조미료로식초 (5% 이상 ) 를사용할수도있고, 음료용 (3% 이하 ) 으로사용할수도있어 (Keum JH 1999) 초기산도가높을수록식초의가공및활용범위는더넓어질것으로판단된다. 3. 당도의변화당도는식초의맛과향에영향을주는데 (Jo DJ 등 2014), 흑마늘의첨가량을달리하고설탕을첨가해 14 Brix로조절하여발효시킨흑마늘식초의발효기간에따 Table 2. Changes in acidity of vinegar added with different levels of black garlic during fermentation period (%) Fermentation period (days) BG3 1.22±0.02 a1)c2) 2.37±0.06 bd 3.56±0.00 cd 4.63±0.04 dd 5.35±0.01 ed 6.13±0.05 fd 6.44±0.06 gd 7.04±0.06 hd 1) a-h BG6 0.92±0.04 ab 1.89±0.03 bc 3.07±0.02 cc 4.41±0.02 dc 5.05±0.11 ec 5.85±0.05 fc 7.21±0.02 gc 7.50±0.09 hc BG9 0.81±0.03 aa 1.29±0.03 bb 2.09±0.02 cb 2.96±0.03 db 3.69±0.06 eb 4.27±0.02 fb 5.80±0.04 gb 6.33±0.04 hb BG ±0.03 aa 1.20±0.06 ba 1.80±0.08 ca 2.47±0.03 da 3.08±0.05 ea 4.17±0.03 fa 5.19±0.07 ga 5.87±0.03 ha Means with different superscripts within the same row are significantly different (p<0.05). 2) A-D Means with different superscripts within the same column are significantly different (p<0.05) ; 32(1):16-26

5 20 심혜진 서원택 최명효 김경화 신정혜 강민정 Korean J Food Cook Sci Table 3. Changes in sugar contents of vinegar added with different levels of black garlic during fermentation period ( Brix) Fermentation period (days) BG3 7.50±0.71 b1)c2) 8.50±0.71 dc 8.00±0.00 cc 8.00±0.00 cc 7.00±0.00 ac 7.00±0.00 ac 7.00±0.00 ac 7.00±0.00 ac 1) a-d BG6 6.00±0.00 cb 5.50±0.71 bb 5.00±0.00 ab 5.00±0.00 ab 5.00±0.00 ab 5.00±0.00 ab 5.00±0.00 ab 5.00±0.00 ab BG9 5.00±0.00 NS3)A 5.00±0.00 AB 5.00±0.00 B 5.00±0.00 B 4.00±0.00 A 4.00±0.00 A 4.00±0.00 A 4.00±0.00 A BG ±0.71 A 4.50±0.71 A 4.50±0.71 A 4.50±0.71 A 4.00±0.00 A 4.00±0.00 A 4.00±0.00 A 4.00±0.00 A Means with different superscripts within the same row are significantly different (p<0.05). 2) A-C Means with different superscripts within the same column are significantly different (p<0.05). 3) NS : Not show a significant difference within the same row. 른당도의변화를측정한결과는 Table 3 과같다. 알코올발효전설탕을가하여가용성고형분함량을동일하게조절하였음에도불구하고, 알코올발효직후당도는 Brix 로차이가있었다. 흑마늘의첨가량이높을수록흑마늘식초의당도가높았는데, 흑마늘의농도가높은 BG3 와 BG6 군과농도가낮은 BG9 과 BG12 군에서의당도변화양상이서로차이가있었다. 즉, BG3 군의당도는초산발효 3 일후 8.50 Brix 로일시적으로증가한이후 8.00 Brix 로낮아졌고발효 12 일에 7.00 Brix 로감소한이후부터는차이가없었다. BG9 군과 BG12 군의경우발효 9 일까지는변화가없다가발효 12 일에유의적으로감소하였고, 그이후부터는숙성기간에따른차이가없었다. 