Đề tài anthocyanin và những nguyên liệu chứa anthocyanin

Truong Dai hoc Ky Thuat Cong NgM TP.HCM
Khoa Cong nghe Thvc Ph~m

BO MON

Cong Nghe Thuc Ph~m

DO ANMON

HOC
•

Cong Ngh~ Thvc Ph~m
(MSMH: 20471014)

DE TAl:
ANTHOCY ANIN

vA NHONG

NGUYEN

LIBu CHUA

ANTHOCYANIN

GVHD: Co Tdn Thj Cue Phuong
SVTH: 1. Huynh Thj Thanh Tuy~n_0851100344
2. Tr~n Thi Xuan Hong , 0851100091
Nganh: Cong Nghe Thuc Ph~m

Narn hoc: 2011


Mt}clt}c

I. T6ng quan v~ Anthocyanin

3

1. Gioi thieu

4

2. C~u true hoa h9C cua Anthocyanin

4

3. Tinh chat cua Anthocyanin

5

Cong dung

7

4. Su phan b6 cua Anthocyanin

8

5. Qua trinh sinh tong hop Anthocyanin

8

5.1. Con duong sinh t6ng hop Anthocyanin trong t~ bao thuc v~t

9

5.2. Cac y~u t6 anh huong d€n qua trinh sinh t6ng hop

9

6. Sir chuyen d6i

C&U true cua

Anthocyanin trong mo i truong long

9

7. MQt s6 y~u t6 anh huang d€n dQ mau cua Anthocyanin

11

7.1 . C~u true

12

7.1.1 C~u true chuyen hoa

13

7.1.2. C~u true hoa h9C

14

7.2. PH

15

7.3. Nhiet dQ

16

7.4. Oxy

17

7.5. Enzyme

19

7.6. Anh sang

20

7.7. Duong va cac san pharn bien tinh cua chung

22

7.8. Cac ion kim loai

25

7.9. Sunphurdioxide/So-)

28

7.10. Acid Ascorbic

30


8. Kha nang irng dung va cac nguon nguyen lieu trong san xuat Anthocyanin

hien nay .. 34

9. Vai tro cua cac hop chat Anthocyanin

37

9.1. D6i voi thuc v~t

40

9.2. D6i voi sire khoe con nguoi

12

9.2.1. Heat tinh chong oxy hoa

13

9.2.2. Heat tinh chong ung thu

14

9.2.3. Heat tinh chong cac

benh tim mach

15

K~t luan

16

II. Cac nguyen li~u co chua Anthocyanin

17

1. Blip cai tim

19

1.1. T6ng quan

20

1.2. Thanh ph~n hoa h9C

22

Gioi thieu v~ phuong phap trich ly

25

Cac y~u t6 anh huang d~n qua. trlnh trich ly

28

1.3. Quy trinh cong nghe chiet tach Anthocyanin tir blip cai tim

30

Ti~n hanh thi nghiem

14

Phuong phap thi nghiem

15

Muc dich thi nghiem

16

Chu§n bi thi nghiem

17

B6 tri thi nghiem
Phuong phap nghien cuu
Ket qua nghien

CUD

0 •••••••••••••••••••

0 •••••••••••••••••••

19
20
22

1.4. K~t luan

25

2. Gao nep than

19

2.1. Tcng quan

20


2.2. Thanh phan hoa h9C

22

2.3. Qua trinh va tinh che Anthocyanin

tt'l' gao nep than

30

2.4. Nhan xet va k~t luan

15

3. Dau tay

19

3.1. T6ng quan

20

3.2. Thanh phan hoa h9C

22

3.3. Phuong phap nghien ciru

30

3.3.1. Nguyen lieu

14

3.3.2. Phuong phap

15

3.3.3. Ti~n hanh thi nghiem

16

3.3.4. K~t qua nghien ciru v~ cac di;ictinh cua Anthocyanin

17

Nhan xet

16

3.4. K~t luan

17

III. Cac ch~t Anthocyanin thuong mai

17

IV. Phuong phap nghien ciru, bao v~ mau do cua Anthocyanin

19

l.Phuong phap nghien ciru

20

So d6 nghien ciru

22

2. Bao v~ man do cua Anthocyanin

22

Ml}c Ll}c_Bang:
Bang l.Cac Anthocyanin trong mot

s6 nguon

thuc vat..

Bang 2. Thanh phan hoa h9C cua bap cai
Bang 3.

Anh huang cua dung moi den ham luong va do mau cua Anthocyanin

17
19
20

Bang 4. Ty i~ dung moi va bam hrong Anthocyanin

17

Bang 5. Thanh phan hoa h9C cua gao nep than

19

Bang 6. Thanh phan dinh duong cua qua dau tay

20


Bang 7. K~t qua ham hrong Anthocyanin thea dO chin cua qua dau

17

Bang 8. Ph§n tram man con lai thea thai gian a 9Soc tai cac PH khac nhau cua
Anthocyanin tho chi~t trong dung moi mroc Sulfite va etanol/Hjf)

19

Ml}.CLl}.c_Hinh:
Hinh 1. cAu true cua mot s6 Anthocyanin tv nhien

17

Hinh 2. Con duong sinh t6ng hop Anthocyanin

19

Hinh 3. SI! chuyen hoa cAutrue cua phan tIl' Anthocyanin trong moi truong long

20

Hinh 4. cAu true chuyen hoa cua Anthocyanin trong nuoc

17

Hinh S. Anh huang cua PH len t6c do thuy phan cua qua dau duoc dun nong tai 4SoC trong
truong hQP co Oxygen hoac Nitrogen
19
Hlnh 6. Sir bien tinh cua Anthocyanin 3,S_diglucoside tai PH 3,7

20

Hinh 7. Sir bi~n tinh cua Anthocyanin voi phan ung oxy h6a Catechol.

