著者 : ADRIANA FARAH, TOMAS DE PAULIS, LUIZ C. TRUGO,PETER R. MARTIN
雑誌 : J. Agric. Food Chem. 2005, 53, 1505-1513
紹介者 : 北河 広大
2013.1.18(Fri)
1
Effect of Roasting on the Formation of
Chlorogenic Acid Lactones in Coffee
Introduction
コーヒー
ポリフェノール: クロロゲン酸
アルカロイド: カフェイン
世界で最も多くの国で飲用される嗜好飲料
生豆には多糖類, アミノ酸. タンパク質, 脂質が含まれる
焙煎によって化学変化し, 数百種
類におよぶ成分が焙煎豆に含有
アラビカ種 :コーヒー豆専門店で売っているもので高価
カネフォラ種(ロブスタ種) : インスタントコーヒーの原料で安価
一般的に苦味が強いといわれている
品種
3
Introduction
Quinic acid
O
O
HOOC
OH OH
OH
OH
OH
Caffeic acid(CA)
1 3 4 5 6 2Chlorogenic acids (CGAs)
コーヒー中(5-10%)に含有
O
OH
OH
HO
O
HO
R
COOH
4-caffeoylqunic acid (4-CQA)(R=OH)
4-feruloylqunic acid (4-FQA)(R=OMe)
COOH
OR
3
R
1
O
OR
2
OH
3,4-diCQA (R
1=CA, R
2=CA, R
3=H)
3,5-diCQA (R
1=CA, R
2=H, R
3=CA)
4,5-diCQA (R
1=H , R
2=CA, R
3=CA)
5-caffeoylqunic acid (5-CQA)
Introduction
O
OH
O
HO
O
O
HO
R
Chlorogenic lactones (CGLs)
4-caffeoy-1,5-quinide (4-CQL)(R=OH)
4-p-coumaroyl-1,5-quinide (4-p-CoQL)(R=H)
4-feruloyl-1,5quinide (4-FQL)(R=OMe)
薬理学特性
ラジカル捕捉能による抗酸化作用
鎮痙作用
発がん性物質の変異原性の抑制
焙煎過程でのCGA, CGLの構造決定、定量を行う
コーヒーの苦みの要因と言われている
5
Experimental
HPLC測定
×
Sample : arabica cv. Bourbon; C. arabica cv. Longberry; C. canephora cv. Robusta
Roasting : max. temperature (230ºC) : 0 , 5-15 min
HPLC測定条件
Flow rate : 1.0 mL/min
Detection : UV (325 nm)
Mobile phase :
(A) 10 mM citric acid solution, pH2.5(6N HClで調整) : methanol= 80 : 20
(B) metahnol
Column : ODS-C18 250 × 4.6 mm 5μm
グラジエント法
light roast
(6min)
light medium roast
(7min)
dark roast
(9min)
Experimental
定量方法 ( HPLCのピーク面積を元に、モル吸光係数比較した方法 )
C =
RF ε
1MR
2A
ε
2MR
1C : 求めたい物質の濃度 ( g L
-1)
)RF : 5-CQAのレスポンスファクタ (expressed in g L
-1)
ε
1: 5-CQAのモル吸光係数
ε
2: 求めたい物質のモル吸光係数
MR
1: 5-CQAの分子量
MR
2: 求めたい物質の分子量
A : 求めたい物質のピーク面積
Weight Loss : %WL = 100
WAR × 100
WBR
重量減少率 ( 焙煎中の水の蒸発などによるもの)
WBR : weight before roasting
WAR : weight after roasting
求めたい異性体濃度
7
Results and Discussion
焙煎前
焙煎後
Figure 1. HPLC separation of chlorogenic acids in green C. arabica cv. Bourbon. 1 =3-CQA; 2=3-FQA; 3=5-CQA; 4=4-CQA;
5=5-FQA; 6=4-FQA; 7=3,4-diCQA; 8=3,5-diCQA; and 9=4,5-diCQA. The three major peaks are shown off scale to show minor peaks
Figure 2. HPLC separation of chlorogenic acids and lactones in C. arabica cv. Bourbon roasted to light medium roast after 7min of being roasted at a maximum temperature of 230 ºC. The three major peaks are shown off scale to show the very minor peaks 1=3-CQA; 2=3-FQA; 3=5-CQA; 4=4-CQA; 5=3-CQL; 6-FQA; 7=4-FQA; 8=4-CQL; 9=3-pCoQL;10=3-FQL; 11=4-pCoQL; 12=4-FQL; 13=3,4-diCQA; 14=3,5-diCQA; and 15=4,5-diCQA; and 16=3,4-diCQL.
