송절편을 첨가한 송이주의 향기 성분
윤정아1, 신인웅1, 박은희1, 이하연1,2, 김명동1,3*
1강원대학교바이오산업공학부
2강원도농업기술원농식품연구소
3강원대학교누룩연구소
Received: March 25, 2019 / Revised: June 29, 2019 / Accepted: July 8, 2019
송이버섯
(Tricholoma matsutake)
은한국을비롯한동아 시아지역의소나무숲에서자생하며,
담황색표면을갖는 식용버섯으로서비타민B,
칼슘,
철분등의무기질이풍부한 식품이다[1, 2].
항암효과[3],
항산화효과[4, 5],
면역증강[6]
등의다양한생리활성이보고되었으며
,
권등[7]
은송이즙의 결장암세포에대한생육억제효과를보고한바있다.
또한,
송이버섯균사체추출물은
tyrosinase
효소에대한억제활성이우수하고멜라닌생성을감소시키는것으로보고되었 다
[8].
송이버섯은맛,
향기,
식감이뛰어나버섯중에서도으 뜸으로평가되는우리나라전통고급기호식품으로서,
최근인공재배기술이개발되어생산량증대가기대되고있다
[9].
송이버섯의특징적인향기성분은
1-octen-3-ol
과trans- methyl cinnamate
로알려져있으며, 3-octanone, 3-octanol,
β
-fenchyl alcohol
등도송이버섯의품질에영향을미치는주요성분으로알려져있다
[10].
송이버섯의향기성분은생산지역
,
부위등에따라서함량이다르며,
완전히전개된송이 버섯의갓부분에서는trans-methyl cinnamate
함량이가장 높은것으로보고되었다[11].
송이버섯고유의향기특성에 대한소비자들의선호도가높아,
최근가공제품들이다양하 게개발되었으나,
가공공정을거치면서송이버섯고유의향기성분이급격히감소하는문제점이있다
[12].
소나무
(Pinus denisflora, pine tree)
는우리나라 전역에 분포하고있는침엽수로서솔잎,
솔방울,
꽃가루,
송진등대부분의부위가식용으로이용되고있다
[13].
솔잎의항산화[14],
항비만[14],
면역력증진[15]
등의생리활성효능과솔 잎가공품의향미특성에대한연구결과가보고되었으며[16],
목질부에탄올추출물의항균효과
[17]
및줄기추출물의충치억제활성
[13]
도보고되었다.
본연구에서는송이버섯이첨가된약주를제작한후
,
송절 편첨가와숙성기간에따른향기특성을조사하였다. Flavor Compounds in Pine Mushroom Liquor Added with Pine Tree Chips
Jeong-Ah Yoon
1, In-Ung Shin
1, Eun-Hee Park
1, Ha-Yeon Lee
1,2, and Myoung-Dong Kim
1,3*
1
Division of Food Biotechnology and Biosystems Engineering, Kangwon National University, Chuncheon 24341, Republic of Korea
2
Agro-Food Research Institute, Gangwon Agricultural Research and Extension Services, Chuncheon 24203, Republic of Korea
3
Institute of Fermentation and Brewing, Kangwon National University, Chuncheon 24341, Republic of Korea
Changes in flavor compounds in pine mushroom ( Tricholoma matsutake) liquor added with pine tree chips were analyzed using gas chromatography/mass spectrometry. While three flavor compounds were detected in the control, fifteen were detected in the pine mushroom liquor added with pine tree chips. After eight- weeks of aging, the relative concentrations of β-fenchyl alcohol, 2-octanol, and methyl cinnamate, which are distinctive flavor characteristics of the pine mushroom, increased by 67.57%, 2.14%, and 0.94%, respec- tively, when pine tree chips were added (5%). Principal component analysis revealed that although flavor characteristics of the pine mushroom liquor were affected by the increased production of β-fenchyl alcohol due to the addition of pine tree chips, the aging time exerted a greater influence on flavor.
Keywords: Pine mushroom liquor, pine tree chip, flavor compound, GC-MS, aging
*Corresponding author
Tel: +82-33-250-6458, Fax: +82-33-259-5565 E-mail: [email protected]
© 2020, The Korean Society for Microbiology and Biotechnology
2018
년10
월강원도양양군에서수확한송이버섯은불순 물을제거한후냉동보관하였으며,
상온에서해동한후분쇄기
(
한일산업, Korea)
를사용하여분쇄하였다.
수돗물로2
회세척한쌀80 kg
을분쇄하고80
℃에서60
분간증자하 였으며,
상온에서냉각한후종국(
충무발효, Korea) 200 g
을 첨가하여입국을 제조하였다.