초산균은발효시당류보다는알코올을발효기질로사용한다는 Ann YG 등 (1999) 의보고가있는데, 본연구결과발효초기당도에미량변화가있는것은알코올발효이후완전히제거되지않은효모의작용으로당류의일부가분해되기때문으로추정되며, 초산발효가진행되면서발효기질로당류가사용되지않기때문에발효기간의경과에따른차이가없는것으로판단된다. 4. 총폴리페놀화합물함량 폴리페놀성화합물은식물계에널리분포되어있는 2 차대사산물로항산화활성과항암작용을하는생리활성물질로알려져있으며 (Ferreres F 등 2009), 여러가지식품에널리분포되어있어천연항산화제로서의기능을한다 (Chung BH 등 2010). 폴리페놀화합물은과일이나채소에서강하게결합되어있어쉽게흡수될수없는데알코올에서는수용성상태로존재하여체내에흡수가용이해져이용성이증진되고이로인한항산화작용을기대할수있다 (Alonso AM 등 2004, Jo DJ 등 2014). 흑마늘의첨가량을달리하여제조한식초의발효기간에따른총폴리페놀화합물함량을측정한결과는 Table 4 와같다. 초산발효초기흑마늘식초의총폴리페놀화합물함량은흑마늘의첨가량이많을수록더높아 BG3 군의경우 mg/100 ml 이었고, BG12 군에서가장낮은함량으로 mg/100 ml 이었다. 총폴리페놀화합물함량은발효기간의경과와더불어불규칙한증감을보이다가발효 25 일에는 mg/100 ml 의범위로감소하는경향이었고발효초기와동일하게흑마늘의 Table 4. Changes in total polyphenol content of vinegar added with different levels of black garlic during fermentation period (mg/100 ml) Fermentation period (days) BG ±1.18 cdd 64.58±2.18 ed 60.92±0.12 dd 59.81±0.21 cdd 58.25±1.30 bcd 51.71±1.89 ad 57.94±1.09 bcd 56.56±2.56 bd 1) a-e BG ±2.27 bcdc 29.38±0.53 bc 28.75±1.00 abc 32.77±2.62 cdec 33.29±3.95 dec 35.13±0.59 ec 26.60±2.62 ac 30.21±0.24 bcc BG ±1.86 abb 26.75±1.12 cb 20.88±0.59 ab 26.38±1.36 cb 27.13±1.18 cb 30.10±2.39 db 23.21±1.30 bb 27.17±0.71 cb BG ±0.27 cda 17.00±1.00 aa 16.54±1.65 aa 21.08±0.12 da 17.60±1.68 aba 23.67±2.36 ea 20.46±1.94 cda 18.96±0.35 bca Means with different superscripts within the same row are significantly different (p<0.05). 2) A-D Means with different superscripts within the same column are significantly different (p<0.05). 2016; 32(1):

6 Korean J Food Cook Sci 흑마늘의첨가량을달리한식초의품질특성 21 첨가량이많을수록더높게유지되었다. Kim SH 등 (2012) 은시판석류, 블랙베리, 블루베리, 복분자, 선인장, 홍삼, 체리식초의총폴리페놀화합물의함량은 mg/100 ml 의범위로사용된원료의종류, 첨가량및제조방법에따라 2 배이상차이가있다고보고하였는데, 본연구의결과에서도총폴리페놀화합물의함량차이는원료인흑마늘의첨가량에영향을받았음을알수있었다. 식초의경우초산발효과정에서강력한페놀분해및변형으로인해폴리페놀함량이감소하는것으로보고되어있으나 (Andlauer W 등 2000, Jo DJ 등 2014) 본연구결과에서는폴리페놀화합물이초산발효동안불규칙한증감을보이지만일정수준을유지하였다. 이는흑마늘로숙성되면서갈변반응을통해축합 중합과정에참여하고있던페놀화합물들이미생물발효를거치면서분해되어유리되었기때문이며 (Choi DJ 등 2008) 미생물의생육활성도에따라생육환경을적절히유지하기위한분해력이흑마늘의첨가량에따라서로상이하기때문으로추정된다. 