20

Hinh 8. Phan irng ngung tu cua a) Cyanidin va furfural va b) cyanidin ketobase va
furfural

17

Hinh 9. So d6 Jurd d6i voi phan irng thuan nghich giira S02 va Anthocyanin

19

Hinh 10. Sir chuyen hoa Malvin thanh Malvone boi H202 tao thanh

S\I'

oxy hoa

vitamin C

20

Hinh 11. Fla-2-ene duoc tao thanh nr phan ling gitta vitamin C va A

17

Hinh 12. Sir tao phirc gitra Cyanidin va DNA

19

Hinh 13. B~p cai tim

20

Hinh 14. Cong tlnrc cAutao cua Cyanidin 3,S_diglucoside

20

Hlnh IS. Qua trinh trich Iy mot doan

20

Hinh 16. Qua trinh trich ba dean giao dong

17

Hlnh 17. Qua trinh trich nhieu doan nghich dong

19

Hinh 18. So d6 quy trinh cong nghe chiet tach Anthocyanin tir b~p cai tim

20


Hinh 19. 1)6 thi bi~u di~n anh huang cua cac h~ dung mo i.

20

Hinh 20. Anh huang cua ty I~dung moi (Etanol-mroc ) dSn ham IUQ'ngAnthocyanin

19

Hinh 21. Hat nSp than

20

Hinh 22. Qua dau tay

20

Hinh 23. KSt qua ham luong Anthocyanin

a cac nong

d9 S02 khac nhau

20

Hinh 24. KSt qua ham luong Anthocyanin

a cac nhiet

d9 khac nhau

20


I. Tang quan v~ Anthocyanin:
1. Gioi tbi~u:
Cac Anthocyanin hien thuoc nh6m cac chat man tu nhien tan trong mroc Ian nhat trong th€
gioi thuc vat. Thuat ngii' anthocyanin b~t nguon nr tieng Hy Lap, trong do Anthocyanin la

S\T

ket h9]J giira Anthos - nghia la hoa va Kysanesos - nghia la mau xanh. Tuy nhien, khong chi co
mau xanh, anthocyanin con mang d€n cho thuc v~t nhieu mau s~c me ro' khac nhir hong, do,
cam va cac gam mau trung gian. Cac anthocyanin
anthocyanidin

hay aglycon. M6i anthocyanidin

khi mAt h€t nhom dirong duoc goi la

co th~ bi glycosyl h6a acylate boi cac loai

duong va cac acid khac tai cac vi tri khac nhau. Vi th€ hrong anthocyanin
anthocyanidin
2.

nr

Ian han

15-20 IAn.

C§u true boa hoc cua Anthocyanin:
Anthocyanin thuoc nhom cac h9]J chitjlavonoid,

co kha nang hoa tan trong mroc va chua

trong cac khong bao, V~ ban chit, cac Anthocyanin la nhtrng hop chit glycoside cua cac d~n
xuit polyhydroxy va polymethoxy

cua 2-phenylbenzopyrylium

hoac mu6i flavylium.

Cho d€n

nay, nguoi ta da xac dinh duoc 18 loai aglycon khac nhau, trong do 6 Joai ph6 bien nhit Ia
pelargonidin, cyanidin, delphinidin, peonidin, petunidin
Trong W nhien, Anthocyanin rAt hiem khi
hydroxy W do

a vi tri C-3

va maldivin.

a trang thai tu do (khong

bi glycosyl h6a). Nhom

lam cho phan tir anthocyanidin tro nen khoug 6n dinh va lam giarn

kha nang hoa tan cua no so voi anthocyanin tuong (mg. Vi vay, su glycosyl h6a luon di6n ra,
d~u tien 0 vi tri nhorn 3-hydroxy. Neu co them mot phan nr duong sua, vi tri ti€p thea bi
glycosyl h6a thuong g~p nhit la

a C-5. Ngoai

ra, su glycosyl h6a con co th~ g~p

a cac vi tri C-

7, C-3', C-5 '.
Loai duong ph6 bien nhit la glucose, ngoai ra ciing co mot vai loai monosaccharide (nhu
galactose, rammose, arabinose), cac loai disaccharide (chu y€u la rutinose, sambubiose hay
sophorose) hoac trisaccharide tham gia vao qua. trinh glycosyl h6a.
Su methoxyl h6a cac anthocyanin va cac glucoside tuong zing di6n ra thong thuoug nhat Ia

a vi tri C-3'

va C-5', ciing co the g~p

a vi tri C-7 va C-5.

Tuy nhien, cho d€n nay, nguoi ta v~n

chua tim thay mot hop chit nao bi glycosyl h6a hay bi methoxyl h6a tren tit cit cac vi tri C-3, 5, -7 va -4' do dn thiet phai con it nhAt mot nhom hydroxyl tu do

a C-5,

-7 bay -4' d~ hinh


thanh dang du true quinonoidal base (dang du true cua anthocyanin tlnrong t6n tai trong

khong bao thuc v~t co pH ill 2,5 -7,5).

ORs
Hinh 1: C6.u true cua mot s6 Anthocyanidin

tu nhien. Cac Anthocyanin tuong ung luon

dutrc glycosyl hoa 0' nhom hydroxy C-3
Su acyl hoa ciing co th~ xay ra 6 vi tri C-3 cua phan nr duong hay ester hoa 6 nhorn
hydroxy C-6. Cac nhom acyl hoa ehinh la cac phenolic acid nhu p-coumeric, caffeic, ferulic
hay sinapic acid

va mot loat cac acid nhu acetic, malic, malonic, axalic va succinic.

3. Tinh chit cua Anthocyanin:
Anthocyanin

tinh khidt 0' dang tinh th~ hoac

vo

dinh hinh

la

hO'P eh~t kha phan cue

nen tan t6t trong dung moi phan eve.
Anthocyanin hoa tan t6t trong mroc va trong dich bao hoa. Khi k€t hop voi duong

la

cho phan nr anthocyanin hoa tan han.
Mau s~c anthocyanin thay d6i phu thuoc vao nhiet d(j, cac ch~t mau va nhi~u y€u t6
khac, ... Khi tang s6 luong nhorn OH trong vong benzene thi mau cang xanh d~m.
Mire d(j methyl hoa cac nhorn OH 6 vong benzene cang eao thi mau cang do. Neu
nhorn OH 6 vi tri thir ba k€t hop voi cac g6e duong thi mau s~e ding se thay d6i thea s6
luong cac g6e duong duoc dinh vao nhi~u hay it.


