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Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
1
PentoraffineriePentoraffinerie et chimie des pentoseset chimie des pentoses
Sandrine BOUQUILLONSandrine BOUQUILLON
Wheat bran
Enzymatic transformations
Pentoses :D-xylose
L-arabinose
Arabino-xylo-oligosaccharides
Pentoses syrup
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
2
Enzymatic hydrolysis of hemicelluloses from wheat bran
Wheat bran
Xylanase (Thermobacillus xylanilyticus)
Arabino-xylo-oligosaccharidesX2, X3, X4A, > DP
Xylosidases Arabinosidase (Thermobacillus xylanilyticus)
Structural resolution of the arabinosidasefrom T. xylanilyticus
Arabinose + xylose
Production and characterization of new xylosidases from Bacillus halodurans
Improving thermostability of xylanase
from T. xylanilyticus
2008. Biochemistry 2008, 47, 7441.
Appl. Microbiol. Biotechnol. 2006, 73, 582.
Bioresource Biotechnology 2009, 100, 338.
UMR FARE INRAC. RémondM. O’Donohue
Enzymatic hydrolysis of hemicelluloses from wheat bran
Hydrolysis of wheat bran with an xylanase at laboratory scale (g)
(UMR FARE)
Hydrolysis of wheat bran with an xylanase at laboratory scale (g)
(UMR FARE)
Transposition at semi-pilot and pilot scales
(ARD)
Transposition at semi-pilot and pilot scales
(ARD)
Xylanase Tx-Xyl40 % of xylans are hydrolysed into XOs
Enzymatic hydrolysis versus acid hydrolysis: high purity of pentoses syrup, no furfural molecules produced
Yields of enzymatic hydrolysis of xylans are identical (40 %) at the different scales
ARDF. Martel
UMR FARE INRAC. RémondM. O’Donohue
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
3
Pentoses
D-xyloseL-arabinose
Pentosides
Surfactants
Bran sirup
Enzymatic and chemical transformations
Enzymatic synthesis of alkyl arabinosides
pNP α-L-Araf
or X4A Alcools
Arabinosidasede T. Xylanilyticus
Methyl α-L-arabinoside, 55 %Ethyl α-L-arabinoside, 54 %
isopropyl α-L-arabinoside, 24 %n-butyl α-L-arabinoside, 42 %2-butyl α-L-arabinoside, 41 %
Allyl α-L-arabinoside, 33 %
OHO
OHHO
On
+
Tetrahedron Lett. 2002, 43, 9653.
Carbohydr. Res., 2004, 339, 2019.
Alkyl arabinosides
First arabinosidase described for the enzymatic synthesis of arabinose-based molecules
ICMR UMR CNRSR. Plantier RoyonC. PortellaC. Bliard
UMR FARE INRAC. RémondM. O’Donohue
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
4
Enzymatic synthesis of alkyl arabinosidesUMR FARE INRAC. RémondM. O’Donohue
ICMR UMR CNRSR. Plantier RoyonM. Muzard
Alkyl xylosides
pNP β-D-Xylp Alcools
Xylosidase GH39 de Bacillus halodurans
+ OH
OHO
HO On
Methyl β-D-xyloside, 10,7 %Ethyl β-D-xyloside, 9 %
n-propyl β-D-xyloside, 23,4 %n-butyl β-D-xyloside, 14,9 %n-pentyl β-D-xyloside, 2,5 %
Wheat bran
20 g
(8 g xylans) Xylanase
Tx-Xyl11
OH
OHO
HO
OH
OHO
OOH
OH
OHO
HO
OH
OHO
O
OH
OHO
OOH
+ arabino-xylooligosaccharides
3,15 g
Xylosidase
XylBH39
OHO
HO
OH
O
Propyl β-D-xylopyranoside
965 mg
n- propanol 5%
A two-steps synthesis of propyl β-D-xyloside from wheat bran
J. Mol. Catal. B: Enzymatic, 2009, 58, 1.
ARD WheatoleoB. Estrine
Wheat Bran and Straw
- Plant oils : coco, pko , palm ,- Sugar beet, wheat…
Xylose ArabinoseGlucose
Hydrophilic head Lipophilic tail
Glycosidic bond
Synthesis of surfactants
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
5
ARD WheatoleoB. Estrine A complete range of A complete range of ““greengreen”” products in order to meet all products in order to meet all
formulatorformulator’’s needs (hydrotropes, surfactants and emulsifiers)s needs (hydrotropes, surfactants and emulsifiers)
Short chain products (C4-C8)
Solubilizer / HydrotropeR/6505, …..
