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BI GING
HA HC CC H P CHT THIN NHINi t ng: CN Ha hc
GVGD: ThS. Phm Th Chnh
B mn Ha hu c Khoa Ha hc H Khoa hc
H Thi Nguyn
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NI DUNGCh ng 1: Ph ng php nghin c u
Ch ng 2: CacbohidratCh ng 3: TecpenoitCh ng 4: Steorit
h ng 5: Flavono tCh ng 6: Ancaloit
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CH NG 1PH NG PHP NGHIN C U
1.1 Lch s v i t ng nghin c u1.2 Phn lo i cc h cht thin nhin 1.3 Sinh tng h p cc h p cht thin nhin1.4 Qui trnh nghin c u cc h p cht thin nhin
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Nghin cu chuyn su
Xut pht
-Nhim v
Phn lp, nhn dng,nhc im
Xcnh cu trc
Tng h p cc h p cht phn t nh
Nghin cu hot tnh sinh hc
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1.2 Phn loi cch p cht thin nhin
H p cht s cp
n o
H p cht th cp
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H p cht s cpProtein
Cacbohidrat
Protein
Lipit
Axit Nucleic
Lipit
Axit Nucleic
Lipit
Axit Nucleic
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H p cht th cp
Protein
Tecpenoit
Steorit
Lipit
Axit Nucleic
Lipit
Axit Nucleic
Ankaloit
Flavonoit
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1.3 Sinh tng h pcch p cht thin nhinCO2+ H2O
quang hp
CacbohiratCOOH
OHOH
HO
OH
COOH
O
CH2
COOH
Tanin
amino
axitnucleic
PO43-
phenylpropan
CH3COCOOHaxit pyrovic
CH3COOHaxetic
axit bopolyketides
CH3COH
CH2COOHCH2CH2OH
axit Mevalonictecpensteroit
protienpolipeptitancanoit
Purines
aminoaxit
N2
chu trnh axit citric
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1.4 Qui trnh nghin c ucch p cht thin nhin
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CH NG 2
CACBOHIDRAT2.1 i c ng vcacbohidrat
2.2 Monosaccarit2.3 Oligosaccarit2.4 Polysaccarit
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2.1i c ng v cacbohidrat
Khi nim: Cacbohidrat hay cn gi l saccarit,gluxit, l cc h p cht hu c khng mu, t nhiuc v ngt, dtan trong n c, dkt tinh, c tmthy trong thc vt, ng vt, a s c cng thc
n 2 m.
Ngoi ra theo ngh a rng cacbohidrat c cN,S v khng phi u c v ngt.
Tn gi cc ! ng ring bit kt thc b"ngui oz (ose)
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Phn loi: da theo thnh ph#n v tnh cht cacacbohidrat
Cacbohidrat
Cacbohidrat n gin haymonoscarit (khng th thyphn c).VD: glucoz , riboz , fructoz ...
Cacbohidrat ph c
tp khi thy phnhon ton cho ccmonosaccarit.
Oligosaccaritto nn t 2 -10phn tmonosaccarit.VD: Saccaroz , lactoz .
Polysaccarit (glycan)to nnt l n h n 10 n hng vnmonosacarit: tinh bt,
xenluloz , glycogen
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-Ch c nng:+ Lm nhin liu cung
cp t i 60% n$ng l ng cho c thsng.
+ Lm khung cu trc vv b o v, th! ng c mt % cc
c' ng nh % m ni v vb o vng vt.
+ Lin kt v i protein vlipit mng, ng vai tr lmph ng tin vn chuyn tn hiugiacctbo.
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2.2 Monosaccarit2.2.1 Phn loi-nh ngh a: Monosaccarit l h p cht polyhidroxicacbonyl,phn tc nhiu nhm OH % cc nguyn tcacbon knhau.VD: glucoz , fructoz , riboz
CH2OH
CHOH
CHOH
CHOH
CHOH
CHO CH2OH
CHOH
CHOH
CHOH
C CH2OHO
CH2OH
CHOH
CHOH
CHOH
CHO
CH2OH
CHOH
CHOH
CHOH
CHOH
CHO CH2OH
CHOH
CHOH
CHOH
C CH2OHO
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-Phn loiMonosaccarit
-Da theo nhm C=O:
+ C=O l andehit: andoz
- Da theo s nguyn t C:
+ 2C (bioz ), 3C (trioz ),
,
6C (hexoz ), 7C (heptoz )
- Andoz
- Xetoz
CH2OH
CHOH
CHOH
CHOH
CHOH
CHO CH2OH
CHOH
CHOH
CHOH
C CH2OHO
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2.2.2 Cu hnh ca monosaccarita, Cng th c FisherQui nh cch vit cng thc hnh chiu fisher ca cc
monosaccarit:- Nhm c nguyn t cacbon soxi ha cao n"m trn
(nh ca trc th)ng ng (b*c-nam) (v tr s1).
