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ANION T
GVHD: TS. BI TH B U HU B MN HA KHOA KHOA H C T NHIN IH C C N TH
C n Th 09/2010
N I DUNG BO CO
1. T 2. N 3. K 4. K ng quan i dung v ph ng php nghin c u t qu v th o lu n t lu n v ki n ngh
1. T ng quan
Ch t ho t ng b m t (CH BM) t khi ra i gi m t vai tr kh quan tr ng trong cu c s ng.
M ph m Ch t t y r a (40%) Th c ph m
S n
D t may
c ph m
http://www.rsc.org/chemistryworld/issues/2003/July/amphiphiles.asp
CH BM c t ng h p t ngu n nguyn li u d u m b phn h y sinh h c ch m. Ngu n ti nguyn thin nhin c n ki t, v n nhi m mi tr ng v i nhi u ha ch t c h i t n t i dai d ng, Nghin c u t ng h p cc CH BM thn thi n v i mi tr ng t nh ng ngu n nguyn li u ti t o: d u th c v t v m ng v t.
M in m basa.
M c ny c dng s n xu t: d u th c ph m, m bi tr n, d u biodiesel, th c n ch n nui, T n d ng cc g c hydrocarbon c a cc acid bo trong m c s n xu t CH BM l h ng i kh m i Vi t Nam. Nghin c u t ng h p CH BM sinh h c anion t m c basa
Ch t ho t
ng b m t l g?
L nh ng ch t c kh n ng h p ph trn b m t phn chia pha, c tc d ng lm gi m n ng l ng t do v s c c ng b m t phn chia pha (khl ng, l ngl ng, l ngr n). C u t o:
Phn lo i CH BM
D a vo b n ch t c a nhm a n c, CH BM c phn thnh 4 lo i bao g m: CH BM anion, CH BM cation, CH BM khng ion v CH BM l ng tnh. CH BM khng ion CH BM anion CH BM cation CH BM l ng tnh
V d :
CH BM anion CH BM cation CH BM l ng tnh
CH BM khng ion
CH BM sinh h c l g?
Thu t ng CH BM sinh h c (biosurfactants) c th hi u l: + CH BM c s n xu t b i vi sinh v t. + CH BM thn thi n v i mi tr ng c s n xu t t ngu n nguyn li u c kh n ng ti t o nh : d u th c v t, m ng v t. Nh ng h p ch t ny c kh n ng ho t t ng t nh CH BM thng th ng. ng b m t
u i m CH BM sinh h c
i u ch t ngu n nguyn li u ti t o: d u th c v t, m ng v t. c tnh th p, kh n ng b vi khu n phn h y cao, thn thi n mi tr ng, ng d ng trong nhi u l nh v c: b o v mi tr ng, nng nghi p, ch m sc y t , ch bi n th c ph m, d c ph m,
c)
M c basa
Thnh ph n: Triglyceride: 85-90 % Diglyceride, monoglyceride Acid bo t do RCOOH Ch t mu, phospholipid v vitamin
2.2 Ph
ng php nghin c u
M c l h n h p ester c a glycerol v i cc acid bo no v khng no. Acid oleic chi m t l cao nh t l 33,6%. xc nh c u trc c a s n ph m CH BM sinh h c anion, v c ng nh tm i u ki n t i u cho ph n ng.
kh o st.
2.2 Ph
ng php nghin c u
Kh o st cc y u t nh h ng n hi u qu c a cc qu trnh chuy n ha: t l mol tc ch t, th i gian, nhi t , l ng ch t xc tc. Trong qu trnh kh o st, y u t kh o st t t nh t l y u t m khi ph n ng k t thc th tc ch t chnh ph n ng h t thng qua vi c ki m tra b ng s c k l p m ng. Qu trnh kh o st c ti n hnh trn c s thay i m t y u t c n kh o st v c nh cc y u t cn l i. Qu trnh c l p l i v i cc y u t cn l i trn c s s d ng k t qu t i u c a cc y u t v a tm c. Xc nh c u trc c a s n ph m b ng ph ng php o ph 1H-NMR v 13C-NMR, ph DEPT.