물14 L,
탁주 제조용효모(Saccharomyces coreanus,
충무발효) 100 g
을 첨가하고25
℃에서4
일간발효하여밑술을제조하였다.
제조된밑술 에입국70 kg,
물100 L
를첨가하고25
℃에서48
시간발효 하여1
단담금을하였으며,
분쇄한쌀240 kg,
누룩(
송학곡 자, Korea) 4 kg,
물496 L,
분쇄송이버섯1 kg
을첨가하고25
℃에서3
일간발효하여2
단담금을하였다.
여과지(mixed cellulose ester filter, HM, Korea)
를사용하여여과한발효 액에1 cm
2크기로절단한송절편(
천년약초, Korea)
을첨가 하여10
℃에서8
주간숙성하였다.
숙성이완료된시료는원 심분리(5,867 × g, 20
분)
하여상등액을회수한후,
여과지를 사용하여여과하였다.
회수한시료
5 ml
를용기(Supelco, USA)
에넣고밀봉한 후SPME fiber (50/30
µm DVB/CAR/PDMW, Supelco)
에30
분동안흡착시켰다.
흡착된향기성분을250
℃에서3
분 간열탈착한후DB-5MS (30 m × 0.32 mm, Agilent, USA)
컬럼과질량검출기
(5975C, Agilent)
가연결된기체크로마토그래프
(7890A, Agilent)
를사용하여분석하였다.
주입구와 컬럼의온도는각각250
℃와280
℃으로설정하였고,
이동상 으로1.0 ml/min
유속의헬륨(He)
가스를5:1
의분할비율(split ratio)
로유지하였다.
Box-Whisker’s
도표[18]
는XLSTAT (Addinsoft, France)
을사용하여작성하였으며, SIMCA (version 14, Umetrics, Sweden)
를 사용하여 주성분 분석(Principal Component Analysis, PCA)
을하였다.
모든측정은3
회반복하였으며,
통 계분석은SigmaPlot (version 11, SPSS Inc., USA)
을이용 하여 평균값 및표준오차를 계상하였다. SPSS Statistics (SPSS Inc.)
를사용하여Duncan
의다중범위검증[19]
을실 시하였다.
송절편을첨가한송이주의휘발성성분을분석한결과총
15
종류의향기성분이검출되었다(Table 1).
송절편을첨 가하지 않은 대조구 송이주에서는3-methyl-1-butanol, benzaldehyde, 2-phenylethanol
등의향기성분이동정되 었으나, 2-octanol,
β-fenchyl alcohol
및methyl cinnamate
와같은송이버섯특유의향은검출되지않았다
.
또한ethyl
acetate
와cinnamaldehyde
는송절편을첨가하지않은대조 구송이주에서검출되지않았으며,
송절편을첨가한경우는Table 1. Volatile compounds in pine mushroom liquor added with pine tree chip.
(Relative peak area, %)
Compound Odor Source
Reten- tion time (min)
Aging time (week)
0 2 4 6 8
Control 5% 10% Control 5% 10% Control 5% 10% Control 5% 10% Control 5% 10%
Ethyl acetate Ethereal PTC 02:32 ND 0.22 0.31 ND 0.20 0.17 ND 0.30 0.16 ND 0.23 0.24 ND 0.22 0.21 3-Methyl-1-butanol Fruity PML
(Nuruk, Mushroom)
03:91 1.97 3.25 3.53 2.71 3.25 1.57 0.96 0.32 2.78 2.67 2.23 1.18 2.59 2.30 1.52
2-Methyl-1-butanol Roasted PTC 03:97 ND 1.80 1.80 ND 1.13 0.82 ND 0.72 0.72 ND 0.23 0.60 ND 0.20 0.38 Benzaldehyde Sweet PML, PTC 08:03 1.41 3.98 3.97 1.94 3.69 6.11 1.41 4.82 6.50 4.03 4.97 6.70 4.47 5.00 7.14 2-Octanol Fresh PTC 08:61 ND 0.38 0.38 ND 0.67 1.23 ND 1.63 1.58 ND 1.64 1.81 ND 2.14 1.89
m-Tolualdehyde Sweet PTC 10:12 ND 0.47 0.47 ND 0.61 0.65 ND ND ND ND ND ND ND ND ND
2-Phenylethanol Floral PML (Nuruk)
10:63 96.62 83.75 83.42 95.35 51.33 34.93 97.63 41.75 23.23 93.30 27.65 23.57 92.94 19.69 17.00
Diethyl succinate Fruity PTC 11:52 ND 0.56 0.55 ND 0.56 0.78 ND 1.06 1.32 ND 1.41 2.47 ND 1.56 2.21
Ethyl octanoate Fruity PTC 11:78 ND 0.58 0.58 ND ND ND ND ND ND ND ND ND ND ND ND