- Nguyn t cacbon bt i (C*) khng vit ra mchnh l giao im ca cc trc th)ng ngvn"m ngang.
- Cc nguyn tH v nhm OH n"m % cc trc ngang(trc ng-ty) (nguyn tHcthkhng vit ra).
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VD: Biu din phn t glucoz b"ng cng thc chiuFisher
Nhm nguyn t cacbon c s oxiha cao
Nguyn t cacbon bti C*
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b, Cu hnh t ng i D,L- xc nh cu hnh t ng i D,L ca cc monosaccaritng! i ta xt cu hnh ca nguyn t cacbonchiral (C*) n"mxa nhm cacbonyl nht (C4 % pentoz , C5 % hexoz ). Sau so snh v i cu hnh ca C* trong phn tglyxerandehit.
+ C cu hnh D khi OH n"m % bn ph i ca cngthc chiu Fisher.
+ C cu hnh L khi OH n"m % bn tri ca cng thcchiu Fisher.
- +ng phn D v L l mt cp i quang, nn +ng phn Dl nh ca +ng phn L qua g ng v ng c li.
- +ng phnepimer l cc monosaccarit ch( khc nhau vcu
hnh ca nguyn tcacbon s2 (C2)
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V d v cu hnht ng i D,L camonosaccarit
Nguyn t C* xa nhmCHO nht D, L- nh vt qua g ng
-OH bn phi-OH bn tri
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V dvcc cp ng phn epimer ca cc pentoz
Cu hnh ca C2 khc nhau
Cp ng phnepimer
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Cc cp epimer ca hexoz
Cp ng phnepimer
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- Cu hnh tuyt i R,S ca monosaccarit c xcnh theo hthng danh php ca Can, Ingol v Preloc,ngh a l phn cp ca cc nhm th.
CHOHO H
CH2OH
H OHH OH
(2S, 3S, 4R, 5R)- Mannose
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2.2.3 Cu trc vng ca monosaccarit- Monosaccarit khng tham gia c ht cc ph n ng ctrng cho nhm cacbonyl. iu ny c Tollens giithch da trn phn ng ca nhm cacbonyl v i nhmhidroxy trong mi tr! ng axit to ra hemiaxetal (I) vaxetal (II).
- Khi to vng, nguyn t C % nhm cacbonyl tr% thnhnguyn tcacbon bt i C * , n c gi l nguyn tC anome.
RCHO R'OH (H ) R C OHOR'(I)
R'OH (H+
) R C OR'OR'(II)
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a, Cng th c Tollens- Cng thc Tollens biu din cc phn tmonosaccarit d idng hnh chnht:
+ Mt cnh chiu di l cng thc Fisher camonosaccarit.
+ Cnh chiu di cn li c trung im l nguyn t
oxi tham gia lin k t hemiaxetan.+ Hai cnh chiu rng l cch biu din lin kt bnh
th! ng.
- Trong tr! ng h p andohexoz , skt h p ca OH % C5 tora vng 6 cnh c tn l pyranoz , OH % C4 cho vng 5 cnhgi l furanoz .
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- C1 (andoz ), C2 (xetoz ) gi lC-anome nn HO-C1(C2) gi lOH-anome.- V i dy+ng phn D:
+ OH-anome n"m bn phi ca cng thc gi l
+ng phn ,+ OH-anome n"m bn tri ca cng thc gi l+ng phn -
H OHH OH
O
CH2OH
HO H
H OH
1
2
3
4
56
, -D-glucopyranoz
HO HH OH
O
CH2OH
HO H
H OH
1
2
3
4
56
- -D-glucopyranoz
HO HH OH
CH2OH
OHO H
1
2
3
4
56
H OH
- -D-glucofuranoz
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HOCH2 OH
H OHHO H
1 2
3
4
56HOCH2 H
O
HOCH2HO
HHO
OHH
12
3
4
5 6HOCH2H
O
, -D-fructofuranoz -L-fructofuranoz
- V i dy +ng phn L: l nh qua g ng ca dy D.
HO CH2OH
H OH
HO H
12
3
4
56HOCH2 H
O O
HOCH2H65
4
3
21
OHH
HHO
OHCH2OH
- -D-fructofuranoz --L-fructofuranoz
D, L- nh vt qua g ng
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b, Cng th c Haworth- Cng thc Haworth biu din cu hnh ca monosaccarit rrng h n, c biu th b"ng mt hnh 6 ( pyranoz ) cnhhoc 5 ( furanoz ) cnh, n"m trn mt mt ph)ng vung gcv i mt ph)ng giy v i 1 nguyn toxi n"m % pha sau.
O
Furan Pyran
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- Dy ng phn D: nhm CH2OH n"m % pha trn mt
ph)ng vng:+ +ng phn , khi OH-anome n"m % pha d i mt
ph)ng vng (-CH2OH vOH-anome ng c chiu nhau).
+ +ng phn - khi OH-anome n"m % pha trn mtph)ng vng (-CH2OH vOH-anome cng chiu).