5. S-allyl-L-cysteine(SAC) 함량 흑마늘첨가량을달리하여알코올발효한발효물중의 SAC 함량은흑마늘의첨가량에비례하여흑마늘의첨가량이가장많은 BG3 군에서 mg/l 였고, BG6 군에서는 1.69 mg/l 가검출되었으나흑마늘첨가량이적은 BG9 군과 BG12 군에서는 SAC 가검출되지않았다 (Table 5). BG3 군의 SAC 함량은초산발효 25 일까지 mg/l 로통계적인유의차가없이유지되었으며, BG6 군의 SAC 함량은발효 12 일까지유의차가없다가발효 15 일이후부터그함량이증가하기시작해발효 25 일에는 2.20 mg/l 였다. Tak HM 등 (2014b) 은 probiotics 를접종한발효물에서흑마늘의첨가농도가많을수록 SAC 함량도높 았다고보고하였는데이는본연구의결과와도일치하는경향이었다. SAC 는흑마늘에함유되어있는대표적인생리활성성분으로항당뇨, 항산화, 면역증강, 뇌신경세포보호등의활성을지니며 (Amagase H 2006), 동물모델계에서 ajoene, diallyl sulfide 류등과함께여러가지발암원에의해유발되는암발생을억제하며, 지질대사를조절하여혈중콜레스테롤수준을저하시키고, 혈소판활성화저해를경유한혈전생성을억제하는작용이있어결과적으로심혈관계질환에대한예방효과가있다 (Kim KM 등 2001). 본연구를통해 SAC 의함량은초산발효를통해감소하지않음을알수있었는데, 흑마늘을일정농도이상사용하여발효물을제조할경우식초의기능성을강화하는데도움을줄수있을것으로기대된다. 6. 유기산함량흑마늘첨가비율을달리한식초의발효중유기산함량을분석한결과는 Table 6과같다. 흑마늘식초의주요유기산으로 acetic acid의함량이가장많았으며, 이어서 citric acid, lactic acid, succinic acid 및 propionic acid의순이었다. Acetic acid는발효기간이경과함에따라점차그함량이증가하여발효 25일에는 mg/100 ml의범위였다. 미숙감귤과즙의첨가비율을달리하여제조한식초의유기산으로 lactic acid와 acetic acid가 98% 정도를차지한다는 Yi MR 등 (2014) 의보고와복분자식초 (Hong SM 등 2012a) 와참다래식초 (Woo SM 등 2007) 에서주요유기산은 acetic acid라고보고되어있는데본연구에서흑마늘식초의주요유기산도이들의연구와동일한결과였다. 풍미를향상시키는역할을하는 succinic acid 또한 acetic acid와동일한경향으로발효기간의경과와더불어점차증가하여발효 25일에 mg/100 ml의 Table 5. Changes in S-allyl-L-cystenine content of vinegar added with different levels of black garlic during fermentation period (mg/l) 1) Fermentation period (days) BG ±0.82 NS1) 13.29± ± ± ± ± ± ±1.30 BG6 1.69±0.24 a2) 1.88±0.18 a 1.74±0.16 a 1.71±0.07 a 1.81±0.10 a 1.99±0.17 ab 2.00±0.18 ab 2.20±0.17 b BG9 ND 3) ND ND ND ND ND ND ND BG12 ND ND ND ND ND ND ND ND NS: Not significant. 2) a-b Means with different superscripts within the same row are significantly different (p<0.05). 3) ND: not detected. below 0.01 mg/l ; 32(1):16-26

7 22 심혜진 서원택 최명효 김경화 신정혜 강민정 Korean J Food Cook Sci Table 6. Changes in organic acid content of vinegar added with different levels of black garlic during fermentation period (mg/100 ml) 1) a-h Sample code BG3 BG6 BG9 BG12 Fermentation days Lactic acid Acetic acid Citric acid Succinic acid Propionic acid Total ±6.21 g1)c2) ±92.52 ac ±6.14 cd ±12.47 ac 77.09±12.85 ab 5, ±1.90 fd ±33.84 bd ±0.59 bd ±1.24 bc 76.33±5.32 ad 5, ±5.28 ed ±29.37 cd ±5.36 bd ±0.68 cd 76.17±4.15 ad 5, ±1.48 dd ±0.74 dd ±8.64 abd ±0.38 dd 72.07±3.21 ac 5, ±0.54 cd ±7.23 ed ±2.06 ad ±4.26 dd 73.12±4.36 ad 5, ±0.47 bcd ±2.18 fd ±6.18 abd ±0.02 ded 70.49±1.97 ad 6, ±0.54 