3. K t qu v th o lu n
3.1 Kh o st trn ngu n nguyn li u acid oleic 3.1.1 Ph n ng ester ha gi a acid oleic v acid lactic
COOH Acid oleic (1) CH3 HO COOH p-TsOH, to O Acid 2-(oleoyloxy)propanoic (3) O COOH CH3
-CH2-CH= -CH2-CH2-CO-
-CH=CH-COOH
-CH3
-CH=CH-
-CH=CH-
-CH3
-CH2-CH= -CH2-CO-
-CH2-
-CH=CH-COOH
-CH-COOH -CH=CH-COOH
-CH2-CH= -CH-CH3
-CH2-CH3
-CH2-CO-
-CH=CH-
-CH-COOH
-CH=CH-
-CH-COOH
-CH-CH3
-CH3
Kh o st nh h
ng c a t l mol tc ch t
nh
Gi tr 150C 8 gi
ng acid oleic)
5% 700
Y u t thay i l t l mol tc ch t acid oleic v acid lactic, t ng ng l: 1:7, 1:8, 1:9, 1:10
B n m ng kh o st nh h ng c a t l mol tc ch t (EtOAc:MeOH=5:2)
1:7
1:8
1:9
1:10
T l mol t t nh t
Kh o st nh h
ng c a th i gian ph n ng
Cc y u t c nh T l mol tc ch t Nhi t ph n ng Xc tc p-TsOH (% so v i l ng acid oleic) T c khu y (vng/pht) Y u t thay i l th i gian ph n ng, l n l kho ng: 6 gi , 7 gi v 8 gi .
B n m ng kh o st nh h ng c a th i gian ph n ng (EtOAc:MeOH=5:2)
Th i gian t t nh t
6 gi 7 gi 8 gi
ng c a nhi t nh
ph n ng Gi tr 1:10 8 gi 5% 700
ng acid oleic)
Y u t thay
B n m ng kh o st nh h ng c a nhi t ph n ng (EtOAc:MeOH=5:2)
Nhi t
130C 140C 150C
t t nh t
Kh o st nh h xc tc
Cc y u t c T l mol tc ch t Th i gian ph n ng Nhi t T c ph n ng khu y (vng/pht) nh Gi tr 1:10 8 gi 150C 700
ng c a l
ng ch t
4% 5% EtOAc:MeOH=5:2 Y
u t thay
i: l
ng ch t xc tc 4% v 5%
K t lu n: l
ng ch t xc tc thch h p nh t l 5%
T l mol tc ch t = 1:10 Th i gian ph n ng: 8 gi Nhi t ph n ng: 150C L ng ch t xc tc: 5% so v i kh i l ng acid oleic T c khu y: 700 vng/pht
EtOAc:MeOH=5:2
Hi u su t: 84,42%.
T ng h p methyl oleate
Cc y u t T l mol acid oleic : methanol Xc tc H2SO4 c Gi tr 1:10 5% k/l acid oleic 4 gi 80C 600 vng/pht
T ng h p methyl oleate
Methyl oleate
Hi u su t ph n ng 88,9%
PE:EtOAc=3:1
-COOCH3 -CH2-CH=
-CH2-
-CH3 -CH2-CO-CH=CH-
Kh o st nh h
ng c a t l mol tc ch t
nh
Gi tr 160C 10 gi
ng acid oleic)
5% 700
B n m ng kh o st nh h ng c a t l mol tc ch t (EtOAc:MeOH=5:2)
1:5
1:6
1:7
T l mol t t nh t
Kh o st nh h
ng c a th i gian ph n ng
B n m ng kh o st nh h ng c a th i gian ph n ng (EtOAc:MeOH=5:2)
8 gi
Th i gian t t nh t
9 gi
10 gi
ng c a nhi t nh
ph n ng Gi tr 1:7 10 gi 5% 700
ng acid oleic)
Y u t thay
B n m ng kh o st nh h ng c a nhi t ph n ng (EtOAc:MeOH=5:2)
140C
150C
160C
Nhi t
t t nh t
Kh o st l
ng ch t xc tc
Gi tr 1:7 10 gi 160C 700
u t thay
i: l
ng ch t xc tc 2%, 3%, 4% v 5%
B n m ng l ng ch t xc tc (EtOAc:MeOH=5:2)
2%
3%
4%
5%
K t lu n: l
ng ch t xc tc thch h p nh t l 5%
T l mol tc ch t = 1:7 Th i gian ph n ng: 10 gi Nhi t L T c ph n ng: 160C khu y: 700 vng/pht ng ch t xc tc: 5% so v i k/l acid oleic
Hi u su t: 77,18%.