Wetting / Foaming Degreasing SurfactantsR/6781, …
EmulsifiersR/6669, …
Middle chain products (C8-C14)
Long chain products (C14-C22)
Synthesis of surfactants
ARD WheatoleoB. Estrine RadiaRadia®®EasysurfEasysurf : : Properties and applications
Glucose Glucose basedbased SS. . Pentose basedPentose based SS..
HO O
HOOH
OCnH2n+1
OH
m
R1O
HOOH
O (CH2)n CH3
R2
m'
Glucosides(wheat - starch origin)
Biodegradable
Mildness
Pentosides(Wheat bran and straw origin)
Biodegradable
Mildness
HLB
CMC
Solubility
Degreasing
γ O/W
Wetting
Can’t be solubilized in oils Oil solubility
Synthesis of surfactants
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
6
RadiaRadia®®EasysurfEasysurf: building : building pentosespentoses based based surfactant according a surfactant according a biorefinerybiorefinery conceptconcept
BiorefineryBiorefinery conceptconcept : : valorization of non food agricultural byvalorization of non food agricultural by--products rich in products rich in pentosespentoses..
Alkyl Poly Alkyl Poly PentosidesPentosides : : new generation of sugar based surfactantsnew generation of sugar based surfactants
-- low environmental impactlow environmental impact-- rapid and complete biodegradabilityrapid and complete biodegradability-- low low ecotoxicecotoxic behavior behavior -- powerful performance capabilitiespowerful performance capabilities-- ideal candidates for a broad range of applicationsideal candidates for a broad range of applications
ARD WheatoleoB. Estrine RadiaRadia®®EasysurfEasysurf : : Properties and applications
Synthesis of surfactants
2 processes (homogeneous catalysis)
Telomerization of butadiene with pentoses
French Patent CNRS 2001, N° 0116363, 2003, PCT WO 03053987.Eur. J. Org. Chem. 2004, 2914.Green Chem. 2005, 7, 219.J. Mol. Cat. 2005, 244, 93.
Sugar / Pd = 150PPh3 / Pd = 3Butadiene/Pd = 900DMF, 75 °C, 1 hHigh [pentose]
up to 95% conversion of sugar≈ 70 % monooctadienyl-xylosides
Sugar / Pd = 150Amine / Pd = 150TPPTS / Pd = 3H2O, 80°C, 1 hHigh [pentose]
up to 99% conversion of sugar≈ 70 % monooctadienyl-xylosidesOr ≈ 60 % dioctadienyl-xylosides
OOH
HO OH
OO
HO
HO
OH+ isomers
HOPd(OAc)2 / PPh3
DMF
OOH
HO OHO
O
HO O
H2O
HO
HO+ isomers
Pd(acac)2TPPTS
C12H25NMe2
EtNPr2i
D-xyloseL-arabinose
Synthesis of surfactants
ICMR UMR CNRSS. BouquillonJ. Muzart
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
7
Surfactant behavior - monooctadienyles : “medium”- dioctadienyles : “good”- crude mixture : “good”
Crude mixture :6% Xylose, 62% Monooctadienyles, 27% Dioctadienyles, 5% Trioctadienyles
Carbohydr. Res. 2006, 341, 1938.
Useless separations
Application to bran syrup
(bran syrup = xylose + arabinose + glucose + …)
Composition of the mixture1% Bran syrup67% Monooctadienyles31% Dioctadienyles1% Trioctadienyles
20,00
25,00
30,00
35,00
40,00
45,00
50,00
55,00
60,00
65,00
70,00
1,00 10,00 100,00 1000,00
concentration (mg/L)
surf
ace
tens
ion
(mN
/m)
“Good” behavior as surfactant
ICMR UMR CNRSS. BouquillonJ. Muzart
Synthesis of surfactants
Glycosylations
Optimal conditions (n = 0, 5, 6) : PTSA, alcohol, 20 h, 70% ≤ yields ≤ 80%
Simple and rapid syntheses of surfactants- monocatenar- bolaform
From free D-xylose
Metatheses
C10, C18, C20
Grubbs I [Ru] 7% mol 3 h, 40°Cn
n = 1, 5, 6O
O
OH
HO
HOO
OOO
OH
HO
HO
HO
OH
OH
n nα or β
αα or ββ 57-90%
OOH
HO OH
HO + HO "H+"O
O
HO OH
HOn n
n = 1, 5, 645ºC-80ºC, 24 h
"H+" = Amberlite IR 120 resin, PTSA, AcCl
Yields = 18-81%
Carbohydr. Res. 2007, 342(2), 154.