β-Fenchyl alcohol Camphor PTC 11:89 ND ND ND ND 35.09 51.36 ND 46.79 61.30 ND 59.80 61.36 ND 67.24 67.57 2-Phenylacetic acid Sweet PTC 12:51 ND 0.42 0.42 ND 0.44 0.40 ND 0.37 0.27 ND 0.21 0.27 ND 0.11 0.07 Phenylethyl acetate Floral PTC 12:00 ND 2.78 2.77 ND 1.80 1.37 ND 0.87 1.09 ND 0.50 0.55 ND 0.26 0.34 Cinnamaldehyde Sweet PTC 13:00 ND 0.38 0.38 ND 0.40 0.33 ND 0.39 0.42 ND 0.31 0.47 ND 0.34 0.74 Methyl cinnamate Sweet PTC 14:54 ND 0.76 0.75 ND 0.83 0.28 ND 0.98 0.63 ND 0.82 0.78 ND 0.94 0.93
Ethyl palmitate Waxy PTC 22:78 ND 0.67 0.67 ND ND ND ND ND ND ND ND ND ND ND ND
ND: Not detected
PTC: Pine tree chip
PML: Pine mushroom liquor
Fig. 1. Box-and-whisker’s plot of volatile compounds of which relative concentration increase in pine mushroom liquor added
with pine tree chip. Relative peak area for each compound in the given sample was shown with average and standard error deter-
mined from three independent measurements. Pine mushroom liquors were stored at 10 ℃ for 8 weeks.
숙성기간동안유사한수준의상대적함량을유지하였다
.
대조구송이주에서송이버섯고유의향이검출되지않은것 은송이주제조과정에서향기성분이손실된것으로판단되 며,
송이버섯의첨가량,
시기,
부재료등에대한고려가필요 할것으로사료된다.
달콤한 향을 나타내는
benzaldehyde [20]
및methyl cinnamate [21],
과일향을나타내는diethyl succinate [22]
는송절편을첨가하였을때숙성기간이경과함에따라증
가하는경향을나타냈다
. Benzaldehyde
는송절편을첨가하지않은대조구송이주를
8
주동안숙성하였을때숙성초기보다약
3
배높은함량을나타냈으나,
전체휘발성성분의4.47%
수준이었다.
그러나송절편을10%
수준으로첨가한실험구는숙성기간이경과함에따라꾸준히증가하여
8
주 간숙성후7.14%
으로대조구송이주보다약1.6
배높은함 량을나타내었다.
송절편을10%
첨가하여8
주동안숙성한 경우methyl cinnamate
의상대적함량은0.93%
수준이었 지만,
최소감지농도[23]
가낮아송절편을첨가한송이주의향 기에영향을미칠것으로판단되었다.
송절편을 첨가한 실험구에서
3-methyl-1-butanol, 2- methyl-1-butanol, 2-phenylethanol
및2-phenylacetic acid
는Fig. 2. Principle component analysis of volatile compounds in pine mushroom liquor with different content of pine tree chip
(PTC) and aging time. Panel A is score plot ( ★ : pine mushroom liquor, ■ : 5% PTC, two weeks, ▲ : 5% PTC, four weeks, ◆ : 5% PTC,
six weeks, ● : 5% PTC, eight weeks, □ : 10% PTC, two weeks, △ : 10% PTC, four weeks, ◇ : 10% PTC, six weeks, ○ : 10% PTC, eight weeks)
and panel B is loading plot. The loading plot illustrates the flavor components ( ● ) that are responsible for the pattern appears in panel
A. Pine mushroom liquors were stored at 10 ℃ for 8 weeks.
송절편의첨가량과관계없이숙성기간이경과함에따라감 소하는경향을나타냈다
.
장미향을부여하는2-phenylethanol [22, 24]
의경우숙성8
주후에대조구보다약5
배낮은상 대함량을나타내었고ethyl octanoate
와ethyl palmitate
는 송절편의첨가량과관계없이숙성2
주후부터검출되지않 았으며, m-tolualdehyde
는숙성4
주이후에는검출되지않 았다.
송이버섯의 특징적인 향기 성분의 하나인 β
-fenchyl alcohol
은송절편을10%
첨가하였을때,
숙성기간이경과 함에 따라상대적인함량이 지속적으로증가하여 숙성8
주후에는
67.54%
로가장높은비중을차지하는성분으로나타났다
.