T l mol acid oleic v acid lactic: 1:10 Nhi t : 150C Th i gian: 8 gi Xc tc p-TsOH: 5% Hi u su t: 84,42%
T l mol methyl oleate v acid lactic: 1:7 Nhi t : 160C Th i gian: 10 gi Xc tc p-TsOH: 5% Hi u su t: 77,18%
Khi t ng h p t nguyn li u m c
M c X phng ha Acid ha Acid bo t do
M c
CH3OH/KOH
Methyl ester
Giai o n base ha
NaOH
Acid 2-(oleoyloxy)propanoic
PE:EtOAc=3:1
Transester ha h n h p
Cc y u t T l mol s n ph m : MeOH Xc tc KOH Th i gian ph n ng Nhi t T c ph n ng khu y Gi tr 1:5 1% k/l s n ph m 2 gi 65C 600 vng/pht
PE:EtOAc=3:1 Hi u su t 86,7%
-CH2-
-CH3
-CH2-
-CH3
-CH2-CH-CH2-CO-CH-OH -CH2-
-OCH3 -COO-
-CH3
-CH-OH
-CH-OH
-OCH3
-CH3
-CH2-CO-
-CH2-CH2-CH-
-CH3
-CH-COOH
-CH-OCO-
HO-CH-CH3
-CH-OH
-CH-CH3 -CH-CH3
-CH3
-CH2-CO-CH2-CH- -CH2-
-COO-
Kh o st nh h
ng c a t l mol tc ch t
nh
Gi tr 160C 8 gi
ng acid oleic)
5% 700
B n m ng kh o st nh h ng c a t l mol tc ch t (EtOAc:MeOH=5:1)
1:7
1:8
1:9
T l mol t t nh t
Kh o st nh h
ng c a th i gian ph n ng
Cc y u t c nh T l mol tc ch t Nhi t ph n ng Xc tc p-TsOH (% so v i l ng acid oleic) T c khu y (vng/pht) Y u t thay i l th i gian ph n ng, l n l kho ng: 6 gi , 7 gi v 8 gi .
B n m ng kh o st nh h ng c a th i gian ph n ng (EtOAc:MeOH=5:1)
6 gi
7 gi
8 gi
Th i gian t t nh t
ng c a nhi t nh
ph n ng Gi tr 1:9 8 gi 5% 700
ng acid oleic)
Y u t thay
B n m ng kh o st nh h ng c a nhi t ph n ng (EtOAc:MeOH=5:1)
Nhi t
t t nh t
Kh o st l
ng ch t xc tc
Gi tr 1:9 8 gi 160C 700
u t thay
i: l
ng ch t xc tc 3%, 4% v 5%
B n m ng l ng ch t xc tc (EtOAc:MeOH=5:2)
3%
4%
5%
K t lu n: l
ng ch t xc tc thch h p nh t l 5%
T l mol tc ch t = 1:9 Th i gian ph n ng: 8 gi Nhi t L T c ph n ng: 160C ng (5) khu y: 700 vng/pht ng ch t xc tc: 5% so v i kh i l
Hi u su t: 72,64%.
Giai o n base ha
NaOH
T ng h p methyl ester
Cc y u t M c basa (g) Methanol (g) KOH (g) Th i gian ph n ng Nhi t ph n ng T c khu y Gi tr 84 16 1 2 gi 65C 600 vng/pht
T ng h p methyl ester
PE:EtOAc=14:1
PE:EtOAc=3:1
Transester ha h n h p
Cc y u t T l mol h n h p : methanol Xc tc KOH Th i gian ph n ng Nhi t T c ph n ng khu y Gi tr 1:5 1% k/l h n h p 2 gi 65C 600 v/ph
Transester ha h n h p
PE:EtOAc=3:1
S n ph m CH BM anion (4')
EtOAc:MeOH=5:2
(Hi u su t 61,32%)
Hi u su t 75,18%
HCOOH/H2O2
HO COOH p-TsOH, to
O R'' C
NaOH
R= R'= HO OH R''=
O OH
OH
Xc tc p-TsOH
EtOAc:MeOH=5:1
Hi u su t 68,53%
3.3 nh gi ch t l
ng s n ph m
nh gi kh n ng t o nh
Pha tr n cc t l khc nhau v % kh i l CH BM anion, paraffin v n c. Cc y u t c Nhi t T c khu y khu y Th i gian khu y nh Gi tr 30C 15 pht 600 vng/pht ng c a:
nh gi kh n ng t o nh c a CH BM (4')
T l % v kh i l ng trong h n h p 30% CH BM + 35% n c + 35% paraffin 30% CH BM + 30% n c + 40% paraffin 30% CH BM + 25% n c + 45% paraffin 30% CH BM + 15% n c + 55% paraffin 30% CH BM + 10% n c + 60% paraffin 25% CH BM + 40% n c + 35% paraffin 25% CH BM + 35% n c + 40% paraffin 20% CH BM + 50% n c + 30% paraffin 20% CH BM + 30% n c + 50% paraffin K t qu khng b n khng b n khng b n khng b n Nh b n khng b n khng b n khng b n khng b n
Nh Nh Nh Nh Nh Nh Nh Nh
nh gi kh n ng t o nh c a CH BM (7')
T l % v kh i l ng trong h n h p 30% CH BM + 45% n c + 25% paraffin 30% CH BM + 40% n c + 30% paraffin 30% CH BM + 35% n c + 35% paraffin 30% CH BM + 30% n c + 40% paraffin 30% CH BM + 20% n c + 50% paraffin 25% CH BM + 35% n c + 40% paraffin 25% CH BM + 30% n c + 45% paraffin 20% CH BM + 25% n c + 55% paraffin 20% CH BM + 30% n c + 50% paraffin Nh Nh Nh Nh Nh Nh Nh Nh K t qu khng b n khng b n khng b n khng b n Nh b n khng b n khng b n khng b n khng b n
Ch p hnh h nh t ng b n d i knh hi n vi i n t
CH BM anion (4')
CH BM anion (7')
Xc
nh n ng
micelle t i h n (CMC)
Trong dung d ch n c: khi v t m t n ng no th cc phn t CH BM s t t p h p l i t o thnh micelle. N ng micelle t i h n l n ng m t i cc phn t CH BM b t u t o micelle. Chnh s hnh thnh cc micelle lm thay i tnh ch t v t l (s c c ng b m t, d n i n) c a cc dung d ch CH BM.