bd ±20.17 gc ±4.24 bd ±5.54 efd 68.07±0.94 ad 6, ±1.90 ad ±1.59 gc ±3.71 cd ±8.08 fd 65.36±1.03 ad 6, ±9.40 dd ±2.81 ab ±0.40 ec ±12.33 ab 54.26±9.53 bb 3, ±3.83 cb ±6.25 bc ±1.54 dc ±0.23 ab 47.12±0.43 abc 3, ±0.29 bc ±0.04 cc ±1.00 cb ±2.87 bc 45.44±0.00 abc 3, ±0.51 bc ±6.45 dc 93.49±8.59 cb ±4.99 cc 38.34±5.38 ab 4, ±0.54 bc ±0.25 ec 94.16±7.57 cb ±3.38 cc 43.23±0.66 ac 4, ±1.80 bc ±5.25 fc 53.63±1.58 aa ±0.59 cdc 40.89±0.13 ac 5, ±3.20 ac ±20.92 gd 82.04±2.68 bb ±6.06 dec 41.41±0.01 ac 5, ±1.00 ac ±12.40 hd 54.16±0.11 aa ±1.61 ec 45.48±0.30 abc 5, ±4.31 fb ±7.76 aa ±3.93 cb 95.74±2.04 aa 11.15±0.09 aa 2, ±2.35 ec ±3.40 bb ±3.17 bb ±1.77 ba 11.37±0.09 aa 2, ±0.20 db ±2.21 cb ±1.72 abc ±0.25 cb 11.84±0.07 ba 2, ±0.39 cb ±2.12 db ±0.49 abc ±2.57 db 13.17±0.10 ca 3, ±0.16 ab ±0.69 eb ±0.79 ac ±0.16 eb 13.82±0.19 da 3, ±0.41 abb ±1.13 fb ±1.20 dec ±1.84 fb 13.83±0.09 da 3, ±0.38 abb ±0.67 gb ±0.41 cdc ±1.17 eb 14.61±0.16 ea 4, ±1.13 ab ±3.25 hb ±0.13 ec ±0.47 fb 16.14±0.01 fa 5, ±0.42 ea ±4.67 aa 85.52±0.76 fa 90.80±1.51 aa 20.10±5.19 ba 2, ±1.48 da ±0.04 ba 80.26±1.91 ea ±0.00 ba 22.47±1.26 bcb 2, ±3.17 ca ±7.79 ca 75.89±1.14 da ±1.15 ca 24.36±0.10 bcb 2, ±1.61 ca ±0.73 da 53.51±0.04 aa ±0.16 ea 11.88±0.71 aa 2, ±0.75 ba ±11.97 ea 72.54±1.70 bca ±0.96 dea 26.65±0.32 cb 3, ±0.23 aa ±6.60 fa 70.22±1.32 bb ±1.59 fa 24.01±2.41 bcb 3, ±1.49 aa ±13.40 ga 70.36±0.09 ba ±1.27 da 21.66±0.31 bcb 3, ±1.47 aa ±24.44 ha 74.10±0.97 cdb ±0.43 ga 22.91±3.11 bcb 4,489.6 Means with different superscripts within the same levels of black garlic are significantly different (p<0.05). 2) A-D Means with different superscripts within the same fermentation days are significantly different (p<0.05). 2016; 32(1):

8 Korean J Food Cook Sci 흑마늘의첨가량을달리한식초의품질특성 23 범위였으며흑마늘의첨가량이많을수록그함량이더높았다. 식초발효에있어서군냄새의원인이되는 (Jeong YJ & Lee MH 2000) lactic acid 의경우발효됨에따라감소하는경향으로발효전과비교하여발효 25 일차의 lactic acid 잔존율은 BG3 군에서 76.5% 인반면 BG6, BG9 및 BG12 군은각각 17.1%, 16.2% 및 11.46% 로흑마늘의첨가량이적을수록잔존율도낮았다. 초산발효시균주사멸기동안공급되는영양분이불충분할경우 acetic acid 가아닌부산물로써 lactic acid 가생성되거나 (Woo CH 등 2000), 발효초기단계에서젖산균이생육하여 lactic acid 를생성한다는보고 (Yoon SR 등 2010) 가있는데, 흑마늘을첨가하여숙성한식초에서숙성과더불어 lactic acid 함량이감소하는것으로보아발효초기에는젖산균에의해 lactic acid 가생성되었으나발효기간의경과와더불어정상적인초산발효가유도됨으로써점차 lactic acid 가감소된것으로추정된다. 