Phn 2 DC LIU CHA ANTHRANOID

1. 2. 3. i hong Nhu Phan t dip 4. 5. 6. Mung tru Tho quyt minh L hi

tham kho :
1- H th 2-Cht cht 3-Ba kch 4-ct kh c
1

NOI DUNG 1. nh danh thc vat & dc lieu 2. Mo ta thc vat, bo phan dung 3. Thanh phan hoa hoc chnh Anthranoid Tannin 4. Chiet xuat

5. nh tnh
6. nh lng Theo DVN II

Theo DVN III

7. Tac dung sinh hoc Cong dung
3

La

Toan cay

1. NH DANH
ai hoang gm nhieu loai thuoc chi Rheum, ho Polygonaceae

DTQ quy nh 3 loai - R. palmatum L. - R. officinale Baillon

DVN III quy nh dung - R. palmatum L. - R. officinale Baillon

- R. tanguticum Maxim ex Balf.

- R. palmatum officinale

palmatum : hnh ban tay

officinale : dc dung
6

2. MO TA Cay: than thao, ln (2 m) La: la ln (30 cm), moc thanh cum t than re, cuong dai, co be cha

(Polygonaceae), mep la xe thuy chan vt sau ( R. palmatum sau hn R. officinale),

mat di noi gan o tm nhat. Than re: rat phat trien (bo phan dung) Hoa: ngon, thng moc thanh chum Qua: co 3 canh

Hnh ngon cay mang hoa

La va ngon hoa

PHAN BO - Trung quoc, chau Au - Viet Nam con phai nhap THU HAI - Thu than re t cay tren 3 tuoi

- Cat bo re con
- Thai phien phan than re - Bao quan 1 nam mi dung
10

BO PHAN DUNG
Rhizoma Rhei

Than re a cao vo, say kho cua cac loai ai hoang - Rheum palmatum L. - Rheum officinale Baillon - Rheum palmatum officinale, ho Polygonaceae

11

BO PHAN DUNG
Rhizoma Rhei

12

2. Manh mo mem

1. Manh ban

Soi bt

3. Si

5. Hat tinh bot

4. Calci oxalat hnh cau gai

13

3. THANH PHAN HOA HOC Chu yeu : anthranoid (3% - 5%) va tannin (10%, PC > PG)
@. Aglycon (anthraquinon)

- anthraquinon t do dang oxy hoa

- anthraquinon dimer dang kh

khoang 0.1 0.2%

@. Glycosid (anthraglycosid) - glycosid dang oxy hoa - glycosid dang kh (anthron, anthranol) - glycosid dang dimer
14

khoang 2 4%

THANH PHAN HOA HOC

@. Anthraquinon t do dang oxy hoa
OH
8

O
1

OH

R6 O

R3

R6 - Chrysophanol - Aloe emodin - Rhein - Emodin - Physcion H H H OH OMe Me CH2OH COOH

R3

Me Me
15

THANH PHAN HOA HOC

@. Glycosid vi aglycon dang oxy hoa hay dang kh

- chrysophanol - Aloe emodin - Rhein - Emodin - Physcion @. Glycosid hoac aglycon dang dimer kh - Rheidin A, B, C, OH gan glucose

- Sennidin A, B, C,
- Palmidin A, B, C,
16

Cu tao cua cac dimer aglycones

Anthron 1 Rhein Aloe emodin Emodin Chrysophanol Physcion Aloe emodin Aloe emodin Emodin Rhein Rhein Rhein Rhein Rhein Emodin Chrysophanol Chrysophanol va Anthron 2 Tao thanh Sennidin A va B Sennidin C Rheidin A Rheidin B Rheidin C Palmidin A Palmidin B Palmidin C

17

Cau truc cac dimer anthrones

OH O OH

R6 R6

R3 R3

OH

OH

Cac dimer aglycon

18

Cau truc cac dimer glycosid.

glc

OH

COOR COOH

glc

OH

Cac dimer glycosid

19

4. NH TNH
4.1. Phan ng Borntrager : cua anthraquinon (t do va mi sinh) cua chrysophanol (t do va mi sinh) 4.2. Phan ng tao chelat vi Mg acetat

4.3. Phan ng vi Pyridin MeOH

4.4. Th nghiem vi thang hoa (ket hp vi Borntrager) 4.5. nh tnh so sanh 4.6. nh tnh phan biet
20

5. NH TNH 4.5. nh tnh so sanh

- Chiet bang MeOH, co dch chiet en can

- Thuy phan bang HCl (BM 30 phut) - Chiet anthraquinon bang ether, boc hi ether,

- Hoa cn / CHCl3, cham SKLM (silica gel F254)

