간장박 가수분해물에서 생성된 반응향 성분의 주성분 분석

차용준(Yong-Jun Cha),왕문봉(Wenfeng Wang),김진현(Jin Hyeon Kim),석화영(Hwayeong Seok) 한국식품영양과학회 2019 한국식품영양과학회지 Vol.48 No.1

간장박 가수분해물로부터 부가성이 있는 소스류를 개발하고자 반응표면분석법의 중심합성계획법에 따라 15개 실험구의 향기성분을 SPME/GC/MSD법으로 분석하여 각 실험구간의 savory odor 및 taste의 특성강도와의 상관성을 PCA법으로 비교하였다. 실험구에서 동정된 향기성분은 총 79종이 동정되었으나, PCA 분석 결과 savory odor에서는 45종, savory taste에서는 43종이 상관성이 있었다. Savory odor에서는 함황화합물(8종), 산류(3종), 알코올류(7종), 알데히드류(9종), 케톤류(5종), 테르펜류(2종), 피라진류(2종), 퓨란류(3종), 페놀류(2종), 에스테르류(3종) 및 기타화합물(1종)의 기여도가 높았다. Savory taste에서의 기여도는 함황화합물류(6종), 알데히드류(10종), 알코올류(6종), 케톤류(5종)을 제외한 나머지 그룹은 savory taste에서 동정된 화합물과 같았다. 이들 화합물을 odor value(OV)로 계산하면 4종의 화합물, 즉 반응향으로부터 생성된 dimethyl trisulfide(OV: 59,783.00, 간장, 삶은 양배추향), 3-methylbutanal(OV: 840.55, 다크초코릿향), methional(OV: 491.10, 간장, 구운 감자향), dimethyl disulfide(OV: 41.95, 마늘, 파향) 등과 같은 화합물이 savory odor 및 taste에 주된 화합물로 관여할 것으로 생각되었다. 또한 동정된 이들 화합물은 중심합성계획법의 fractional point 영역과 잘 일치하는 결과를 보였다. To develop a value added savory sauce from the hydrolysate of soy sauce residue, volatile flavor compounds generated under 15 reaction flavoring conditions designed with response surface methodology were analyzed by Solid Phase Microextraction / Gas Chromatography / Mass Selective Detector. The correlations of the compounds with sensory characteristics (savory odor and taste) were then compared by Principal Component Analysis. A total of 79 flavor compounds were detected, 45 that were correlated in savory odor and 43 that were correlated in savory taste. The compounds correlated in savory odor mainly contained sulfur containing compounds (8), acids (3), alcohols (7), aldehydes (9), ketones (5), terpenes (2), pyrazines (2), furans (3), phenols (2), esters (3), and miscellaneous compound (1). In savory taste, however, except sulfur containing compounds (6), aldehydes (10), alcohols (6), ketones (5), and the other groups were same compounds correlated in savory odor. Based on the odor value (OV) obtained by dividing the contents of each compound by the threshold value, four compounds, dimethyl trisulfide (OV: 59,783.00, soy sauce, cooked cabbage-like), 3-methylbutanal (OV: 840.55, dark chocolate-like), methional (OV: 491.10, soy sauce, baked potato-like), and dimethyl disulfide (OV: 41.95, garlic, green onion-like) formed through reaction flavors were the major compounds with a high contribution of savory odor and taste. These compounds correlated in savory odor and taste also coincided with a fractional point region by central composite design.