- y ng p n : n n qua g ng c a y .
OOH
H
OH
HOH
H
H
OH
H
CH2OHO
H
OH
H
OHH
OH
OH
H
CH2OH
H
- -D-glucopyranoz --L-glucopyranoz
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, -D-xilofuranoz
- -D-xilofuranoz
D-Xiloz
Qu trnh hnh thnh vng ca ! ng 5
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D-glucoz
- -D-glucopyranoz , -D-glucopyranoz
Qu trnh hnh thnh vng ca ! ng 5
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OOH
H
OH
HOH
H
H
OH
H
CH2OHO
OH
H
H
OHOH
H
H
OH
H
CH2OH
- c+ng phn L ta chiu D qua g ng, n gi n nht l
chiu theo ph ng ca trc z
z
OH
OH
H
OHH
OH
OH
H
CH2OH
HO
H
OH
OH
HH
OH
OH
H
CH2OH
H
- -
- -L-glucopyranoz
- -
- -L-mannopyranoz
G ng xy
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2
1
O
HOCH2 H6
5
4
3
21
HO H
H OH
HO CH2OH
OCH2OH
HOCH2 OH
H OH
HO H
1 2
3
4
56HOCH2 H
O
, -D-fructofuranoz --D-fructofuranoz
Cng thc Tollens
* Mi quan hgia cc cng thc biu din monosaccarit
6
5
4
3
O CH2OH
OHOH
HOH
HH
CH2OH O OH
CH2OHOH
HOH
HH
CH2OH
12
34
5
61
2
34
5
6
HO H
H OHH OH
CH2OH
, -D-fructofuranoz --D-fructofuranoz
D-fructoz
Cng thc Haworth
Cng thc Fisher
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c, Cng th c Reeves- Cng thc Reeves m t trng thi thc ca phn t, ccpyranoz c biu din % dng ghbn.
- -D-galactopyranoz
Haworth Reeves
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- Thc t a ph#n cc monosaccarit t+n ti trong thc t % dng cng thc Reeves, kc cc ! ng 5C.
- -D-ribopyranoz (56%) --D-ribopyranoz (18%)
, -D-ribopyranoz (20%) , -D-ribopyranoz (6%)D-riboz
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2.2.4 Tnh chthahc ca monosaccarita, Phn ng ca nhm cacbonyl- Trong dung dch kim cc xetoz d dng chuyn ha
thnh andoz , nn c andoz v xetoz u c ph n ngv i thuc thFellinh v Tollens1CH OH CHOH
6
5
4
32HO H
OHH OH
CH2OH
OHO H
H OHH OH
C
CH2OH
OHOH- OH- HO H
H OHH OH
CH2OH
HO H H OH
CH2OH
H OHH OH
HO H+
D-Fructoz Dng endiol D-Mannoz D-Glucoz
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-Ph n ng oxi ha:
+ Cc andoz c ph n ng v i Br2 /H2O, y l phnng dng phn bit andoz v xetoz .
+ Cc monoz khi b oxi ha b% i HIO4 to ra s nph&m l cc andehit v axit cacboxylic t ng ng khi c*t
HOCH2[CHOH]4CHOBr2, H2O HOCH2[CHOH]4COOH
n t , - o
R CHOH
CHOH
R' HIO4 RCHO + R'CHO
HOCH2 CHOH
CHOH
CHOH
CHOH
CHO + 5HIO4 5HCOOH + HCHO
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-Ph n ng kh
H OH
CH2OH
CHO
H OHOH
HO H
D-Glucoz
HO H
H OH
H OH
CH2OH
CHOHO H
D-Mannoz
H OH
CH2OH
CH2OH
H OHH OH
HO H
D-Sobitol
HO H
CH2OH
CH2OH
H OHH OH
HO H
D-Mannitol
Na-Hg
H+
NaBH4H+
HO H
H OHH OH
CH2OH
OCH2OH
H2Ni
H2Ni
D-Fructoz
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-Ph n ng osazon
HO H
H OHH OH
CH2OH
CHOHO HH OH
CH2OH
CHO
H OH
H OH
HO H
-
+ 3 C 6 H
5 N H N C H
3 C O + 3 C 6
H 5 N H N
H 2
O O H
- annoz
HO H
H OHH OH
CH2OH
OCH2OH
HO H
H OHH OH
2 H C 3
CH3COOH+3 C6H5NHNH2 (Osazon)
C
CH2OH
NNHC6H5
CH=NNHC6H5
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b, Phn ng ca nhm hydroxyl- Ph n ng v i Cu(OH)2
OHOCH2
H
H
HO
HO
H
OHH
OHOCH2
H
H
O
O
H
H
OHOH
H
HO CH2OH
H
H
O
O
H
H
HOOH
H
H
Cu
Cu(OH)2
1
2
3
45
6
12
3
45
6
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- Ph n ng to ete
OOHH H
CH2OH C H 3 O H H C l
( k h a n )
OOCH3
H
OH
HOH
H
H
OH
H
CH2OH
OHH
( C H 3 O ) S O
2 , N a O H
C H 3 I , N a O H
CH3O
OOCH3
HOCH3
HOCH3
H
H H
CH2OCH3
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- Ph n ng to este
(CH3CO)2O
CH3COO
OOCOCH3
H
OCOCH3
HOCOCH3
H
H H
CH2OCOCH3O
OH
H
OH
HOH
H
H
OH
H
CH2OH
O CH2OH
OH
OH
HOH
H
H
CH2OH(CH3CO)2O
O CH2OCOCH3
OCOCH3
HOCOCH3
HH
CH2CH3COO
CH3COO
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- Ph n ng to axetal v xetal vng
OH
OH
OH
HOH
H
H
OH
H
CH2OH
CH3 C CH3O
HCl (khan)
OH
O
O
HOH
H
H
OH
H
CH2OH
C
O OH
HOH
HOH
HH
CHOHCH2OH CH3
O H
H
OH
HH
CHCH2O
OC
CH3
CH3
OO C
CH3
CH3
HCl (khan)
CH3 C CH3O
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2.3 Oligosaccarit- Oligosaccarit l nhng cacbohydrat m khi thy phn honton cho t2 n 10 monosaccarit.