d n
Xc
N ng
nh gi tr CMC c a CH BM (4')
0 5 6 7 8 9 10
CH BM anion (g/l)
mS/cm
d n i n (mS/cm)
3 2.5 2 1.5
2.47
CMC
1.83
Xc
N ng
nh gi tr CMC c a CH BM (7')
0 2 4 6 8 10 12
CH BM anion (g/l)
d n i n (mS/cm)
12 10 mS/cm
10.75
CMC
8 7.28 6 5.02 4 2 0 0 0.33 2 4 6 8 10 2.16 4.14
9.51
g/l 12 14
Xc nh h ng s cn b ng a n n c (HLB)
L s cn b ng t ng ng gi a ph n a n ph n k n c c a CH BM.
c-k
c v
M i lin h gi a tnh ch t c a CH BM v i gi tr HLB c trnh by trong b ng sau: Tnh ch t Khng phn tn trong n Nh W/O Ch t th m t Nh O/W Ch t t y r a Ch t h tr ha tan c HLB 1-3 3-6 7-9 8-15 13-15 15-18
Xc
nh gi tr HLB c a CH BM (4)
O O Sodium 2-(oleoyloxy)propanoate Sodium oleoyl lactylate (4) COONa CH3
Nhm a n c g m: nhm -COONa c k/l mol l 67 g, nhm carboxyl -COO c k/l mol l 44 g. K/l mol ton phn t (4): 376 g V y HLB c a (4) l: 20.[(67+44)/376]=5,9 V HLB=5,9 nn (4) ha tan trong n d u nn c kh n ng t o nh W/O. c t h n trong
Xc
nh gi tr HLB c a CH BM (7)
OH O HO H3 C O O O COONa CH3
Nhm a n c g m: nhm -COONa c k/l mol l 67 g; 2 nhm carboxyl -COO c k/l l 44.2=88 g; 2 nhm hydroxyl OH c k/l l 17.2=34 g. Kh i l ng mol ton phn t (7): 482 g ng d ng lm ch t th m t. V y HLB c a (7) l: 20.[(67+88+34)/482]=7,8 V HLB=7,8 nn c th
Gi tr HLB tnh ton c theo cng th c ton h c khng c p n m t c tnh quan tr ng trong phn t ch t nh ha, l c u trc khng gian c a phn t . C u trc khng gian c a phn t CH BM c nh h ng r t l n n kh n ng t o nh t ng v v ng b n c a nh t ng t o thnh. V v y, v ng b n c a m t h nh t ng c i u ch nh ch t nh ha c thnh ph n ha h c nh nhau, gi tr HLB c tnh ton nh nhau nh ng c c u trc khng gian khc nhau th v ng b n c a nh t ng thu c r t khc nhau.
4. K t lu n v ki n ngh 4.1 K t lu n
+ Tm c i u ki n t i u t ng h p hai CH BM sinh h c anion (4') v (7') t m c basa quy m phng th nghi m. + nh gi s n ph m qua kh n ng t o nh , ch s CMC, HLB.
4.2 Ki n ngh
Xc nh thm kh n ng t o b t, kh n ng t o huy n ph, kh n ng th m t v kh n ng kch ng da c a CH BM t ng h p c. Thay i cation Na+ trong c u trc c a s n ph m CH BM thnh cc cation khc nh : Ca2+, K+, NH4+,... Nghin c u kh n ng ng d ng c a s n ph m CH BM t ng h p c trong cc l nh v c s n xu t: ch t t y r a, m ph m, d c ph m, cng ngh th c ph m,