Académique Documents
Professionnel Documents
Culture Documents
6 7
1
Cykliske oligosakkarider
2
Hydrophobic cavity
Secondary hydroxyl groups
7.8 Å
3
Complex formation
[GCD]
G + CD GCD Kass = (M-1)
[G][CD]
4
CGTase enzyme
5
Practical production of cyclodextrins
Selective precipitation of
Selective complexants: one type of cyclodextrin
α-CD: decanol
β-CD: cyclohexane, limonene, cyclodecanone
γ-CD: cyclohexadec-8-en-1-on, cyclododecaone 6
Cyclodextrin karakteristika
7
Cyclodextrin opløselighed
8
Important cyclodextrin derivatives
9
Cyclodextrin struktur
10
α-cyclodextrin
β-cyclodextrin
11
γ-cyclodextrin
δ-cyclodextrin
12
Cyclodextrin kompleksdannelse
Dipol-dipol interactions
Release of ”high-energy” water
Hydrogen bonds
14
Guest-molecules I
15
Guest-molecules II
16
Guest-molecules III
Misfolded protein
Protein-detergent
intermediate
Ad cyclodextrins
+
Active protein !
17
Guest-molecules IV
18
Guest-molecules V
Anti-aging concentrate:
Vit. C and vit. A-β-CD
complex
19
Possible effects of complex formation between
a guest molecule and α-, β- og γ-cyclodextrin
Enhanced/reduced - aqueous solubility
- bioavailability
Enhanced/reduced stability against - hydrolysis
- oxidation
- UV-light induced degradation
- heat
- reduced volatility
Reduction of unwanted taste and odour
Areas of application:
- Analytical chemistry (e.g. chiral separations)
- Medical industry
- Food industry
- Chemical industry
- Studies of molecular interaction
20
Cyclodextrins – for efficient and safe delivery of drugs
21
Selective extraction using cyclodextrins
Removal of cholesterol from eggs and dairy products
22
Cyclodextrins in textile finishing
controlled release of e.g. perfumes
23
Analytical chemistry – chiral separations
24
Cyclodextrin anvendelse - bioteknologi
25
Cyclodextrin anvendelse - bioteknologi
26
Enzyme mimics
27
Cyclodextrin-protein interaction Phosphoglycerat kinase
N D
+CD
DCD Dagg
28
Cyclodextrin toksikologi
29
From Dr. Jens Moldenhauer
Cyclodextrin derivater – ændret selektivitet
30
Large cyclodextrins
Cyclodextrins with DP>8
OH
OH OH
HO O
O O OH
O
HO HO O OH
OH O
O
OH HO
O
HO OH
O
8 O OH
9 HO OH
10, 11, 12…..
6 7 HO
O
OH
O
HO HO O OH
OH
O O
HO
O O O
HO
OH
HO HO
HPAEC-PAD
B. macerans CGTase
Amylomaltase
D-enzyme
CGTases
6 10 15 20 25 30 35
32
D.P.
Purification of large CD
High D.P.
CD9 ? ALL ! mixtures
Amylomaltase
D-enzyme
CGTases
6 10 15 20 25 30 35
D.P.
Chemical synthesis CD9
Wakao et al. (2002) J.ORG.CHEM. 67:8182
3 x maltotriose 33
Store cyclodextriner - oprensning
34
Store cyclodextriner - karakteristika
Table 1: Nomenclature and some properties of cyclodextrins.
Glycosyl Semisystematic name Generic namea Abbreviation Molecular Aqueousd,e Surface tentiond,e Specifice Half life ofe,f
units weight solubility (mN/m) rotation [α]25 D ring opening
[g per 100 ml] (h)
6 cyclomaltohexaose α-cyclodextrin α-CD 972.9 b 14.5 72 147.8 33
7 cyclomaltoheptaose β-cyclodextrin β-CD 1135.0b 1.85 73 161.1 29
8 cyclomaltooctaose γ-cyclodextrin γ-CD 1297.2b 23.2 73 175.9 15
9 cyclomaltononaose δ-cyclodextrin CD 9 1459.3b 8.19 73 187.5 4.2
10 cyclomaltodecaose ε-cyclodextrin CD 10 1621.4b 2.82 72 204.9 3.2
11 cyclomaltoundecaose ζ-cyclodextrin CD 11 1783.6b >150 72 200.8 3.4
12 cyclomaltododecaose η-cyclodextrin CD 12 1945.7b >150 72 197.3 3.7
13 cyclomaltotridecaose θ-cyclodextrin CD 13 2107.9b >150 72 198.1 3.7
14 cyclomaltotetradecaose ι-cyclodextrin CD 14 2270.0b 2.30 73 199.7±1.0 3.6
15 cyclomaltopentadecaose κ-cyclodextrin CD 15 2432.2b >120 73 203.9±0.4 2.9
16 cyclomaltohexadecaose λ-cyclodextrin CD 16 2594.3b >120 73 204.2±0.7 2.5
17 cyclomaltoheptadecaose µ-cyclodextrin CD 17 2756.4b >120 72 201.0±0.6 2.5
18 cyclomaltooctadecaose ν-cyclodextrin CD 18 2918.6b - - - -
19 cyclomaltononadecaose ξ-cyclodextrin CD 19 3080.7b - - - -
20 cyclomaltoeicosaose ο-cyclodextrin CD 20 3242.9b - - - -
21 cyclomaltoheneicosaose π-cyclodextrin CD 21 3405.0b - - - -
22 cyclomaltodoicosaose - CD 22 3567.2c - - - -
23 cyclomaltotriicosaose - CD 23 3729.3c - - - -
24 cyclomaltotetraicosaose - CD 24 3891.4c - - - -
25 cyclomaltopentaicosaose - CD 25 4053.6c - - - -
26 cyclomaltohexaicosaose - CD 26 4215.7c - - - -
27 cyclomaltoheptaicosaose - CD 27 4377.9c - - - -
28 cyclomaltooctaicosaose - CD 28 4540.0c - - - -
29 cyclomaltononaicosaose - CD 29 4702.2c - - - -
30 cyclomaltotriacontaose - CD 30 4864.3c - - - -
31 cyclomaltohentriacontaose - CD 31 5026.5c - - - -
n - - CD n n·162.14 - - - -
a
[22-27], b calculated from the molecular formula and confirmed by mass spectroscopy [22-28], c
calculated from the molecular formula and confirmed by mass spectroscopy [28], d observed at
25°C, e [24, 51], f In 1M HCl at 50 °C.
35
δ-cyclodextrin egenskaber
36
Store cyclodextriner – kompleks dannelse
37
Fujiwara et al. (1990) Chem.Lett. 739 Saenger et al. (1998) Chem.Rev. 98:1787 Harata et al. (1998) Supramol.Chem. 9:143
Endo et al. (1999) Anal.Sci. 15:613 Saenger et al. (1998) Chem.Rev. 98:1787
2x
38
Saenger et al. (1998) Chem.Rev. 98:1787 Kitamura (2000) Cyclic Polymers 125
CD26-krystalstruktur
CD26- krystalstruktur
V-amylose
39
”Cycloamylose” - properties