- Oligosaccarit hay gp nht l cc disaccarit v trisaccarit.2.3.1 Disaccarit- saccar cac o ra c o ra monosaccarngh a l khi thy phn hon ton 1 phn t disaccarit s. thu c2phntmonosaccarit.
- Cc disaccarit thi nhin quan trng l: saccaroz , mantoz ,lactoz v xenlobiz
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- C cng thc phn t: C12H22O11, tn ha hc l: 2-O-, -D-
glucopyranozyl-- -D-fructofuranozit hay , -D-glucopyranozyl-(10 2)-- -D-fructofuranozit.
6
5
6
5
4
2
1 2
1
O H
CH OHOHH
CH2OHO H
HOH
H
OH
H
CH2OH
O
- Khi thy phn saccaroz trong dung dch axit long hocenzim thu c mt l ng b"ng nhau D-(+)-glucoz vD-(-)-fructoz . S thy phn ny gy ra s i du quay cct (+) sang (-), v vy qu trnh ny cn gi l qu trnhnghch o ! ng, h/ n h p trn c gi l ! ng nghch
o.
433
HOHOHH
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b, Lactoz
- Lactoz hay cn gi l ! ng sa c v ngt km h nsaccaroz , c vai tr quan trng trong dinh d1 ng ca tr2 em.Trong sa ng! i c t 6-7% lactoz , sa b ch( c 4-5%
lactoz .- C CTPT: C12H22O11, tn ha hc: 4-O-- -D-
galactopyranozyl-(10 4)-, -D-glucopyranoz
OH
OH
HOH
H
H H
CH2OH
OH
O
OH
HOH
H
OH
H
H
CH2OH
HO
1
23
4
5
6
4
5
6
3 2
1
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2.3.2 Trisaccarit- Trisaccarit l olisaccarit c cha 3 gc monosaccarit.Trisaccarit phbin nht v bit r h n c l rafinoz , c tnha hc: , -D-galactopyranozyl-(10 6)-, -D-glucopyranozyl-(10 2)-- -D-fructopyranozit
5
6
OHOH
CH2OH
2
3 4
5
6
1
23
4
4
5
6
3 2
1
OH
OH
HOH
H
H
OH
H
CH2OH
HOH
H
HO
O H
CH2OHOH
HOH
H
CH2OH
O
1
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2.4 Polysaccarit- Polysaccarit l nhng polyme thin nhin, c cu to thng tr$m, hng nghn m*t xch l cc monosaccarit, lin ktcht ch. v i nhau qua lin kt glucozit.
- Polysaccarit c to thnh tmt loi monosaccarit c gi l homopolysaccarit, i din cho nhm ny l: tinh
, , .
- Polysaccarit c to thnh t hai loi monosaccarittr% ln c gi l heteropolysaccarit, hay gp nht trongthin nhin l: pectin, aga, hemixenluloz
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2.4.1 Tinh bt- Tinh bt l mt loi polysaccarit rt ph bin trong thinnhin. L thc $n quan trng ca c ng! i v ng vt.
- Tinh bt c d tr trong cc m thc vt d i dng ccloi ht, cqu (go, m3, ng, khoai , s*n, chui, ng), tpchung chyu trong cc loi ng' cc, go cha 78-80% tinh
, - , -70%...- Hm l ng tinh bt phthuc loi, ging, th! i v, a l vthnhng khc nhau.
h h h b l l h h h h
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- Vmt ha hc tinh bt l polyme sinh hc c to thnh
t cc monome l , -D-glycopyranoz lin kt v i nhau qualin kt 1,4 v 1,6-glucozit. c chia lm 2 loi:
+ Amyloz c to thnh t cc monome l , -D-
glycopyranoz lin kt v i nhau qua lin kt 1,4 glucozit.CH2OHCH2OH
L thnh ph#n chnh ca go t2 v cc ging ngu cc c t ixpcao(b% l n).