2 1 3 4 5 6 7 9 10 11 12 13 14 15 16 8 1 2 3 4 5 6 7 8 9
roasting
roasting
degree
time (min)
3-CQ A
4-CQ A
5-CQ A
3-FQA
4-FQ A
5-FQA
3,4-DiCQ A 3,5-Di CQA 4,5-Di CQA
C. arabica cv. green
0
483.3 ± 6.1
543.5 ± 9.3
3126.1 ± 29.7
28.3 ± 0.9
40.1 ±1.8 210.7 ± 1.8
236.2 ± 4.0 254.9 ± 4.7 278.9 ± 12.5
Bourbon
very light
5
996.0 ± 13.7
1277.7 ± 43.4
2808.5 ± 8.8
74.3 ± 2.7
73.2 ±2.7 167.0 ± 2.3
164.1 ± 5.1 152.3 ±20.9 190.5 ± 4.6
light
6
816.1 ± 13.1
999.6 ± 45.1
1995.8 ± 19.9
47.8 ± 7.9
68.0 ±3.8 109.1 ± 8.2 119.7 ± 2.3 88.6 ± 3.8 127.8 ± 4.0
light medium
7
458.5 ± 23.4
590.4 ± 51.2
1103.5 ± 40.9
34.2 ± 2.6
43.9 ±1.6
87.3 ± 5.9 51.7 ± 3.7 35.2 ± 1.4 50.1 ± 1.6
dark medium
8
198.6 ± 10.1
281.6 ± 11.0
447.5 ± 22.9
17.6 ± 3.1
30.7 ±5.2
66.0 ± 4.8 14.0 ± 3.0 12.2 ± 2.0 16.6 ± 1.5
dark
9
122.8 ± 3.0
155.8 ± 7.6
244.3 ± 17.9
9.7 ± 0.2
19.9 ±1.0
22.1 ± 0.8
7.4 ± 1.2
5.1 ± 2.7
9.2 ± 1.8
very dark
10
80.1 ± 2.0
71.3 ± 3.3
159.6 ± 9.9
7.6 ± 0.5
13.7 ±0.0
12.6 ± 0.7
Nd
2.2 ± 0.8
Nd
C. arabica cv. green
0
478.2 ± 85.3
473.5 ± 12.7
3605.8 ±33.2
22.9 ± 2.1
34.5 ±0.3 234.9 ± 5.4 234.3 ± 3.0 263.5 ± 14.7 342.6 ± 4.9
Longberry
very light
5
950.7 ± 11.1
1234.3 ± 76.1
3102.2 ± 7.2
62.9 ± 3.5
65.2 ±2.0 165.8 ± 7.2 189.1 ± 5.1 176.0 ± 10.8 281.4 ± 11.6
light
6
804.7 ± 11.6
933.0 ±20.4
1724.1 ± 19.0
42.2 ±10.9 56.8 ±3.0 107.0 ± 5.9 94.3 ± 7.0 72.5 ± 11.2 118.9 ± 29.5
light medium
7
343.8 ± 23.8
494.8 ± 12.4
815.7 ± 37.6
41.1 ± 3.7
42.2 ±5.7
68.4 ± 6.2 40.9 ± 4.3 36.3 ± 9.0 54.1 ± 2.3
dark medium
8
180.8 ± 12.6
265.0 ± 9.5
376.4 ± 8.5
14.6 ± 1.1
22.6 ±5.0
43.1 ± 2.3 11.3 ± 1.2 11.2 ± 0.4 15.8 ± 0.6
dark
9
110.1 ± 9.6
156.2 ± 5.5
218.6 ± 5.2
9.2 ± 0.9
17.0 ±1.0
14.5 ± 0.9
3.4 ± 0.2
5.1 ± 0.2
6.1 ± 0.8
very dark
10
53.0 ± 8.4
51.3 ± 1.7
104.7 ± 11.3