풍미소스류 제조를 위한 간장박 효소가수분해물의 최적화

차용준(Yong-Jun Cha),왕문봉(Wenfeng Wang) 한국식품영양과학회 2017 한국식품영양과학회지 Vol.46 No.12

양조간장 가공부산물인 간장박을 부가성이 높은 소재로 재활용하기 위해 단백질 분해효소를 이용하여 효소가수분해물의 최적 조건을 규명하였다. 반응표면분석법을 통하여 얻어진 가수분해율(%)은 37.789+2.833[S]+2.811[E/S]+1.895[S]²+3.733[S][Time]과 같은 식을 얻을 수 있었다. 그러나 반응 모형식에서 얻어진 정상점(stationary point)은 안장점(saddle point)을 나타내고 있어, 능선분석(ridge analysis)을 통하여 반경(radius) 1.0에서의 예측치는 43.83±(1.59)2%의 가수분해율을 나타내었다. 이 조건 값에서 실제 실험을 한 결과 41.86±1.30%의 값을 얻어 예측치보다는 약간 낮은 가수분해율을 얻었다. 이러한 최적의 가수분해 조건은 기질농도=8.79%(w/v; 간장박 무게/증류수), 기질에 대한 효소농도[E/S]=0.43%(w/v, Flavourzyme<SUP>TM</SUP> 500 MG: Protamex<SUP>Ⓡ</SUP>=1:1 ratio), 반응시간[Time]=4.43시간으로 나타났다. 간장박의 유리아미노산 함량은 2,764.51 mg%(건물량 기준: 4,137.87 mg%)에서 효소가수분해 후에는 570.86 mg%(건물량 기준: 23,205.77 mg%)로 건물량 기준으로 5.6배가 증가하였다. This study was performed to determine the optimal hydrolysis conditions for production of soy flavoring from soy sauce residue (SSR) as a by-product of soy sauce with commercial proteases. Using three variables (substrate concentration, enzyme/substrate ratio, reaction time), response surface methodology (RSM) based on a five level central composite design was applied to evaluate the degree of hydrolysis as the dependent variables. A model equation obtained from RSM showed an R-square value of 0.81 with a lack of fit of 0.10 (P<0.05). Optimal hydrolysis conditions for making SSR hydrolysate were obtained as follows: 8.79% (w/v) substrate concentration (pH adjusted to 7.0), 2 h reaction time with 0.4% (v/w) of Alcalase<SUP>TM</SUP> 2.4 L, followed by 0.43% (w/w) Protamex<SUP>®</SUP> plus Flavourzyme<SUP>TM</SUP> 500 MG (1:1 ratio), and a reaction time of 4.43 h. The hydrolysis ratio obtained under these optimal conditions was 41.86%, which was lower than the predicted value (43.83%). The total amount of free amino acids in the hydrolysate of SSR was 5.6 times higher than that of SSR on a dry basis.

반응향을 적용한 간장박 가수분해물로부터 Savory Flavor의 생성

차용준(Yong-Jun Cha),왕문봉(Wenfeng Wang) 한국식품영양과학회 2018 한국식품영양과학회지 Vol.47 No.2

간장박 가수분해물에 0.5%의 fructose와 0.33%(w/v)의 glutamic acid, proline 0.99%(w/v), methionine 0.42%(w/v) 및 glycine 0.41%(w/v)를 넣고 93°C에서 120분간 반응향을 유도한 가수분해물(RFT)을 대조구(Control)와 함께 휘발성 향기성분을 분석한 결과, 총 82종의 휘발성 성분이 검출 동정(RFT에서 68종, 대조구에서 59종)되었으며, 방향족화합물(15종), 알데히드 및 케톤화합물(12종), 산류(9종), 알코올류(11종), 에스터류(9종), 퓨란류(9종), 질소 및 황함유화합물류(13종) 및 기타화합물류(4종)로 구성되었다. 퓨란류가 함량면에서는 가장 많았으며(Control: 1,466.38 ng/g, RFT: 1,011.29 ng/g) 반응향을 통하여 31% 정도 감소하였다. 질소 및 황함유화합물은 반응향을 통하여 65.7배 증가하였다(P<0.05)(Control: 7.86 ng/g, RFT: 516.47 ng). 방향족화합물 및 산류의 함량은 반응향을 통하여 유의하게 감소하였고(P<0.05), 알데히드류는 증가하였다. 특히 3종의 함황화합물인 dimethyl disulfide(상한 양파, sour), dimethyl trisulfide(간장, 조리한 양배추) 및 methional(간장 및 구은 감자향)과 3-methylbutanal 등은 각각 12, 0.01, 0.2 및 0.2ng/g의 매우 낮은 역치로 인하여 반응향을 통하여 생성된 가수분해물의 savory flavor에 크게 관여할 것으로 생각되었다. Reaction flavored sauce (RFT) was made from hydrolysate of soy sauce residue (Control) by adding 0.5% fructose, 0.33% glutamic acid, 0.99% proline, 0.42% methionine, and 0.41% (w/v) glycine into Control for 120 min at 93°C. The volatile flavor compounds were compared between RFT and Control using solid phase microextraction/gas chromatography/mass selective detector (SPME/GC/MSD). A total of 82 compounds were detected in samples (68 RFT, 59 Control), which were composed of aromatic compounds (15), aldehydes and ketones (12), acids (9), alcohols (11), esters (9), N- and S-containing compounds (13), and miscellaneous compounds (4). Furans were the most abundant (1,466.38 ng/g in Control, 1,011.29 ng/g in RFT) and decreased by 31% after reaction flavor, whereas N- and S-containing compounds increased 65.7 times through reaction flavor (P<0.05). The amounts of aromatic compounds and acids decreased, whereas aldehydes increased (P<0.05). Particularly, three S-containing compounds, including dimethyl disulfide (rotten onion-like, sour, and 12 ng/g threshold), dimethyl trisulfide (soy sauce-like, cooked cabbage-like, and 0.01 ng/g threshold), and methional (soy sauce, baked potato-like, and 0.2 ng/g threshold) formed through reaction flavor contributed to the savory flavor of RFT.