송이버섯의주요향기성분으로알려진2-octanol
또한송절편을
10%
첨가하였을때,
숙성기간의경과에따라함량이증가하여
8
주후에는1.89%
의상대적인비율을나타냈다
.
송절편을 첨가하지 않은 대조구에서는2- phenylethanol
의함량이숙성과정동안유지된반면,
송절 편을첨가한송이주에서는2-phenylethanol
함량이감소하 면서이성질체인β-fenchyl alcohol
의함량이증가하는경향 을나타내어송절편의첨가가2-phenylethanol
을β-fenchyl alcohol
로변환시키는데기여하는것으로사료된다.
또한,
β- fenchyl alcohol, 2-octanol
과Methyl cinnamate
는대조구 에서는검출되지않았고,
송절편을첨가한송이주에서검출 되어송절편으로부터유래된것으로판단되었다.
송절편의첨가에의해함량이증가하는
5
점의향기성분 의함량변화를나타냈다(Fig. 1).
과일향을나타내는diethyl succinate
는송절편을5%
첨가하였을때숙성4
주차부터함 량이증가하여8
주차에는1.56%
의비율을나타냈다.
송절편 을10%
수준으로첨가하였을때benzaldehyde
의상대적함 량은숙성2
주후부터증가하여8
주차에는7.14%
의상대적 비율을나타내었으며,
이는5%
의송절편을첨가한실험구에 비해약1.5
배높은수준이었다.
송이버섯의주요향기성분인
2-octanol, methyl cinnamate
의상대적함량은숙성기간이경과함에따라꾸준히증가하 여5%
의 송절편을 첨가하였을 때 숙성8
주 후에는 각각2.14%
와0.94%
의수준으로나타났으나,
송절편의첨가량에의한영향은크지않은것으로나타났다
.
β-Fenchyl alcohol
의경우송절편을첨가한후2
주동안숙성하였을때검출 되었으며,
상대적인함량은숙성기간이경과함에따라지속적으로증가하여숙성
8
주후에는67%
이상의비율을차지하였으나
,
송절편의첨가량에따른차이는미미한것으로나 타났다.
송절편의첨가에의한β-fenchyl alcohol
과2-octanol
의변화를고려하였을때,
송이주의송이버섯향을보완하는 데는송절편의첨가량보다는숙성기간을조절하는것이보 다적합할것으로판단되었다.
주성분분석결과제
1
주성분은97.9%,
제2
주성분은1.9%
의기여율을나타내어총
99.8%
의누적기여율을나타냈다(Fig. 2).
송절편을5%
첨가한송이주의경우PC2
를기준으 로아래쪽에분리되었고, 10%
의송절편을첨가한경우위쪽 에분리되어송절편의첨가량에의하여향기성분의차이가 발생한것으로판단되었다(Fig. 2A).
숙성기간이경과함에 따라PC1
을기준으로우측으로이동하여송절편을첨가하 였을때숙성에의해향기성분이유의적으로변화하는것 을확인하였다.
또한97.9%
의기여율을보였던PC1
에서계 수가가장큰변수는β-fenchyl alcohol
로서송절편의첨가후 숙성기간에따른상대적함량의증가가향기성분의유의적 인차이를유발한것으로판단되었다(Fig. 2B). 1.9%
의기여 율을보였던PC2
에서계수가큰변수는2-phenylethanol
으 로서송절편을첨가한후숙성기간이경과하면서상대적인 함량이유의적으로감소함에따른것으로판단되었다.
즉,
송 절편첨가에의한 β-fenchyl alcohol
함량의증가가송이주의 송이버섯향을유의적으로증진시킨것으로판단된다.
본연구를통하여송절편을첨가한송이주의향기성분변 화에대하여조사하였으며
,
숙성기간동안송이버섯특유의 향기성분이유의적으로증가하는것을확인하였다.
전통주 에가격이저렴한송절편을첨가하여송이버섯특유의향을 부여함으로써전통주의부가가치를증진시킬것으로기대되 었으며,
송절편의첨가시기,
첨가방법등에대한추가연 구가필요할것으로사료된다.
요 약
송이버섯이첨가된전통주를제조한후송절편을첨가하 여첨가량과숙성기간에따른향기성분의변화를기체크 로마토그래피질량분광법을통해조사하였다
.
송절편을첨 가하지않은대조구에서는총3
종의향기성분이검출되었 으나,
송절편을첨가한송이주에서는총15
종의향기성분 이검출되었다.
송절편을5%
첨가한실험구에서송이버섯 특유의향기성분인β-fenchyl alcohol
과2-octanol, methyl
cinnamate
은숙성기간동안상대적인함량이증가하여8
주후에는각각