Cac

Anthocyanin ciing phu thuoc nit manh vao pH cua moi tnrong:
)io>

Khi pH> 7 cac Anthocyanin co mau xanh va khi pH < 7 cac Anthocyanin co mau do.

)io>

o pH = 1 cac Anthocyanin thuong a dang mu6i oxonium man cam d~n do.

)io>

o pH = 4+5

chung co th~ chuyen v~ dang baza Cacbinol hay baza Chalcon khong

mau.
)io>

o pH = 7+8

lai v~ dang bazo Quinoidal Anhydro mau xanh.

Mau sitc cua anthocyanin can co the thay d6i do hfrp thu

a tren

polysaccharide. Khi dun nong

lau dai cac anthocyanin co the pha huy va mfrt mau,

Anthocyanin co buoc song hfrp thu trong mien nhin thay, kha nang hfrp thu cue dai tai buoc
song 510+540nm. D<) hfrp thu la y~u t6 lien quan mat thi~t d~n mau sitc cua cac anthocyanin
chung phu thuoc vao pH cua dung dich, nong d<) anthocyanin: thuong pH thuoc vung acid
manh co d<) hfrp thu Ion, nong d<)anthocyanin cang Ian d<) hfrp thu cang manh.
Tom lai, trong moi tnrong acid, cac anthocyanin Ia nhirng bazo manh va co the tao
muoi b€n virng voi acid. Anthocyanin ciing co kha nang cho muci voi bazo. Nlnr v~y chung

co tinh chfrt amphote. Mu6i voi acid thi co mau do, can mudi voi kiern thi co mau xanh.

* Cong dung:
Anthocyanin la chfrt mau thien nhien duoc su dung kha ph6 bien va an toan trong thuc
pham, tao ra nhieu mau sitc hfrp d§n cho m6i san pham.

Anthocyanin la h9P chfrt co nhieu hoar tinh sinh h9C qui nhu:
)io>

Kha nang chong oxy hoa cao nen duoc sir dung d~ chong lao hoa, hoac chong oxy
hoa cac san pham thuc pharn, chong viern, chong cac tia phong

X~'"

)io>

Han ch~ S\I suy giam sire d~ khang, S\I phat tri~n cua cac t~ bao ung thu.

)io>

Ngoai ra, Athocyanin can co vai tro thu hut con trung giup cho

S\1'

thu phfrn cua cay

di~n ra t6t han,
4. S\I' philo

b6 cua Anthocyanin:

anthocyanin t~p trung

a nhfrng cay

hat kin va nhtrng loai ra hoa, ph~n Ian nam 6' boa va qua,

ngoai ra ciing co 6' la va r~. Trong nhttng loai thuc v~t nay, anthocyanin duoc tim thay chu y~u

6' cac lap t~ bao n~m ben ngoai nhu bi~u bi,


Cac hop chat

anthocyanin xu§t hien rong rai trong khoang it nh§t 27 ho, 73 10lE va trong va s6

giong thuc v~t sir dung lam thuc v~t (Bridle va Timberlake, 1996). Cac ho thirc v~t nhu vitaceae
(nho) va rosaceae (cherry, dau tay, mam xoi, tao, ... ) la cac nguon anthocyanin chit y~u. Ben
canh do con c6 cac ho thuc v~t khac nhu solanceae ( ca tim), saxifragaceae (qua ly do va den),

ericaceae (qua viet quoc) va brassicaceae (bap cai tim). Cac loai anthocyanin pho bien nll§t la
cac glucoside cua cyanidin, k~ d~n la pelargonidin, peonidin va delphinidin, sau do petuidin va

maldivin.

se hrong

cac 3-glucoside nhieu g§p 2,5 I~n cac 3,5-glucoside. Loai anthocyanin hay

g~p nhat chinh la Cyaidin-S-glucoside.

Bang 1: Cac Anthocyanin trong mot s6 nguon thuc v~t

Ten thuc v~t

Ten thong thuong

Loai Anthocyanin

Alliumcepa

Cu hanh do

Cy-3-glucoside, 3-galactoside, 3diglucoside va 3-laminarriobioside,
Pn-3-g1ucoside

Brassica oleraea

B~p cai tim (red cabbage)

Cy-3-sophoroside-5-g1ucoside cacyl
h6a voi malonoyl, p-coumaroyl, dip-coumarol.feruloyl, diferuloyl,
sinapoyl va disinapoyl

Fragaria spp

Dau tay (strawberry)

Pg va Cy-3-glucoside

Glycine maxima

f)~u nanh (vo )

Cy va Dp-3-glucoside

Hibicus sabdariffa L

Hoa b1,ltdam

Raphanus sativus

Cu cai do (re)

Pg va Cy-3-sopboroside-5-glucoside
acyl hoa voi p-coumaroyl, feruloyl,
caffeoyl.

Vitis spp

Nho

Cy, Pn, Dp, Pt va Mv mono va
diglucoside; danh tv do va dang acyl
b6a

Cy = cyanidin, Pg= pelagorindin,
malvidin

Pn= peonidin,

Cy, Pn, mono-

Dp= delphinidin,

Pt

va biosides

petunidin, Mv=


5.