- Khai trien 2 chieu vi 2 he dung moi

- Phat hien : UV 254 nm (so vi chuan)

21

5. NH TNH 4.6. nh tnh phan biet D Phap

Khi lan loai Rheum rhaponticum hay R. undulatum : se co Rhaponticosid (xanh da tri sang / UV 365) kiem tra bang SK G vi he BAW (4 : 1 : 5) / UV

C T
hRf = 50 55 70 80 95

mau th T a b lan rhaponticosid

22

6. NH LNG 6.1. Phng phap Auterhoff (DVN II)

-Thuy phan trc tiep vi AcOH bang, va ether

- un soi 15 phut hoi lu (Sinh han nc rat lanh)

- e nguoi, tach lay ether .

- lac dch ether vi dd (NaOH + NH3)

- Tach lp kiem (mau o), un hoi lu 15 - o quang (550 nm) - So sanh vi dung dch giai mau CoCl2 - (A cua d.dch CoCl2 1% # A cua d.dch istizin 3,6 ppm) ai hoang phai cha 2,5% anthranoid, tnh theo Istizin
23

6. NH LNG 6.2. Phng phap DVN III, 2002

- Chiet m (g) mau bang nc nong cach thuy. - e nguoi, them Na bicarbonat, lac, loc lay dch - Oxy hoa bang FeCl3 2% nong, thuy phan (HCl nong) - Chiet aglycon bang ether, can ether + Mg acetat / MeOH - o o hap thu A 515 nm (khong dung chuan) - Ket qua c tnh trc tiep X% = 64 A / 100m ai hoang phai cha 2,2% anthranoid (tnh theo rhein)
Mun nh lng cac anthranoid acid ta lc dch chit ether vi Na bicarbonat ;

24

7. TAC DUNG VA CONG DUNG

- Dang kh / dc lieu ti co tac dung kich ng can lu kho - Hoat chat thc s (/ ai trang) : aglycon dang kh mi sinh

- C che : nhu ong c trn (ruot, t cung, bang quang ...)

- Tac ong sau khi uong : cham (nhuan, xo , tay) - chuyen hoa : co qua sa, mt t qua gan, chu yeu : phan

Chu y:
- Khong dung : thai phu, ang hanh kinh, ang cho con bu, tr - Ngi co nguy c ket soi oxalat, viem bang quang

- Dung lau : tao bon

- oi khi nc tieu va phan bi nhuom hong
25

- Cac vi khuan tai ruot gia cat

Sennoside A, B, C, D (8 O-glycosid) + (Sennidin) - Sennidin b kh tiep rhein anthron + anthron khac

co tac dung nhuan tay.

- Sau khi uong khoang 8 h : co tac dung. - Sau 24 h thai tr - T 24 48 h : ng tieu (30%), phan (20%) : lng thai ch con khoang 2%

- Tang thai : nc tieu, Natri va Kali

26

7. TAC DUNG SINH HOC

- Cac anthraquinon (Rhein, Emodin, Aloe emodin)

c che Bacillus subtilis, Staphylococcus aureus.

- Rieng Rhein (co COOH)

c che cac vi khuan yem kh chu yeu cua he tieu hoa

(nh c che c che chuoi ho hap te bao tai giai oan ty the)
can tr chc nang kh cua NADH dehydrogenase) -Emodin khang khoi u va chong di can cua te bao ung th (2006) -Lieu dung : 0,1g (Bo); 0,15g (nhuan); 0,5-2g (So)
27

MT VI BI THUC THNG DNG

Tr chng lipid huyt cao: dung con chiet xuat ai hoang , lam thanh vien 0,25g,moi ngay uong luc sang sm 3 vien x 3 tuan, kt qua tt; s bnh nhan tri glyceride va beta-lipoprotein
cao t kt qu 76%;

Tr chung trng v thc nhiet, tao bon :

Tr chan thng do te nga:

ai hoang : 10 - 15g, Hau phac : 8g, Ch thc :8g, sac uong Mang tieu : 10g ( hoa ung) neu bung chng; i hong, ng qui lng bng nhau tn bt mn, 10g x 2 ln/ngy, ung vi ru. Tr bong gn, huyt au do t ng, trong ung ngoi xoa. Tr xut huyt tiu ha trn: dng bt (vin hoc sir) i hong mi ln ung 3g, ngy 3 ln ,kim tra phn m tnh hoc dng tnh nh mi thi ung, Bnh qun thi gian cm mu l 2 ngy,

28

PHAN TA DIP

29

30

31

Cassia angustifolia (L hp)