H
OH
HOH
H
H HH
OH
HOH
H
HH
O OO
4 1 4 1
n
A l i h h l D
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+ Amylopectin c to thnh tcc monome l , -D-
glycopyranoz lin kt v i nhau qua lin kt 1,4 v 1,6glucozit.
O
OH
OH
HOH
H
HH
CH2OH
O1
L thnh ph#n chnh ca go np v cc ging ng' cc c d2o l n
O H
OH
HOH
H
H H
CH2
O H
OH
HOH
H
H H
CH2OH
O OO
4 1 4 1
n
6
2.4.2 Glycogen
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- Glycogen l polysaccarit d trca c th ng vt, th! ngtp trung trong gan (khong 20%) v trong c b*p (kho ng4%), cn c gi l tinh bt ng vt.
- L cht r*n dng bt, mu tr*ng v nh hnh, d tan trongn c, phn t khi kh ng 1 tru vC, c cu trc t ng tamylopectin nhng mc phn nhnh cao h n.
CH2OH
OH
OH
HOH
H
H H
CH2O
H
OH
HOH
H
H H
CH2OH
O OO
O
O
H
OH
HOH
H
H H
O
4 1 4 1
n
1
6
2 4 3 X l l
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2.4.3 Xenluloz - Xenluloz l mt polysaccarit cao phn t, khng c tnh! ng, l thnh ph#n chnh ca mng tbo thc vt , l c s% xy dng cu trc g/ ca thc vt. Xenluloz c nhiu trongtt c cc loi g/ (40-60%), trong bng ln t i 98%.- Xenluloz c to thnh t cc monome l --D-
, .
n
1414
O
OH
HOH
H
H H
CH2OH
H
O
OH
HOH
H
H H
CH2OH
HOO
O
2 4 4 Ag
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2.4.4 Aga- Aga l mt polygalactopyranzit, c trong mt s loi rong tbin v mt sc thvi sinh vt. Aga cn gi l thch tr*ng, c dng nhiu trong cng nghip thc ph&m.
- Khi thy phn aga ng! i ta nhn c D-galactoz , L-galactoz v axit sunfuric theo t l9:1:1.
- Cc m*t xch ca aga l D-galactoz c g*n v i nhau quaC1 v C3. n m*t xch th10 li c L-galactoz , % v tr s1 v 4 ca L-galactoz th to thnh mch, cn % v tr s 6ca n b este b% i axit sunfuric; mch cko di lin tc nhvy. (cng thc lb i tp sinh vin tv. ).
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CH NG 3TECPENOIT
3.1 Khi nim3.2 Monotecpenoit3.3 Secquitecpenoit
3.4 Ditecpenoit3.5 Tritecpenoit3.6 Tetratecpenoit
3.7 Polytecpenoit
3 1 Khi nim
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3.1 Khi nim- Tecpen hay cn g i l tecpenoit l nh ng h p ch t h uc ch a C, H v O t n t i trong thin nhin m c b khung cacbon g m nhi u m t xch gi ng v i khungcacbon c a isopren, t c l c th bi u di n b i cngth c (iso-C 5)n v i (n 2). O
khng theo qui t c !u n"i v#i uiSqualen
Zerumbon
1 2
34
56
78
910
11
Oximenisopren
!uui
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Loi tepen Khung cacbon S l ng CMonotecpen (iso-C5)2 10-
- phn loi tecpen ng! i ta c$n c vo sl ng n v isopren h p thnh phn bit:
5 3
itecpen (iso-C5)4 20Tritecpen (iso-C5)6 30Tetratecpen (iso-C
5)8
40
3 2 Monotecpenoit
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3.2 Monotecpenoit3.2.1 Axiclic monotecpen- Cc monotecpen khng vng l d4n xut ca 2,6-
imetyloctan, % h#u ht cc monotecpen ny u chanhm isopropyliden (a) (+ng phn -) v mt s t chanhm iso ro en l b +n hn , .
2
6
(b)(a)2,6-imetyloctan
a Hidrocabon tecpen
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a, Hidrocabon tecpen- i v i hirocacbon tecpen loi ny, ch( c haihirocacbon ng c cp n l Oximen v Mirxen ,m/ i cht u c 3 lin kt C=C. Chng xut hin trong tinhd#u basil (Ocimum basilicum ), v tinh d#u cy nguyt qu(laurel oil). C hai u c cha ni i lin h p, chng ch(hn bit c v i nhau b% i v tr caccni i.