7. 무기물함량 발효가완료된흑마늘식초의무기물함량을분석한결과는 Table 7 과같이, 흑마늘의첨가량이많을수록총량도많아 BG3 군에서총 2, mg/l 가정량되었으나 BG12 군에서는 mg/l 로정량되어약 25% 수준에불과하였다. 가장함량이높은 K 의경우에도흑마늘의첨가량에영향을받아 BG3 군에서가장함량이높아 1, mg/l 였고, 전체무기물의 68% 를차지하고있었는데그외시료에서도 K 이전체무기물중 % 를점유하고있었다. 다음으로함량이높았던 P 의경우도동일한경향이었고전체무기물의 % 를차지하여 K 과 P 이흑마늘식초중의주된무기물임을알수있었다. 흑마늘식초중의무기물은원료인흑마늘에서기인하는것으로마늘의무기물은 K 과 P 이가장많이함유되어있고이들이전체무기물의약 90% 정도를차지하며, 그외 Mg, Ca, Na 등이검출된다는 Kim BM 등 (2009) 의보 고와일치하는결과였다. 식초에서 K 의함량은발아현미식초는 mg/l(joo KH 등 2009), 복분자식초에서는 1, mg/l (Hong SM 등 2012a), 오이식초에서는 1, mg/l(hong SM 등 2012b) 로정량되어식초의주무기물이며, 그외의미량성분은식초제조시첨가된원료들에따라달라진다고보고되어있다 (Jeong YJ 등 1996). 8. 항산화활성 DPPH 라디칼소거활성은아스코르빈산및토코페롤, polyhydroxy 방향족화합물, 방향족아민류에의해전자나수소를받아불가역적으로안정한분자를형성하고환원되어짐에따라짙은자색이탈색되는원리이며 ABTS 라디칼소거능은 potassium persulfate와의반응으로생성된 ABTS + 자유라디칼이시료내의항산화물질로부터수소를제공받아안정한물질로변화되면서라디칼특유의푸른색을잃게되는성질을이용한것으로, 라디칼의종류에따라결합하는페놀물질의종류가다르기때문에 DPPH 및 ABTS 라디칼의소거활성은차이가난다고보고되어있다 (Chung BH 등 2010, Hong SM 등 2012a). 흑마늘의첨가량을달리하고보당하여생산되는알코올농도를동일하게조정한다음 25일간초산발효하여제조한식초의항산화활성을 DPPH 및 ABTS 라디칼소거능을통해측정하였다 (Table 8). 흑마늘의첨가비율이높을수록항산화활성이더높았고, DPPH보다는 ABTS 라디칼소거활성이더우수하여활성의절대값이높았다. 흑마늘의첨가량이가장많았던 BG3군은 100 mg/ml 농도로첨가되었을때 DPPH와 ABTS 라디칼소거활성이각각 90.56% 와 98.98% 로가장높았고흑마늘의첨가량이가장적은 BG12군의경우동일한농도에서라디칼소거활성은각각 47.85% 와 54.06% 에불과하였다. 25일간숙성된흑마늘식초의 DPPH 및 ABTS 라디칼소거활성을 IC 50 값으로환산한결과는 Table 9와같다. 흑마늘의첨가비율이높을수록 IC 50 값은더낮았으며, 흑마 Table 7. Mineral content of 25 days fermented vinegar added with different levels of black garlic (mg/l) 1) A-D Minerals K Mg Zn P Na Ca Mn Total BG ±16.5 D1) ±0.96 D 2.18±0.09 D ±8.25 D 34.60±0.82 C 47.91±3.12 D 0.90±0.02 D BG ±9.08 C 56.41±0.92 C 0.22±0.01 C ±1.18 C 23.75±2.82 B 23.84±3.61 C 0.33±0.00 C BG ±21.55 B 43.80±1.25 B ND 2) ±7.37 B 15.52±0.39 A 9.96±1.41 A 0.16±0.02 B BG ±9.19 A 33.70±0.87 A ND ±0.92 A 19.62±7.85 AB 16.33±3.26 B 0.05±0.03 A Means with different superscripts within the same column are significantly different (p<0.05). 2) ND: means not detected ; 32(1):16-26