32

1. M TA Co 2 loai thng dung: - Cassia angustifolia Vahl., Phan ta dip n

- Cassia acutifolia Del., Phan ta dip Ai cp

Cy: nho, cao n 1 m, moc thanh bi. La: kep lng chim chn, loai C. acutifolia co t 4 5 i la chet, C. angustifolia co 5 8 i, inh nhon. Hoa: moc thanh chum nach la, canh mau vang, co 10 nhi,

co 3 nhi lep.
Qua: loai qua u det, cha 6 8 hat
33

1. C iM THC VT Phan t : Cassia angustifiolia Vahl. Cassia acutifolia Del. Phan ta l hp (L hp) (L nhn) Phan ta l nhn

Ngun gc
Trng nhiu L, qua S l cht Vit Nam

Arab
n di, hp nhiu hn

Phi chu
Ai cp ngn, mp it hn +++
34

2. THANH PHN HOA HOC @. Cac anthranoid dang t do (0,05 0,10%) Rhein, aloe emodin, chrysophanol @. Cac dimer anthranoid (2-3%): Sennosid A, B = dirhein anthron Sennosid C, D = rhein anthron + aloe emodin anthron @. Cac flavonoid: kaempferol, isorhamnetin @. Cht nha: gy au bng, tan trong cn va nc nong

nhng bi tua khi ngui. Do o cn ngui va loc loai

nha trc khi ung.
35

Glc

OH

Glc

OH

rhein
H H COOH COOH H H

rhein
COOH CH2OH

rhein
Glc O O OH Glc O O OH

aloe emodin

Sennosid A, B (homo-dianthron) hot cht chnh

Sennosid C, D (hetero-dianthron)

36

3. INH TNH 3.1. Phn ng Borntraeger (Anthranoid + kim mu ) 3.2. Sc k lp mng Dch chm: dch cn Phan t dip H dung mi: n-propanol-EtOAc-nc (4:40:30) Pht hin: phun HNO3 25%, sy 120 OC/10 pht, phun tip dung dch KOH 5%/ cn 50 %. Kt qu phi cho 2 vt nu ta ca sennosid B (Rf 0,1-0,2) v 2 vt sennosid A (0,3-0,35). Tin hnh song song vi mu chun

37

SC K LP MNG

mu = dch chit cn nc bn = silica gel F254 hdm = n-PrOH EA H2O (4 : 40 : 30) sau khai trin : - oxy ha vt - hin mu vt = HNO3 nng, sy kh = KOH / ROH

so vi 05 vt chun

sennosid A, B, C, D v rhein glucosid

38

4. INH LNG Phng phap D Phap 1972 - Chiet m (g) mau bang nc nong cach thuy. - Acid hoa = HCl, lc vi CHCl3, loi CHCl3. - e nguoi, them Na carbonat, lac, loc lay dch - Oxy hoa bang FeCl3 10%, thuy phan (HCl nong)

- Chiet aglycon bang ether, can ether + KOH 1N

- o o hap thu A 500 nm - o hp thu ca 1 dd chun 1,8-diOH anthraquinon bit nng .

- Tnh kt qu, bit 1 mg 1,8-diOH anthraquinon ~ 1,797 mg sennosid.

39

NH LNG dch nc nng dch nc acid

Na2CO3,(pH 7-8) + (FeCl3 + HCl, )

bt PTD

+ vi git HCl, ra = Cf (loi chlorophyll + AQ + nha)

dch thy phn + oxy ha

chit kit = Et2O

dch ether ln acid, mui

ra = H2O KOH

o Abs. 500 nm // dd. chun Istizin

dch ether

cn ether

mu
40

1 mg Istizin # 1,8 mg sennosid

TAC DUNG & CNG DUNG Cng dung ch yu : nhun ty

Ung:
C ch:

C tc dung sau 8 12 gi
(thut: tc dung nhanh hn) Kiu AQ (tng nhu ng c trn)

- kch thch tiu ha (1 2 gam l)

- nhun trng - ty, x (3 4 gam l) (5 7 gam l)

Chu y:
S dung:

Loi b cht nha

(gy au bung)

bng cch ra vi ru, lnh dch nc . . . L (ch yu); Qu (b ht); Sennosid A, B.