MirxeOximen
b Dn xut ancol tecpen
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b, Dn xut ancol tecpen-5 ng v i 2 khung hirocacbon tecpen c nhng ancol tecpencha mt hoc 2 lin kt i, u l nhng cht c mi th m ctrng, nhng n h ng qu tch c t tinh d#uhoah+ng, tinh
d#u s OHCH2OH
Linalool l mt ancol bc 3 quang ht, l thnh ph#n ca nhiuloi tinh d#u, nh tinh d#u cy o i h ng v trong tinh d#u htmi n xut hin v ihml ng kh cao.
Linalool
CH2OH
NerolGeraniolitronellol
2
c Dn xut cacbonyl tecpen
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c, Dn xut cacbonyl tecpen
Citronellal
CHO
Geranial (Citral a)
CHO
Neral (Citral b)
CHO
H+
*C CH
H
CO
CH3H
C CH
H
CO
CH3
C CH
H
CO
CH3
OH-, H2O
(CH3)2CO
citral
C O
3 2 2 Monoxiclic monotecpen
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3.2.2 Monoxiclic monotecpen- C$c monoxiclic monotecpen %u l& d'n xu(t c)a p*menthan+ p*menthan xu(t hi,n d-#i hai dng khngquang hot. c$c /ng ph0n cis v& trans.
HH
77
7
H H
p-menthan cis - p-menthan trans - p-menthan
2
345
6
89 10
1 2
345
6
8
910
1 2
345
6
8
910
a, Hidrocacbon tecpen
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* 1rong s" 23 /ng ph0n c)a menthanien c4 th5 t/n ti. ch6 c4 7 /ng ph0nd-#i 0y -c tm th(y trong tinh d!u th8c v9t:
***
*terpinen *terpinen terpinolen *phellandrene *phellandren limonen; R
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*Benthanol ho c menthan*D*ol. C2?- @E?F. l& ancol no c4 ba trung t0mchiral trong ph0n tG. v& kHt quI c4 t$m /ng ph0n l9p th5+ C(u hnt-ng "i giJa nh4m hiroxi v& nh4m isopropyl K -c x$c LnhM
neo*menthol v& neo*isomenthol E nh4m n&y Lnh h-#ng cis v#i nhau.cOn N mentol v& isomenthol chPng l& trans c)a nhau+
H
;Q
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trong tinh d!u bch 9u kh(u+ Thi l c*1erpineol v#i dung dLch axitsunUuric loKng c4 th5 thu -c hirat c)a 2.V*tecpin. C2?@E?F E+
O
(H2O )
(H*)
*O H
H3C O H(H+)H2O
H2OO H
*1erpineol 2.V*tecpin 2.V* Cineol
* Carvomenthol. C2?@E?F c4 cng thWc nh- sau
OH
c, Cacbonyl tecpen
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*Carvon . p*methan*7.V;X
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pulegon. isopulegon v& piperiton. t(t cI chPng %u c4 nh4m xeto N vL tr_ CD+
isopulengon
H
OH
Pulegon
O
Piperiton
O
* Benthon. p*menthan*D*on. C2?@2VF. chWa E nguy]n tG cacbon b(t"i xWng. v& t/n ti N 3 /ng ph0n quang hot+
D,L-isomenthonD,L-menthon
OO
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* C$c xeton no v#i nh4m chWc oxo tr]n CE nh- N Carvomethon
OH
O
OH
O
Isocarvomenthon
Neoisocarvomenthol
Isocarvomenthol
OH
Neocarvomenthol
Carvomenthon
Carvomenthol
OH
3.2.3 Bixiclo monotecpen
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p- C$c monotecpen hai vOng -c ph0n loi theo ` nh4mvOng no nh-: thu an. caran. pinan. boran. isocamphan.Uenchan. v& isobornilan+
fenchanIsobornilanIsocamphan
hujan
Bornan (Camphan)PinanCaran
a, Nhm pinan
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* @irocabon khng no quan tr ng v& * pinen l& c$c th&nhph!n ch) yHu ;V?*X? < c)a tinh d!u thng+
* inen ;2 7?C< * inen ;273?C+. uphorbiaceaceM n4 l& ch(t /ng g0y ung th-+
OH OH
PhorbolO OH
H HH
CH2OH
3.5 Tritecpen1(t cI c$c tritecpen mAt vOng Hn n m vOng v& c$c hp ch(t
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kh$c b t ngu/n t[ squanlen. CD?@ ?+ o v9y c$c tritecpen cOng i l& c$c squalenoit
HO H
H
H
H
H
Lanosterol
HO H
Squalen
HOH
H
H
R
HOH
H
H
Hopan anfa-amyrin R=CH3 (beta-amyrin)R=COOH (axit oleanolic)
3.6 Tetratecpen1etratecpen hay cn gi l carotenoit l& c$c ch(t m!u th8c ph m. hay