Qua trinh sinh tbng hcyp Anthocyanin:

5.1. Con dU'O'ngsinh tbng hQ'pAnthocyanin

trong t~ bao thuc v~t:

Anthocyanin thuong narn trong cac mo hoa va qua, trong cac lop t~ bao bieu bi va duoi
bieu bi cua la va than thuc v~t. Tnroc day, co nguoi cho rang qua trinh sinh t6ng hop
anthocyanin di~n ra trong cac bao quan hinh du n~m ben trong khong bao, duoc goi la cac
anthocyanoplast. Cac bao quan nay xuat hien Tong rai 6' ca cac cay mot la mam va cay hai la
mam. Tuy nhien, thea nghien ciru cho th§y qua trinh sinh t6ng hop anthocyanin co th€ khong
di~n ra trong cac anthocyanoplast do 6' day co ham IUQ'nganthocyanin cao va pH thap, trong khi
do pH t6i thich cua t§t cit cac enzyme duoc bi~t tham gia vao con duong sinh t6ng hQP.flavonoid
la pH trung tinh.
Qua trinh sinh tong hop anthocyanin duoc di~u hoa boi mot h~ thong cac gen. Anthocyanin
chi xuat hien 6' cac loai thuc v~t tren can rna khong co 6' cac loai dong v~t, vi sinh v~t hay thuc
v~t diroi mroc. Nguyen nhan do qua trinh sinh t6ng hop anthocyanin doi hoi phai co v~t lieu khoi

dftu di ttl' qua trinh quang hop. Duoi tac dung cua emzyme Chalcone synthase, Chalcone duoc
tao thanh thong qua phan ung ngung tu giita 1 phan tu' acid cinammic hoat hoa (coenzyme A cua
4-coumaric acid hay it g~p han la cua ferulic, caffeic, 5-hydroxy ferulic hay sinapic acid) va 3
phan nr malonyl-CoA. Acid cinammic hoat hoa duoc I§y nr Lsphenylalanine qua con duong sinh
t6ng

hop phenylpropanoidigiun

Hydroxylase, 4-Coumarat-CoA

cac enzyme

Phenylalanine-ammonialyase,

Cinammate-A-

ligase). Malonyl-CoA duoc tao thanh nr Acetyl-CoA qua phan

ung xuc tac boi enzyme Acetyl-CoA carboxylase. Ti~p theo, phan nr Chalcone duoc dong vong
thong qua phan irng xuc tac boi enzyme Chalcone isomerase hinh thanh cecflavanone

d6ng phan

(nhu naringenini. Sau do, chinh cac hop ch§t nay duoc chuyen hoa thanh cac dihydroxyflavanol
(flanva-3-ol) boi enzyme flavanone-3-hydroxylase,

d6ng thai co th~ k~t hop voi ca enzyme 2-

hydroxylase va mot enzyme dehydratase. Cac dihydroxyflavonol duoc xem la cac ti~n ch§t cua
anthocyanidin. Cac enzyme xuc tac cho qua trinh chuyen hoa nr cac dihydroxyflavonol thanh cac

anthocyanidin cho d~n nay v~n chua duoc xac dinh ro rang, co th~ la cac oxydo-reductase voi
cac hop ch§t trung gian la.flavan-3,4-diol (leucoanthocyanidin).

Su khac nhau 6' nhom th~ vong

B co th€ b~t dftu 6' giai doan cinammic acid, nhung chu y~u di~n ra 6' giai doan hinh thanh cac
hqp ch§t trung gian CI5 (rum chalcone/flavanone)

sau do.


Cac hop chat anthocyanidin nr nhien se duoc glycosyl h6a ngay l~p nrc 0 nh6m hydroxy C-

3 do chung khong b~n trong moi tnrong long. Qua trinh glycosyl h6a ti~p theo, n~u co, se xay ra
thea dang bac thang, b~t dftu nr viec g~n cac phan tir duong vao g6e S-glycosyl va hoac nhorn 5hydroxy. Cac uridine diphosphat (UDP)-duong dong vai tro la chat eho glycosyl eho tfrt ca cac
enzyme glycosyl-transferase.

Qua trinh acyl h6a Anthocyanin co th~ xay ra sau qua trinh glycosyl

h6a, xuc tac boi cac enzyme acyltransferase.

5.2. Cac y~u t6 anh hurrng d~n qua trinh sinh tang hop:
Qua trinh sinh ding hop anthocyanin bi tac dong boi cac y~u t6 moi tnrong nhu: anh sang,
nhiet d9, cac hormone thuc vat, nguon dinh duong, nhttng tac dong co hoc va sir tfrn cong cua
cac loai gay benh. Trong do, anh sang ehinh la y~u t6 quan trong nhfrt. Anh sang hong ngoai hoat
hoa cac phytocrome mau, la ehfrt cam irng eho cac enzyme trong con duongjlavone-glucoside

va

ttl' do, giup t6ng hop anthocyanin trong t~ bao. Ngoai ra, cling thuong cftn d~n tia UV ben canh

cac phytocrome

hoat d9ng d~ cam irng cac enzyme. Trong moi tnrong nuoi cfry t~ bao

Haplopappus gracilis, chi co tia UV co buoc song nho han 345nm moi kich thich duoc qua trinh
t6ng hop anthocyanin. DU'6'i tac dung cua tia UV, hoat tinh cua cac enzyme phenylalanineammonia-lyase, chalcone, synthase va chalcone isomerase tang len dang k~.
Qua trinh tieh tu Anthocyanin trong la cay con lien quan d~n rmrc d9 phat trien ella la, su
thieu hut cac ehfrt khoang da luong nhir N, P, rmrc d9 ti~p xuc ella la voi tia UV. Ngoai ra, su
t6ng hop anthocyanin cling co th~ la mot phan ung ella thuc v~t chong lai su tfrn cong ella cac
loai an co cling nhu cua cac loai nam moe.


Quang

hc;lP

CO2 + H20

~

+

CHO

co,

R'

I

--

H!OH

I
ICH.OP

C-OP

II
CH,

d

HCOH

HO

"'/
t

Shikimik acid pathway

ROO

HO

Anthocyanid in

Flavan - 3 - 01

6x-

IC

H,.

HOwH

~

~ AA
~OH

R"

OH

OH

L-phenylalanine

+

R'

IA

HO

0

R"

Flavanone

•

OH

General Phenylpropanoid Metabolism

Anthocyanin
OH

o~o

HO

R-

OH

3 acetyl - CoA

1

R~~

0

Chalcone
OH

3CO.

3 - Malonyl - CoA

Cinammic acid

!