41

Chng chi nh: Kiu AQ

5. TC DNG VA CNG DNG Tac dng kch thch tiu hoa, nhun va ty tu theo liu s dng.

- Liu gip tiu hoa: 1-2 g l

- Liu nhun: 3 4 g l - Liu x: 5 7 g

Chng chi inh i vi ngi co thai, vim t cung, bang

quang. Dang dung: thuc hm hoc thuc tht. Tuy nhin nn

ra cn hoc loc loai nha trc khi dung tranh au

bng.
42

Lc mu v ty c c th bng Tr PHAN TA DIP

i vi nhng ngi b bnh gan nh vng da, x gan, p xe gan, vim gan Hepatitis A,B,C,E hay ung th gan.. s c du hiu chn n v khi xt nghim ch s men gan SGOT v SGPT (serum glutamic oxaloacetic transaminase v serum glutamic pyruvic transaminase) tng cao hn bnh thng gp 2-5 ln lm tiu hy t bo gan. Du hiu khi bnh khi no th ch s men gan gim. Tt c cc bnh gan sau khi ung Phan T Dip vi liu cao 12g/ln, ngy ung 2 ln, b Phan T Dip vo 1 ly nc si ngm 30 pht, hay nu si cho thuc thm ra tr thnh nu hng m, ung ht 1 ln mt ly, vn n ung bnh thng, khi i cu ra phn en lng tiu chy, tip tc ung cho n khi i phn d dng v phn khng lng nt na m tr li phn do, mu vng, th ngng. Khi i th men gan SGOT, SGPT gim xung bnh thng th khi bnh. Ung phng bnh th liu 4g/ ngy c tc dng lc mu v gim men gan.

43

MUNG TRU

44

45

46

47

1. M T
Tn khoa hoc: Cassia alata L. Fabaceae Dang cy: nho; cao 1,5 m 3 m, thn g mm, d = 10-12 cm.

L: la kep lng chim chn, dai 30-40 cm, co t 8-14 i la

chet hnh trng, gc va inh la u trn. Cm hoa: moc thanh bng dai 12-14 cm, rng 5-6 cm, mang cac hoa mau vang sm. Qua: loai qua u, dai 8-16 cm, c 2 canh sut theo chiu doc cua qua, bn trong co 40-60 hat.

48

2. THANH PHN HO HOC

@. Trong la co cha cac dn cht anthranoid: chrysophanol, aloe emodin, rhein, emodin. @. Trong r co 2 dn cht anthraquinon c phn lp: - 1,3,8-OH, 2 CH3-anthraquinon (1) - 1,5-OH, 2-CH3, 8-OCH3, 3-O-glucosyl anthraquinon (2)

@. Kaempferol
OH O OH CH3 OH O

OMe O

OH CH3 O-glc

OH

(1)

(2)

49

3. TC DNG VA CNG DNG

La co tac dng nhun va ty tu theo liu s dng. La cn dung cha hc lao bng cach gi nat ri xat vao

ni bi nm.

50

THO QUYT MINH

51

52

53

54

55

1. M T
Tn khoa hoc: Cassia tora L. Fabaceae Cy: nho, cao 30-90 cm, moc hoang nhiu ni trong nc. L: kep, lng chim chn, gm 3-4 i la chet, la km hnh si dai 1 cm. La chet hnh trng ngc. Hoa: moc k la, mau vang, co t 1-3 chic. Qua: loai qua u hnh tr, dai 12-14 cm, trong cha vai chc hat

56

2. B PHN DNG

B phn dung la hat gia

3. THANH PHN HO HOC

Hat cha chu yu la cht beo va anthranoid:

Chrysophanol Physcion Aloe emodin Rhein

Emodin
Cac glycosid cua cac aglycon trn

57

3. THANH PHN HO HOC

Ngoai ra cn cha mt s dn cht khng thuc nhom anthranoid nh: Rubrofusarin nor-rubrofusarin Rubrofusarin 6-gentibiosid toralacton

4. CNG DNG
ng y dung cha au mt o, mt m, chay nhiu nc mt, quang ga. Cn dung ch nhc u, mt ngu, giai nhit, b thn Lu : khi s dng nn sao vang loai bt cht c
58

Aloe vera L.

Aloe ferox Mill.

Asphodelaceae
(Alloen = ng, ting Arab)

59

60

61

1. M T THC VT
Aloe vera L. Thn cao Hoa L c gai C nhiu < 0.5 m mu vng mp Vit Nam Aloe ferox Mill. 2 5 mt mu mp + di Nam Phi

Aloe vera L. var. chinensis (Haw.) Berger, Asphodelaceae

62

Aloe spp.
Chi Aloe 180 loi 04 loi dng lm thuc. Trong 04 loi ny, c 02 loi thng dung Aloe vera L. = A. vulgaris Lam. = A. barbadensis Mill. = L hi Barbade Aloe ferox Mill.

= Bitter Aloe = L hi x Cape

63

Aloe vera L.

Aloe ferox Mill.