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cOn g i l& c$c s c t" polyen+ Caroten l& h n hp c)a D /ng ph0n. . v& * caroten. >ycopen g0y ra m!u th'm c)a c& chua v& nhi%uloi quI kh$c+
*
anfa-caroten
beta-caroten
gama-caroten
Lycopen
3.7 Polytecpen* olytecpen hay cn gi l polypren, trong cao su thin nhin l
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mt s n ph&m quan trng (chu i ca ;w
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CH NG 4STEROIT
4.1i c ng4.2 Cc sterol4.3 Cc axit mt
4.4 Cc steroit vitamin4.5 Cc steroit hocmon
4.1 i c ng* \A khung c)a c$c steroit c(u to bNi b"n vOng cacbon d_nh kHt v#i
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nhau 5 to th&nh penhiro xiclopenta a phenanthren. C2`@EV. haycOn g i l& gonan ho c steran+
27
262524
232221
20
19
18
B
C D12 8
9
10
11
12 13
14 15
16
1717
16
1514
1312
11
10
982
1 DC
BA
- c i m d!nh "#t $%ng + C$c vOng v& \ c4 th5 d_nh kHt v#i nhauho c theo cis ho c theo trans. vOng \ v& C lun trans. vOng C v& th-fng trans. tuy nhi]n c ng th-fng g p s8 d_nh kHt cis. th_ dj nh- c$c cacdenolit v& c$c buUadienoit+
CholestanGonan
3
4
56
776
54
3
- Sh4m metyl N nguy]n tG cacbon s" 2? -c dZng l&m i5m chu n+C$c nh4m thH v& c$c nguy]n tG hidro -c Lnh vL N cZng ph_a tron
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ph0n tG nh- nh4m n&y -c ch6 Lnh l& c$c nguy]n tG M c$c nh4mthH ho c nguy]n tG hiro N ph_a ng-c li c)a vOng l& c$c nh4m +@ai /ng ph0n l9p th5 l& **cholestan v& **cholestan. c$c vOng\ C v& C -c d_nh kHt trans+
1717
**Cholestan **Cholestan; *\: trans< ; *\: ciseucoanthoxianin cOn -c g i l Ulavan*D.3*diol+
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Thi un si v#i n-#c ho c etanol c4 m t axit @Cl.leucoanthoxianin s chuy5n h4a thnh anthoxianin+C$c ch(t thuAc nh4m ny m#i ch6 tm th(y d-#i dng
aglycon. ch-a tm th(y N dng glyco it+
h, Nhm catechinCatechin l c$c d'n xu(t Ulavan*D*ol+ o c4 hai trung t0m
khng trZng v9t Inh. chPng t/n ti d-#i dng hai c p diastereome.dj $ hi i hi
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g g g g pv_ dj c$c c p catechin v epicatechin+
1rong s" b"n /ng ph0n quang h c ny c)a catechin thch6 c4 ;=
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% m t c(u trPc. iso Ulavanon kh$c iso Ulavon N ch
khng c4 li]n kHt i giJa CE v CD. loi hp ch(t ny c ngkhng cho phIn Wng mu xianidin+
5.3 inh t ng h p c+c h p ch/t lavonoit- 6 c$c Ulavonoit mAt n vL C2 c sN bao gif c ng c4 m tnh- -c th5 hi,n N c(u trPc sau:
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(
* \zng c$c th_ nghi,m $nh d(u bzng /ng vL ph4ng x ng-fita K x$c Lnh -c rzng ti5u n vL rCD c4 ngu/n g"c t[ shikimat v ki5u n vL kia ;nh0n thm < c4 ngu/n g"c t[
polyketit+* Ti5u kHt hp oxi c)a vOng -c ch6 ra N hnh tr]n v vOng\ c4 ki5u thH 3*hidroxy. D.3*dihidroxy ho c D.3. *trihidroxy+
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5.4%o*t t0nh sinh h c c2a c+c lavonoit- C$c Ulavonoitc4 t$c djng ch"ng oxi h4a ;antio&idant
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-c hot t_nh sinh h c c)a chPng+ lavonoit c4 khI n ng km hKmc$c qu$ trnh oxy h4a d0y chuy%n sinh ra bNi c$c g"c t8 do hotAng+* 1uy nhi]n. hot t_nh ny th5 hi,n mnh hay yHu phj thuAc vo ci5m c(u to h4a h c c)a t[ng ch(t Ulavonoit cj th5+
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CH NG 6ANCALOIT
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ANCALOIT6.1 Khi nim v vai tr sinh hc6.2 Phn l p ancaloit6.3 Phn loi v danh php
6.4 Mt s ancaloit tiu bi u
6.1 Khi nim v vai tr sinh hc
a, &h+i ni m 'ncaloit l m t nh*m h+p ch t thi n nhi n m h u h#t
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l c/c d0 $%ng ch1a nit2, c* t!nh 3a42, c* trong m t s5 sinh$6t nh t 0nh.