CoASH
ATP

Coenz me A-Esters

a

Hinh 2: Con duong sinh t6ng h9P Anthocyanin. Enzyme: chalcone synthase (a); chalcone
isomerase (b); flavanone - 3 - hydroxylase (c); oxidoreductase (s) (d); glycosyl transferase (e)
GI = nhorn glycosyl; R', R"=H, OH, OCH3 hay OGI
6. 8\1'chuyen d6i

du true

ella Anthocyanin trong moi tmc'rng long:

Trong moi tnrong long, duoi tac dong cua cac gia tri pH khac nhau cua rnoi truong, cAu
true cua phan nr Anthocyanin se trai qua mot s6 chuyen hoa,

su can bang gitta 4 du true Anthocyanin:

6 mot

gia tri pH xac dinh, di~n ra


./

Quinonoidal (anhydro) base (A): mau hoi tim

./

Cation flavylium (AF): man do

./

Carbinol pseudo base (hay hemiacetal) (B): khong man

./

Chalcone ©: khong mau

.:. Phuong trinh chuyen hoa:

B

B
Sir chuyen d6i diu true cua Anthocyanin

+ W

c
trong nuoc

la

do hoat tinh eao cua g6e aglycone

(Anthocyanidin). G6e duong, nhorn methoxyl ciing nhu cac nh6m acyl hoa ciing anh huang dang

k~ d~n str chuyen h6a tren.


,#RJ':,

H¥r?R3', H~OH RliOH
Ie

_

R5_

OOIe

R~'

H

0

H

H.ml._.t.1 (kh4ng m~u)

CI: - _h.l_on. (kh6ng mau)

Tr.n: - _h.l_on. (kh6ng m.u)

/

~:-

Qulnold.11>:1:. hung tinh (helltim)

o

- .~.

Qulnold.11>:1:•• nlon(hellxanh)

Hinh 3: S1!-'chuyen hoa cdu true cua phdn tu'Anthocyanin trong moi truong long
Dang quinonoidal base duoc tao thanh thong thuong
b~n

(y

(y

pH> 3, Cationflavylium tuong d6i

moi tnrong acid (rum pH < 3), Trong moi truong trung tinb hay aeid y~u, Anthocyanin t6n

tai chu y~u

(y

cac dang khong mau, Vi vay,

S\I'

6n dinh ella cac dang mang mau, d~e biet lit dang

quinonoidal base, mot phan lit do su xuat hien cua cac g6c acid g~n vito phan tll' duong, hay eon
goi la su co-pigment hoa noi phan ill', So' di su co-pigment hoa noi phan ill' giup tang do b~n ella
phan nr anthocyanin la do

5\{

x~p chong ella vong thorn trong g6c aeid voi vong pyrylium ella

phan nr anthocyanin, giam bot kha nang bi cac phan tll' nuoc tAn cong hinh thanh cac hop ch~t
carbinol, chalcone khong mau. Ngoai ra, hieu irng copiment hoa ngoai phan tir ciing eo th~ giup
lam ben cac du true quinoidal base hay ionflavylium do 5\1' eo mat ella nhirng plnrc eh~t khong
mau, nhu cac flavone, flavonol, Trong qua trinh xu'

Iy nhiet

va anh sang, qua trinh copigment hoa

ngoai phdn

ttc gilt

vai tro quan trong, ngan chan su mit man co th~ xay ra. Co ch~ phan huy do

nhiet noi chung do sir chuyen hoa thuan nghich cua cac ionjlavylium thanh cac dang chalcone.

Chalcone lit chat trung gian trong ca hai qua trinh phan huy do nhiet va anh sang cua
anthocyanin. Theo cac nghien ciru g~n day (Davis va cting su; 1983; Mazza va Brouillard,1990)
hieu irng co-pigment hoa chinh la

CO"

che lam b~n mau chinh cua anthocyanin trong thuc vat do

no lam giam ti l~ gitla dang kh6ng mang mau (chalcone) va dang mang mau thong qua viec tao
plnrc voi dang mang mau, ngan chan qua trinh chuyen hoa nr dang mang mau sang dang khong
mang mau.
Trong dung dich, Anthocyanin dang kh6ng acyl hoa hay acyl hoa mot dan vi dong vai tro
nhu m(>tch~t chi thi pH, t6n tai o' dang acid hay base tuy thuoc vao gia tri pH.

d pH

acid (pH <

3), dung dich anthocyanin cho man do darn, Khi pH tang, mau s~c cua dung dich se nhat d~n va
chuyen sang kh6ng mau va cuo: cung co mau tim hay xanh duong 6 pH cao (pH> 6).

7. M9t s~ y~u t~ anh huong d~n d9 mau cua Anthocyanin:
So voi da s6 cac chat mau thien nhien, anthocyanin la ch~t mau co d(>ben kern hon, no chi
thS hien tinh ben trong moi truong acid, Ngoai ra, no co th~ phan My tao thanh dang kh6ng mau
va san pham cu6i cung cua S\I'phan huy co dang mau nan cong voi nhirng san pharn kh6ng tan.
•

S\I'phan My anthocyanin co thS xay ra trong qua trlnh trich va tinh ch~ chung, d6ng thai
su phan huy nay con xay ra trong qua trinh xu

•

ly va bao quan cac san pharn thuc pharn,

D(> b~n cua cac anthocyanin phu thuoc vao nhieu y~u t6 nhu: cfru true hoa h9C cua

anthocyanin, pH, nhiet d(>, su co m?t cua copigment, ion kim loai, oxy, acid ascorbic,
S02, anh sang, enzyme, duong va cac san pham bi~n tinh cua chung.
7.1.

ciu true:

7.1.1.CAu true chuyen hoa:
Trong m6i tnrong mroc cac anthocyanin tu nhien gieng nhu ch~t chi thi pH. Do 6 pH thap,
do xanh 6 pH trung gian, va khong man 6 pH cao. Tai pH da cho, t6n tai mot din b~ng gitta 4
cfru true cua anthocyanin va aglycone: quinonoidal (anhydro) bazo (A) mau xanh, cation

flavylium (AH+) mau do, carbinolpseudo base (B), va chalcone (C) kh6ng mau.