64

65

Aloe vera

Aloe ferox

66

2. B PHN DNG
2.1. Dch c c t l = Nha L hi = ALOE 2.2. Gel ca l; Bt l (sau khi thu nha)

3. CCH THU HI - CH BiN 3.1. Thu hoch nha L hi - Phng php th s

- Phng php hin i

3.2. Ch bin Bt l L hi
67

L HI

68

69

70

71

x l L hi

72

co ly gel

73

74

75

3. THNH PHN HA HC
3.1. Cc OMA - aglycon (aloe emodin; dch ti khng c) - C-glycosid (barbaloin ** = aloin A + aloin B) - glycosid hn tp (aloinosid) 3.2. Cc glycosid khc

- aloenin, aloesin
3.3. Carbohydrat (mono- v polysaccharid **) - ng chu y l cc PS kiu gluco-mannan 3.4. Khong, vitamin, enzym, lignin, saponin, sterol, amino acid, salicylic acid.
76

3. THNH PHN HA HC
OH O OH

OH

OH

CH2OH O

CH2OH H glc

aloe emodin
OH O OH

barbaloin **
OH O OMe OH

CH2O H glc

Rha

Me H glc

aloinosid

homonatalosid

77

4. NH TNH NHA L HI
4.1. Ph.ng Borntraeger (+ kim) : anthranoid ni chung

4.2. Ph.ng Schouteten (+ Na borat): anthranoid dng kh

4.3. Ph.ng vi ddch Brom 4.4. Phn ng Klunger (+ ddch CuSO4) 4.5. Ph.ng vi acid periodic; acid nitric
78

Phn bit 2 loi L hi

4. NH TNH NHA L HI
4.2. Phn ng Schouteten dch nc t nha L hi
loi tp = bt Talc

+ bt Na borat
pha long / nc

h.quang vng sng (di UV 365 nm)

4.3. Phn ng cng hp vi Brom dch nc t nha L hi

+ ddch Br2

ta mu vng
79

4. NH TNH NHA L HI
4.4. Phn ng Klunge (A. vera // A. ferox) dch nc t nha L hi

+ dd. CuSO4
NaCl / EtOH

mn bn (vera) vng (ferox)

4.5. Phn ng vi HIO4 (A. vera // A. ferox) dch nc t nha L hi + HIO4 1%

bn (vera)
hng* (ferox)
* mt sau 1 h
80

4.6. Phn ng vi HNO3 (A. vera // A. ferox) dch nc t nha L hi

+ HNO3

nu (vera) xanh vng (ferox) (DVN III)

81

4. NH TNH NHA L HI
4.7. Sc ky (SKLM hay SKG) Dung mi : phn cc (barbaloin >> aloe emodin) Pht hin : - phun, nhung d.dch Na borat hay KOH/cn

- soi UV 365 nm
4.8. Th tan

- trong ammoniac long

- trong cn 60%
82

5. NH LNG BARBALOIN
5.1. Phng php o quang trc tip ( 390 nm) - kt hp SKG, so vi chun - kt hp SKLM, so vi chun 5.2. Phng php o quang gin tip - th.phn + oxy ha = FeCl3 + HCl 4N aloe emodin - chit dch thy phn bng CCl4

- +NaOH 1N; dch kim em o quang 512 nm

- so vi dung dch chun Mg acetat 0.5% / MeOH
83

5. NH LNG BARBALOIN
5.3. Phng php DVN III (2002) p. 401

Lm m bt Nha L hi = MeOH Chit bng nc nng (60 0C 30) Oxy-ha + thy phn bng (FeCl3 + HCl ; BM 4 h) Chit AQ bng Et2O C cn, + d.dch Mg acetat 0.5% / MeOH o Abs. 512 nm (// mu trng l MeOH)

Hm lng hydroxyanthracen (quy v barbaloin %)

quy nh : nha A. vera 28%; A. ferox 18%
84

6. TAC DUNG V CNG DUNG

6.1. Nha L hi (giu AQ) - thng mt, tr tiu ha - nhun, ty (kiu AQ : sung huyt, k thai . . .) 6.2. Gel l L hi (rt t AQ)

- khng khun, khng vim

- cha phng, mau lnh so - m phm 6.3. Bt l L hi (X) - nga v tr to bn
85

86

PHN LP ANTHRANOID
Bt r Nhu EtOH.H2O Dch chit cn c thu hi EtOH, + HCl long, Lc
3 OH

T R NHU
OMe
1 2

CHO

Lp ta VLC, Si-gel / DCM

damnacanthal
O OH
1 2

anthranoid SKC, Si-gel / Benzen - DCM

CHO

3 OH

cc AQ

nor-damnacanthal
87

365 + 254

365

254

ND D

ND D

ND D

88

89

90