3
12
O
O
1211
109
8 7 6
5
4
OCH 3
CH 3ON+
OH
Beberin
4 a' NicotinN
CH3
N
N
O
CH3
OCH3
N
N
CH3
Cofein
b, !ai tr sinh hc
* ncaloit hnh th&nh 5 bIo v, c0y. v c$c ancaloitn4i chung %u r(t Ac v#i Ang v9t+
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g ( g* ncaloit c4 vai trO g0y ph$t djc cho c0y+* ncaloit l& ch(t d8 trJ dinh d-ng nui m!m c0y
cho thH h, sau+* ncaloit l& ch(t trun ian ha ch(t thIi tron u$
trnh trao i ch(t+C4 th5 ancaloit c4 cI b"n chWc n ng tr]n+
6.2 Phn l p ancaloit
a. Sghi%n nh nguy]n li,u ;l$. th0n. r< th&nh bAt r/ing0m v#i dung dLch axit @Cl ;ho c ng0m tr8c tiHp bzng dung
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dLch SaECFD< 5 chuy5n ho$ ho&n to&n ancaloit th&nh mu"iclohidrat d tan+
b. > c l(y dung dLch mu"i ;b bK 5 xG l_ giai onsau
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ancaloit thnh 4 nhm cht nhsau:= Sh4m 2 c4 c$c nguy]n t" C. @. S+= Sh4m E c4 c$c nguy]n t" C. @. S. F+= Sh4m D c4 c$c nguy]n t" C. @. S. Y+= Sh4m 3 c4 c$c nguy]n t C. @. S. F. Y+
C$c ancaloit nh4m D c4 A Ac cao nh(t. th-fng c4 trong n(mAc+
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6.3.2 Danh php
* i,c $nh s" trong vOng ancaloit n giIn tu0n theovi,c $nh s" trong c$c dL vOng K biHt+ 1h_ dj. c$c
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ancaloit loi tropen $nh s" theo ki5u vOng bixiclo:
78 3
21
NCH 3
Atropin
Tropan
9 '
8 '
7 '6 ' 5 '
4 '
3 '2 '1 '
3NCH 3
H
O CO
CH
CH 2OH
1 2
45
8
6
7
5
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* #i c$c vOng phWc tp hn th phIi ch n vOng c sN g!n gi"ng v#ivOng K biHt r/i $nh s" vOng c sN theo ki5u $nh s" vOng K biHtiHp Hn c$c vOng kh$c sao cho c4 tr9t t8 hHt vOng n&y Hn vOnkh$c+
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kh$c*1h_ dj: {$nh s" trong ph0n tG mophin. mAt ancaloit loi
isoquinolin. nHu $nh s" vOng t[ isoquinolin th r(t phWc tp. n]nobinson K bi5u din v& $nh s" theo ki5u vOng phenantren:2
12
34
567
8
9
10
11
1213
14
PhenantrenMophinki5u phenantren
O
HO
N CH3
34
5
67
8
9
1011
1213 14 15
1617
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Ti liu tham khoTi liu tham khoCarey F.A.Carey F.A.Organic chemistryOrganic chemistry (5ed., MGH,(5ed., MGH,20042004)(T)(C)(1335s).)(T)(C)(1335s).
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M. C. Steven, J. M. Russell,M. C. Steven, J. M. Russell, Bioactive Natural Products, detection, Isolation and Structural Bioactive Natural Products, detection, Isolation and Structural Determination Determination . CRC Press,. CRC Press,19931993
. J. A. March , M. B. Smith"Advanced Organic Chemistry. Reactions, Mechanisms and. J. A. March , M. B. Smith"Advanced Organic Chemistry. Reactions, Mechanisms andStructure (Fifth Edition), J. Wiley & Sons,Structure (Fifth Edition), J. Wiley & Sons,20012001..J. Clayden, N. Greeves, S. Warren and P. Wothers,J. Clayden, N. Greeves, S. Warren and P. Wothers,Organic ChemistryOrganic Chemistry , Oxford University, Oxford University
, ,, ,Ng Th Thun, ng Nh Ti, Ha hu c tp 2, NXB GDNg Th Thun, ng Nh Ti, Ha hu c tp 2, NXB GD20122012..
Phm Th Chnh,Phm Th Chnh, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKH, H Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKH, HTN TN Phan Tng S n,Phan Tng S n, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, HQGHN. HQGHN.Nguyn V$n u,Nguyn V$n u, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, HQGHN HQGHN. .
Phm V$n Th(nh,Phm V$n Th(nh, Bi gi ng Ho h c cc h p ch t Thin nhin v ho t tnh sinh l c a chng, Bi gi ng Ho h c cc h p ch t Thin nhin v ho t tnh sinh l c a chng,ti li u ni b , HSP, HTN.ti li u ni b , HSP, HTN.L Huyn Trm,L Huyn Trm,Th c hnh Ho h c cc h p ch t Thin nhin, ti li u ni b , Phng TNTh c hnh Ho h c cc h p ch t Thin nhin, ti li u ni b , Phng TN
HCTN, HKHTN, HQGHN, 2006. HCTN, HKHTN, HQGHN, 2006.
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