6.3 ± 1.1
12.2 ±0.4
7.4 ± 0.8
Nd
Nd
Nd
C. canephora cv.
green
0
924.8 ± 29.9
602.4 ± 12.1
4243.3 ± 15.3
34.1 ± 1.7 57.8 ± 3.0 379.2 ± 18.8 423.5 ± 6.3 400.7 ± 8.9 511.5 ± 2.7
Robusta
very light
5
1257.3 ± 21.4
1481.0 ± 28.5
3802.4 ± 10.5
89.7 ± 4.8 108.0 ±5.7 310.8 ± 17.9 337.2 ± 4.4 279.6 ±18.5 334.3 ± 13.8
light
6
1086.7 ± 96.8
1342.9 ± 42.1
2520.8 ± 77.3
57.1 ± 0.4 110.0 ±0.9 241.7 ± 11.4 217.3 ±11.6 158.6 ± 7.6 205.0 ± 9.5
light medium
7
623.4 ± 6.5
790.9 ± 35.9
1347.1 ± 7.9
79.2 ± 1.5 86.1 ± 4.1 169.8 ±8.0 81.8 ± 3.7 61.4 ± 2.9 91.9 ± 3.8
dark medium
8
334.0 ± 14.0
308.3 ±14.2
448.0 ± 9.6
40.8 ± 1.8 70.1 ± 5.1 73.4 ± 4.3 23.1 ± 1.1 18.0 ± 1.3 19.0 ± 0.8
dark
9
218.6 ±3.3
167.5 ± 3.4
225.8 ± 91.4
24.4 ± 4.4 39.4 ± 1.9 37.7 ± 2.7
6.9 ± 0.5
6.5 ± 0.4
6.0 ± 0.3
very dark
10
108.0 ± 6.9
99.9 ± 10.8
111.0 ± 2.2
14.7 ± 0.7 18.2 ± 1.8 23.4 ± 1.6
2.5 ± 0.6
3.2 ± 0.2
1.9 ± 0.2
Results and Discussion
9
Results and Discussion
0-5 min
焙煎中、高温度になることにより、異性化が起こる
異性化に加えてジエステルの加水分解でCQAが増加していると予想される
最初の5分で5-CQAと5-FQAは減少しているが,3-CQA, 4-CQAと3-FQA, 4-FQAは増加している
6-10 min
CGAの量が時間とともに減少している
炭素間の結合が切れ、CGAの分解が進んでいる
O
O
HOOC
OH OH
OH
OH
OH
HO
HO
CHCH
2
Vinyl Catechol
5-CQA
roasting roasting
degree time (min) 3-CQL 4-CQL 3-FQL 4-FQL 3,4-diC QL 3-pCoQ L 4-pCoQ L
C. arabica cv. green 0 Nd Nd Nd Nd Nd Nd Nd
Bourbon very light 5 71.6 ± 8.7 25.6 ± 1.6 6.5 ± 1.3 1.9 ± 0.2 2.8 ± 0.2 2.1 ± 0.3 0.5 ± 0.0 light 6 160.2 ± 2.3 92.1 ± 2.9 14.1 ± 1.2 7.0 ± 0.4 4.1 ± 0.4 4.6 ± 0.4 5.3 ± 0.2 light medium 7 248.5 ± 9.4 115.3 ± 1.0 28.3 ± 2.0 13.4 ± 0.7 6.6 ± 1.2 7.5 ± 0.4 7.8 ± 0.2 dark medium 8 146.6 ± 9.8 87.7 ± 2.1 29.8 ± 1.6 9.6 ± 0.4 2.1 ± 1.1 7.3 ± 0.7 6.6 ± 0.4 dark 9 95.7 ± 4.7 53.1 ± 3.5 21.2 ± 1.9 7.8 ± 0.3 1.0 ± 0.2 4.4 ± 0.2 4.0 ± 1.6 very dark 10 59.6 ± 10.0 24.8 ± 2.6 15.8 ± 6.0 6.2 ± 0.4 0.7 ± 0.06 2.3 ± 0.2 3.8 ± 0.6 C. arabica cv. green 0 Nd Nd Nd Nd Nd Nd Nd