R

~

OH

-----=:..

R

OH

AH

A

1~

OH
OH
-----=:..
...,....--

+

R

OH

OGI

OH

OH

B

C

Hinh 4: Cdu true chuyen hOGcua anthocyanin trong nutrc
Khi pH < 2,0, cac anthocyanin t6n tai chu y~u dang cation flavylium mau do (Rr=Osdtrcng]
hoac mau vang (R3=H), Khi pH tang, sir m§t proton xay ra nhanh thanh dang quinononidal mau
xanh duong hoac mau do, Dang quinonoidal thirong t6n tai nhu mot h6n hQP vi pKa cua nhom
OH

a vi tri 4',7 va 5

la tuong tu.

Khi d€ yen, su chuyen hoa

xay ra : co

su

tach mroc cua cation flavylium cho ra dang

pseudo base (hemiacetal), Dang nay din bang voi dang chalcone vong
Hai dang Cis (CE) va trans-chalcone-(Cz)
phan img

rna

rna khong

mau,

duoc tao thanh ur carbinol pseudo base boi

vong nhanh va isomer hoa cham. Cit 2 chalcone nay khac nhau so vci chalcone

binh thuong la boi chung co nhorn chirc carbonyl 0' canh vong B, trong do chalcone binh thuong
co nhorn carbonyl
i.

ciu

o' k~ can vong

A.

true hoa hec:
£)9 b~n mau va ctrong d9 rnau cua cac anthocyanin phu thuoc vao vi tri va s6 hrong cua

cac uhorn hydroxyl, methoxyl, duong va cac duong duoc acyl hoa. Khi s6 nhorn hydroxyl trong
vong B tang.cue dai h§p thu

a vung th§y duoc

dich chuyen v~ phia co buoc song dai hon va mau

thay d6i tir cam d~n xanh duong.
Vi du: Buoc song h§p thu cue dai trong dung dich HCL 0,01 % MeOH d6i voi:
• pelgonidin:

A,max

= 520 nrn (cam)


• cyaniding:

Amax

• dephinidin:

Amax

=

535 run (do cam)

=

545 nrn (do xanh)

Khi nhorn methoxyl thay th~ nhorn hydroxyl thi ta thu duoc k~t qua nguoc lai. Nhorn hydroxyl
tai vi tri C-3 co

y

nghia quan trong vi dung dich Anthocyanin

chuyen tir mau cam vang d~n

mau do, f)i~u nay giai thich sir khac nhau giita Anthocyanin co mau do trong khi do 3 deoxyanthocyanin

: apigenidin,

luteolinidin

va tricetinidin

co

mau vang

nhung

3 -

deoxyanthocyanidin

b~n hon cac anthocyanidin khac (Mazza va Brouillard, 1987; Iacobucci va

Sueny, 1983).
Su co m~t cua nhorn hydroxyl tai vi tri C-5 va nhom th~
co mau thong qua

S\1" ngan

a vi tri C-4, ca 2 bien

hoa dang

can cac phan ung hydrat hoa d~n d~n su tao thanh dang khong man.

Khi rmrc do hydroxyl hoa cac aglycone tang, tinh ben cua cac anthocyanin se giam. Tuy
nhien khi tang S\I" methoxyl hoa, se thu duoc k~t qua nguoc lai.
Vi du: su co m~t cua nhom OH 6 vi tri 4' va 7 trong phan tu lam ben h6a dang k~ cac
pigment, trong khi do,

S\T

methoxyl h6a co nhom hydroxyl nay lam giam do ben.

Cac anthocyanin duoc glycosyl hoa va acyl hoa se cho dang mau xanh, Su glycol hoa
nhfrng nhorn OH 1\1" do lam tang tinh ben cua anthocyanin. Vi vay, cac diglucoside b~n hon cac
rnonogluside cua cung mot anthocyanin.
Anthocnin

co chua 2 hay nhieu nhorn acyl (nhu ternatin, platyconin,

cmerarnn,

gntiodenphin va zebrrinin) la ben trong moi truong trung tinh boac acid y~u do lien k~t hydro
gina cac nhorn hydroxyl cua cac nhan phenolic trong anthocyanin va acid vong thorn. Brouillard
(1981-1982) va Goto cung voi cong vien (1982-1983) khao sat rang cac anthocnin diacylate hoa
duoc b~n hoa boi sir lien k~t ch~t kieu sandwich nho

S1,l'

tuong tac giua vong anthocyanin va 2

nhom acyl vong thorn.

7.2. PH:
Trong moi tnrong mroc, pH co anh huong dang k~ len mau sac cua anthocyanin
(Brouillard 1984,Mzza va Brouillard 1987). C~u true, dO ben mau, mau s~c cua anthocyanin
thay d6i theo su thay d6i cua ph. S\1"thay d6i du true cua anthocyanin khi pH thay d6i da: duoc
d~ cap trong phan du true chuyen hoa.


Nam

1956 Lukton

nghien

ciru thfry rang:

a

ph

=

2 - 4.5 thi van toe phan huy

pelargonidin 3- glucoside trong dich ep cua qua dau khong xac dinh duoc khi khong co O2. Khi
co mat O2 ph tang nhanh, su bien tinh tang len manh liet,

+~

5

....E

PH=3,5
02

200

PH=4.0

400

600

800

KOIO

-4

hour-I

Hinh 5: Anh huang cua pH len t6c do thuy phan cua qua dau duoc dun nong tai 45°C trong
truong hop co Oxygen hoac Nitrogen

D~n narn 1972, Adams nghien ciru thfry rang 0- ph = 2 - 4 it anh huong d~n su phan

My cua Anthocyanin trong suot qua trinh gia nhiet khi khong co O2. Khi co mat O2 thi
Anthocyanin bi bi~n tinh rnanh 0- ph tren du true cua chung cung voi dO b~n mau thay d6i voi
sir thay d6i ph.
7.3.

Nhi~t de.>:

Trong qua trinh ch~ bien va bao quan thuc pham, Anthocyanin d~ dang bi bien tinh
duoi tac dung cua nhiet do (Markakis 1974).