9 24 심혜진 서원택 최명효 김경화 신정혜 강민정 Korean J Food Cook Sci Table 8. Antioxidant activities of 25 days fermented vinegar added with different levels of black garlic 1) a-d Items DPPH radical scavenging ability (%) ABTS radical scavenging ability (%) Concentration (mg/ml) BG3 BG6 BG9 BG ±3.32 Ac1)C2) 9.69±0.60 Aa 20.66±1.83 Ab 20.75±3.38 Ab ±3.89 Bc 15.22±1.77 Ba 21.77±0.27 Ab 22.55±4.23 Ab ±1.93 Cb 26.75±1.30 Ca 26.85±3.10 Ba 28.49±2.84 Ba ±1.17 Dc 38.91±1.26 Db 35.15±1.23 Ca 34.14±3.00 Ca ±0.03 Ed 60.17±2.31 Ec 54.11±0.98 Db 47.85±0.98 Da ±0.29 Ad 17.09±0.12 Ac 13.73±0.61 Ab 10.74±2.54 Aa ±0.04 Bd 25.25±0.33 Bc 19.18±0.82 Bb 16.07±0.41 Ba ±0.29 Cd 37.05±0.25 Cc 26.84±0.78 Cb 21.15±0.41 Ca ±1.02 Dd 55.49±0.08 Dc 42.62±0.08 Db 30.45±3.07 Da ±0.04 Ed 81.84±0.29 Ec 66.97±0.49 Eb 54.06±0.37 Ea Means with different superscripts within the same levels of black garlic are significantly different (p<0.05). 2) A-E Means with different superscripts within the different concentration are significantly different (p<0.05). Table 9. IC 50 value of 25 days fermented vinegar added with different levels of black garlic (mg/ml) Items BG3 BG6 BG9 BG12 DPPH radical scavenging activity ABTS radical scavenging activity 늘식초는 DPPH 라디칼에비해 ABTS 라디칼소거에더효과가있었는데, BG3 군의 ABTS 라디칼소거능에대한 IC 50 값은 mg/ml 였다. DPPH 라디칼소거활성에대한 BG6 군의 IC 50 값은 BG3 군에비해약 4.2 배나더높았으나, BG9 군과는대차를나타내지않아흑마늘의첨가비율이낮아짐에비례적으로 IC 50 값이 배까지증가하는 ABTS 라디칼소거능과는차이가있었다. Ⅳ. 요약및결론 흑마늘과물을 1:2(BG3), 1:5(BG6), 1:8(BG9) 및 1:11 (BG12) 의비율 (W/W) 로혼합하여균질화한후설탕을가해고형분함량을 14 Brix 로동일하게조절하고, 7 일간알코올발효시킨후 Acetobacter pasterianus 균을접종하여초산발효시키면서발효 0, 3, 6, 9, 12, 15, 20 및 25 일에시료를취하여품질특성을분석하였다. 발효기간이경과함에따라 ph 는유의적으로감소하였고산도는유의적으로증가하는경향을보였다. 알코올발효직후당도 는 Brix 로차이가있었으며흑마늘의첨가량이많을수록당도도높았으나발효 12 일이후부터는발효기간에따른유의적인차이가없었다. 총폴리페놀화합물함량은초산발효초기에흑마늘의첨가량이많을수록더높았고발효기간의경과와더불어불규칙한증감을보이다가발효 25 일에는 mg/100 ml 의범위였다. 흑마늘식초의유기산으로는 acetic acid 의함량이가장높았으며, S-allyl cysteine 은흑마늘의첨가비율이높을수록더높아 BG3 군에서는 mg/l, BG6 군에서는 mg/l 의범위였고, 여타실험군에서는검출되지않았다. 발효완료된식초의무기물은 K 의함량이가장높아전체무기물의 61-68% 를차지하였으며, 흑마늘의첨가비율이높을수록 DPPH 및 ABTS 라디칼소거활성이더우수하였다. 이상의결과로부터흑마늘을 17% 이상사용하여식초를제조할경우유기산, SAC 함량및항산화활성이증가하여식초의풍미와기능성을강화하는데도움을줄수있을것으로기대된다. Conflict of Interest No potential conflict of interest relevant to this article was reported. Acknowledgements This study was by a grant (Grant No. R ) from the Regional Specialized Industry Development Technology 2016; 32(1):

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