간장박의 휘발성 향기성분에 관한 연구

차용준(Yong-Jun Cha),왕문봉(Wenfeng Wang),차하람(Ha-Ram Cha) 한국식품영양과학회 2016 한국식품영양과학회지 Vol.45 No.12

간장박 및 그 산가수분해물의 휘발성 향기성분을 SPME/GC/MSD 분석법으로 분석한 결과 총 79종의 화합물이 간장박(66종)과 산가수분해물(60종)에서 동정되었다. 에스테르 및 알코올류가 각각 15종으로 가장 많았고, 알데히드류 11종, 산류 9종, 방향족 화합물류 8종, 퓨란류 8종, 케톤류 7종 및 기타 화합물류 6종이었다. 함량 면에서는 간장박에서 알코올 함량(433.37 ng/g)이 가장 많았으며, 다음으로 알데히드류(273.01 ng/g), 에스테르류(236.80 ng/g) 및 방향족 화합물류(180.66 ng/g) 순이었다. 산가수분해물에서는 퓨란류가 249.27 ng/g으로 가장 많았으며(P<0.05), 알코올을 제외한 나머지 화합물류는 15 ng/g 미만이었다. 간장박에서는 4종의 에스테르류, 3-methylbutyl acetate(바나나/배향), ethyl 3-methyl butanoate(익은 과일향), ethylbenzene acetate(와인향), ethyl 3-methyl butanoate(사과향), 3종의 알코올류, 3-methyl-1-butanol(과일/위스키향), 2-phenylethanol(꽃/달콤한향), 1-octen-3-ol(버섯향), 4종의 알데히드류, (E)-2-phenyl-2-butenal(초코렛향), benzaldehyde(알몬드향), 3-methylbutanal(엿기름향), 2-phenylacetaldehyde(꽃향), 4종의 방향족 화합물류, 4-ethyl-2-methoxyphenol(연기향/간장향), 4-ethylphenol(약품향), 4-vinyl-2-methoxyphenol(나무향), phenol(나무향) 및 2종의 퓨란류, fufural(알몬드향), 4-hydroxy-2,5-dimethyl-3(2H)-furanone(카라멜향)이 지배적이었다. 반면에 산가수분해물에서는 furfural, 5-methylfurfural(알몬드향), 3-methyl-1-butanol, 2-phenylethanol, 4-ethyl-2-methoxyphenol, 3-methylbutanal, benzaldehyde 등의 화합물이 지배적이었다. Volatile flavor compounds in soy sauce residue (SSR) and acid hydrolysate of SSR (AHSSR) were analyzed by solid phase micro extraction (SPME)/gas chromatography (GC)/mass spectrometry (MSD) methods. A total of 79 compounds were detected in samples (66 SSR and 60 AHSSR). Quantitatively, alcohols (433.37 ng/g), aldehydes (273.01 ng/g), esters (236.80 ng/g), and aromatic hydrocarbons (180.66 ng/g) were dominant in the volatiles of SSR, whereas furans (249.27 ng/g) were only dominant in AHSSR (P<0.05). Among these, four esters, 3-methylbutyl acetate (banana/pear-like), ethyl 3-methyl butanoate (fruity), ethylbenzene acetate (wine-like), and ethyl 3-methyl butanoate (apple-like), three alcohols, 3-methyl-1-butanol (fruity/whisky-like), 2-phenylethanol (floral/sweet), and 1-octen-3-ol (mushroom-like), four aldehydes, (E)-2-phenyl-2-butenal (chocolate-like), benzaldehyde (almond-like), 3-methylbutanal (malty), and 2-phenylacetaldehyde (floral), four aromatic hydrocarbons, 4-ethyl-2-methoxyphenol (smoky/soy sauce-like), 4-ethylphenol (medicine-like), 4-vinyl-2-methoxyphenol (woody), and phenol (woody), and two furans, furfural (almond-like) and 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like), were major compounds in SSR, whereas seven compounds, including furfural, 5-methylfurfural (almond-like), 3-methyl-1-butanol, 2-phenylethanol, 4-ethyl-2-methoxyphenol, 3-methylbutanal, and benzaldehyde were major compounds in AHSSR.