OH'(JO:::::-O
/.

OGI

OGr

OR

/

I

R

-.Q,

OGI

OR

Hinh 6: S\f bien tinh cua Anthocyanin 3,5 - di Glucoside tai pH 3,7

Khi mot du true cua anthocyanin ben voi su gia tang cua pH thi no ciing b6n voi su gia
tang cua nhiet dQ. S1,l· hydroxyl hoa cac aglycone lam giam tinh b6n cua anthocyanin, trong khi
sir methxyl hoa, glycosyl hoa, acyl hoa se cho k~t qua nguoc lai,
Vi du: Anthocyanin 3- glycoside co dQ b6n nhiet Ian nhl1t tai pH

=

1.8 - 2.0 voi sir co

m~t cua oxy trong khi anthocyanidin 3,5-diglycoside co dQ b6n nhiet Ian nhat tai pH

=

4.0 - 5.0

Co ch~ cua su phan huy nhiet xay ra khong nhfrng phu thuoc vao nhiet dQ rna con phu
thuoc vao ban than anthocyanin do.
Drazdina cho r~ng coumarin glycoside la san pham phan huy phi> bi~n cua anthocyanin
3,5 - diglycoside va co ch~ cua

S1,l· phan

My la: d~u tien, cation flavylium chuyen thanh dang

quinonidal base, tiep theo la hinh thanh nhieu dang san pham trung gian va cu6i cung thu duoc
dftn xuit coumarin va thanh phan tuong ung voi vong B cua anthocyanidin, S\I' bien tinh nay

khong nhung duoc xuc ti~n boi nhiet dQ rna con bi anh huang boi oxy.
Anthocyanidin 3 - glycoside thi khong hinh thanh nhtrng dftn xuit coumrin rna buoc
d~u tien cua
sau do la
glycoside.

S1,l·

S1,l·

phan huy bao gem sir chuyen hoa cua dang carbinol pseudobase khong mau,

rna vong pyrylium d€ hinh thanh dang chalcone tnroc khi thuy phan lien k~t


Adams cho rang, cac anthocyanidin 3-glycoside khi duoc nung nong 6 pH

= 2.0

- 4.0

dAu tien se bi thuy phan lien kSt glycoside (6 100°C) sau do la su biSn d6i aglycone thanh
chalcone. Sir biSn tinh han nira d§n dSn hinh thanh dang san pham mau nau d~c biet ill voi su
co m~t cua oxy.
Khi dun nong lau dai cac anthocyanin co th~ bi phan huy va m~t mau, d~c biet la cac
anthocyanin cua day tay, anh dao, cu cai. Nguoc lai cac anthocyanin cua phuc ben nr den cling
trong di~u kien do lai khong bi thay d6i.Nhin chung khi gia nhiet, cac ch~t man do d~ dang bi
phan huy, con cac ch~t mau vang thi kho hun.

7.4.0xy:

Oxy va nhiet do duoc xem la nhfrng tac nhan d~c trung

XlIC

tien su phan huy cua

anthocyanin, do do rna sinh ra nhirng dang san pham khong mau hoac man nau. Chinh

SI,1'

oxy

hoa true tiSp dang carbinol pseudobase da gay ra sir ket tua va dong vang trong mroc trai cay.
Trong qua trinh dun nong cac anthocyanin bi oxy hoa manh li~t. Oxy va nhiet do la
nhirng tac nhan xuc tien d~c biet nh~t trong mroc ep cua blueberry, cherry (anh dao), currant,
nho, raspberry va dau.
LUQ'nganthocyanin con lai cua dau se 16n hun khi dong chai duoi di~u kien chan khong
hoac nitrogen (Baravingas va Cain, 1965). DO b~n cua cac pigment cua nho con duoc slf dung

nhir la ch~t rnau 6 nuoc giai khat duoc tang len khi dong hOp voi nitrogen.

7.5. Enzyme
Nhi~u enzyme noi sinh trong tS bao cua cay co kha nang lam m~t mau anthocyanin.
Nhirng enzyme nay duoc goi chung la anthocyanase. Dua vao dac tinh cua cac enzyme rna
nguci ta phan lam 2 nhom; Glycosidase va polyphenol oxidase (PPO). Cac enzyme nay thu
duoc ttl' n~m (fugal).
•

Glycosidase: la enzyme thuy phan lien kSt glycoside cua anthocyanin tao ra duong

nr do va aglycone nay kern b~n han r~t nhieu va m~t mall r~t nhanh khi co mat cua
catecol(Huang 1955).


•

Polyphenol oxidase (PPO): tac dung len anthocyanin voi su co mat cua O-diphenol

thong qua co ch~ oxy hoa ket hQP. Theo Gromeck va Markakis, su them vao glycosidase
va PPO xuc tac cho qua trinh peroxide hoa phan huy anthocyanin.

Minh 7: S1,1'
bi~n tinh anthocyanin voi phan ling oxy hoa catechol
Peng va Markakis da: d~ nghi mot co' ch~ rna trong do O-quinine duoc tao thanh boi su
oxy hoa anthocyanin. Blom phan l?p duoc enzyme anthocyanin-glycosidase

nr Aspergillus Niger

va chi ra anh huang cua no trong qua trinh thuy phan lien k~t glycoside cua anthocyanin. PPO la
enzyme co iinh huang y~u len anthocyanin dang quinonoidal base d~ bi thuy phan boi PPO han
dang cation flavylium. T6c d9 phan huy boi PPO phu thuoc vao str thay th~ mo hlnh cua vong B
va rmrc d9 glycosyl boa.
7.6. Anh sang
Cac anthocyanin thuong khong ben khi ti~p xuc voi tia ttl' ngoai, anh sang th~y dUQ'C,va cac
nguon phap xa khac, Anh sang co 2 anh huang d~n anthocyanin:
•

Tang cuong cho qua trinh sinh t6ng hop.

•

Xuc ti~n su bien tinh cua chung.