Longberry very light 5 51.3 ± 1.9 22.5 ± 1.1 1.8 ± 0.0 Nd 3.1 ± 0.3 Nd Nd
light 6 161.2 ± 3.4 94.4 ± 3.1 20.2 ± 1.3 6.5 ± 0.3 6.8 ± 0.6 1.6 ± 0.1 1.9 ± 0.2 light medium 7 210.5 ± 8.6 116.0 ± 4.7 29.7 ± 0.3 11.6 ± 0.6 7.8 ± 0.6 4.4 ± 0.3 2.6 ± 0.3 dark medium 8 163.3 ± 8.1 72.4 ± 1.6 28.4 ± 1.3 9.7 ±0.4 6.1 ±0.5 3.0 ± 0.2 1.1 ± 0.1 dark 9 94.5 ± 4.8 47.9 ± 1.7 15.5 ±2.8 5.6 ± 0.4 1.7 ± 0.4 3.5 ± 0.8 0.6 ± 0.1 very dark 10 56.3 ± 7.7 37.1 ± 0.8 10.2 ± 1.2 3.5 ± 0.2 1.1 ± 0.1 2.0 ± 0.2 Nd C. canephora green 0 Nd Nd 4.0 ± 0.0 9.1 ±0.8
cv.Robusta very light 5 57.7 ± 4.4 25.8 ± 1.4 6.4 ± 0.4 16.4 ± 1.7
light 6 198.8 ± 4.4 110.0 ± 2.1 18.4 ± 0.7 23.6 ± 1.0
light medium 7 253.6 ± 4.3 138.8 ± 2.0 31.1 ± 1.3 25.4 ± 1.0 dark medium 8 165.4 ± 10.6 125.9 ± 8.8 16.6 ± 0.4 10.0 ± 1.2
dark 9 87.6 ± 4.8 45.0 ± 2.0 8.4 ± 1.3 4.3 ± 1.4
very dark 10 54.4 ± 6.7 25.9 ± 2.9 5.1 ± 0.3 0.8 ± 0.2
Results and Discussion
・苦みの要因だといわれているCQLの量はロブスタ種 >アラビカ種
Table 2. Chlorogenic Acid Lactone Content in Green and Roasted C. arabica Cv. Bourbon, C. arabica Cv. Longberry, and C. canephora Cv. Robustaa
11
Results and Discussion
OH
O
O
O
OH
O
HO
HO
O
OH
O
HO
O
O
HO
HO
O
OH
O
O
O
HO
HO
HO
O
OH
OH
HO
O
HO
HO
COOH
OH
OH
O
COOH
HO
HO
O
HO
4-CQA
(equatorial conformer)
(axial conformer)
4-CQL
(intermediate orthoformate)
3-CQL
-H
2O,
4-CQAの熱転位による3-CQLの生成
安定
axial
equatorial
Δ
12
Results and Discussion
Figure 3. Lactones formation during roasting of (a) C. arabica cv. Bourbon; (b) C. arabica cv. Longberry; and (c) C. canephora cv. Robusta coffee beans.
Maximum lactone levels were observed after 7 min of being roasted (i.e., 14% weight loss).