Narn 1964, Siegenrnan eho r~ng nhttng qua tao giong do se chuyen sang rnau xanh khi d~
trong b6ng t6i. Nam 1968 Vanburen va cac cong

S1,1'

tuong trinh r~ng cac diglueoside duoc acyl


hoa

va methyl hoa thi cac Anthocyanin trong nrou ben nheit khi d€ ngoai anh sang,

diglucoside khong bi acyl hoa la it ben han va monoglucoside

cac

la kern ben nhat, nam 1975

Palamidis va Markakis d1:ltim thay r~ng anh sang thuc dAy qua trinh phan huy anthocyanin trong
mroc giai khat co CO2 duoc phdi mau voi anthocyanin tir xac nho. Macccarone va cong

S\T

d1:l

nghien cuu sir quang hoa cua anthocyanin va chi ra rang , anthocyanin diglycosyl hoa tai vi tri C3 va C-5 la ben han cac anthocyanin mono glycoyl hoa tai vi tri C-3 d6ng thai chung ben han so
voi cac aglycone nrong irng,

7.7. Dlfb'ng

6 n6ng

va cac san phiim

bi~n tinh ella chang:

de>100 ppm, duong va cac san pharn phan huy cua chung co tac dung thuc dAy su

phan huy cac anthocyanin, trong do fructose, arabinose, lactose va sorbose co kha nang phan huy
anthocyanin manh han glucose, sucrose, va maltose. T6c de>phan huy cua anthocyanin lien quan
d@nt6c de> phan huy cua duong, Cac san pharn phan huy cua duong g6m co: furfura 1,5hydroxymethyl furfural va acetaldehyde thu duoc ttl" phan irng Mailard hoac til"S\!' oxy hoa cua
acid ascorbic, poJyuronic boac a ban than cac anthocyanin. Nhirng san pham phan huy nay d~
dang ngung tu voi cac anthocyanin hinh thanh nhirng hop chfrt phirc tap co man nau s~m. S\!'
phan huy anthocyanin voi

SI,!"

co m~t cua furfural va HMF true ti~p phu thuoc vao nhiet de>va

duoc thay ro nhfrt la trong mroc trai cay

S\I'

co m~t cua no lam tang them hieu qua phan huy cua

teitca cac loai duong va cac d~n xufrt cua chung.

OH

OH

+
OH

11110

OH
OH

OH

'-oAc~ ~

.....-:

........
H

OH

Jk_Q


Hinh 8: Phan ling ngung tu cua
a) Cyanidin va furfural
b) Cyanidin keto base va furfural

7.8. Cac ion kim loai:
Mot s6 ion kim loai da hoa tri co th~ nrong UtC voi cac anthocyanin co nhorn OH (; vi tri

ortho gay ra hieu irng sau mau (bathocromic). Hien tuong nay xay ra khi kim loai ti~p xuc vo i
anthocyanin trong qua trlnh che bi~n rau qua hoac

S\1' cho

them cac mudi kim loai vao trong thuc

pham.
Sistrunk va Cash dii chung minh dng co th~ ben hoa mau cua dich trich dau bang each them
vao do muoi thiec. Francis (1977) cong b6 rang, cac ion Ca, Fe, Al tao them su bao v~ cho
anthocyanin cua nuoc ep trai man viet qu~t (cranberry), nhung su bien d6i mau xay ra la do

S\1'

tao plnrc giita ion kim loai va tannin, k~t qua sau cung la khong co 19'i.
Trong cong nghiep d6 hop, sir mAt mau cua nhirng trai cay co chua anthocyanin la do co
phan ling voi thiec cua d6 hOp (Culpepper va caldwell, 1972). Trang phan ung voi thiec,
anthocyanin dong vai tro nhu cb~t khir cue catod boac anod. Ch~t klnr cue catod co th~ bi khu
boi hydro moi sinh til" phan irng gi"(1'akim loai va acid, con ch~t khu

CI!C

anod thuong la cac

anthocyanin co it nh~t 2 nhorn hydroxylo vi tri ortho.

7.9. Sunphurdioxide (S02)
Cac anthocyanin thuong bi m~t mall khi co mat cua S02. Hien tuong nay thuong xay ra
trong qua trinh

xu' Iy cac san pham

thuc pham co chira anthocyanin bang S02. Qua trinh khir nay

co th~ la thuan nghich hoac b~t thuan nghich, Trai cay va mroc qua duoc xir Iy bang mot IUQ'ng
trung blnh S02 (500 - 2000 ppm), lam m~t rnau cac anthocynin cua chung tnroc khi ch~ bien,
han nira, chung duoc desunfit hoa va mau anthocyanin duoc phuc h6i. Jurd dii d~ nghi sa d6
phan ung thuan nghich gina S02 va anthocyanin trong do, dang co mau flavylium phan irng voi
ion bisulphate tao thanh chrornene-Z{hoac 4)- sulphonic acid.


Hinh 9: Sa d6 Jurd d6i voi phan irng thuan nghich giu'a S02 va anthocyanin
S02

(y

nong d9 r~t th~p (khoang 30 ppm) co th~ ire che su bien tinh do enzyme cua anthocyanin

trong qua anh dao nhung khong lam mit mau chung (Goodman

va Markakis, 1965 ). Su dy mau

b~t thuan nghich xay ra trong qua trlnh t~y qua. voi luong Ian S02 (0.8 - 1.5%) va soda (004 1.0%) duoc dung trong qua trlnh t~y qua. Phan ung b~t thuan nghich nay chua duoc biet hoan
toano

7.10. Acid ascorbic
Nbi~u nha khao sat (Beatie va cong
1953; Markakis va cong

sir

sir

1943; Pederson va cong su 1947; Kertesz 1952; Mescbter

1957; Starr va Francis 1968) quan sat

S\T

bi6n mit d6ng thoi cua acid

ascorbic va anthocyanin trong nuoc trai cay t6n trti: va d€ nghi mot tuong tac co th~ co gitta 2
hop ch~t nay. Acid ascorbic hien dien trong h<1uh6t cac san pharn trai cay, vitamin nay bi oxy hoa
tao thanh H202 va chinh H2021am m~t mau anthocyanin.