ICMR UMR CNRSS. BouquillonJ. Muzart
Synthesis of surfactants
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
8
Pentoses
D-xyloseL-arabinose
« Fine chemicals »
OHO
OHHO OH
Chemical transformations
Preparation of useful building-blocks
Objective: to develop transformations leading to common intermediates from either of the sugars
D-xylose
L-arabinose
CHOOH
HOOH
CH2OH
CHOOH
HOHO
CH2OH
4
4
OP2P3O
O
O
OP2OP3
OP1X
O
OP2OP3
OP1X
An interestingfunctionnalized intermediate
Reductiveelimination
- Nucleophilic addition
- Olefination
- Intramolecular reactions
- Reductive amination
suppression of the chiral character of C-4
ICMR UMR CNRSC. PortellaR. Plantier Royon
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
9
« Domino » Reactions with organometallic species
O
BnO
I
O
O
OHBnO
HOR
solvent, 0°C
RLi ou RMgBr
~90%
R = Me, n-Bu, iPr, Allyl, Ph
dr = 4/1 to 7/1
OHBnO
O
BnO
I
O
O Y Z
Me3Si LiOHBnO
+OHBnO
OHBnO
OHBnO
Y
Z
S
S
SMe
SMe
SPh
52 - 86%
Large variety of building blocksSimilar results from xylose or arabinose derivatives
J. Org. Chem. 2007, 72, 2271.Carbohydr.Res. 2007, 342, 2450.
ICMR UMR CNRSC. PortellaR. Plantier Royon
Synthesis of heterocyclic compoundsICMR UMR CNRSC. PortellaR. Plantier Royon
O
ORRO ORRO
YYCH2P(O)(OEt)2Et3N / LiCl
N
R
Y
OBn
OBn
*
Fonctionnalization
,Objective: New glycosidase inhibitors
D-xyloseand/or
L-arabinose THF
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
10
Tetrahedron lett. 2009, 50(17), 1902.
Extension to 2nd and 3rd generations and to L-arabinose
O
OHHOOH
O
OAcAcO O
OH
HO AcO2 steps (60 %)
S
Cs2CO3 (4 eq. / Cl atom)O CH
N NMe
PS
ClClN3P3
6
O
AcO OAcO
OAc
O CHN N
Me
PS O
N3P3O
AcO OAc
OOOAc
6
THF, 24 h, 0°C to RT
S (2 eq. / Cl atom)
MeONa (0.5 M)MeOH/CH2Cl2, RT, 12h
O
AcO OHO
OH
O CHN N
Me
PS O
N3P3O
HO OH
OOOH
6
1st generationQuantitative
Synthesis of Phosphorous-based GlycodendrimersICMR UMR CNRSS. Bouquillon
PN P N
PN OO
O O
OO
N
N
NN
N
N
N
NN
N
N
N P
P
PP
P
PS
OO
O
O
S O
OS
O S
SO
S
O
O
O
O
N
N
NN
NN
N
N
N
NN
NN
N
N
N
N
NN
N
N
N
N
N
P
P
P
PP
P
P
P
P
P P
P
SO
O
O
O
S
S OO
SO
O
O
S
O
O
S
O
O S
OO
S
O O
S
O O
S
O
OO
S
S O
O O
O
O
O
OO
O
O
OO
O
O
O
O
OO
OO
OR
ORRO
OR
OR
O
ROOR
OR
RO OR
OR
ROOR
OR
O
O
O
O
O
O
O
O
O
O
OO
OO
O
O
O
O
O
OO
O
O
O
O
O
O
O
OR
OR
OR
OROR
ORRO
ROOR
OR
OR
OR
RO
ROOR
OR
OROR
RO
RO
RO
ORRO
RO
ORRO
RO
ORRO
RO
ORRO
RO
ORRO
RO
RO
RO
RO
ORRO
RORO
RO
RO
ORRO
RO
RO
ROOR
OR
OR
OR
O O
ROOR
OR
Generation 2
Applications :CatalysisNanoencapsulation
R = H, OAc
Synthesis of Phosphorous-based GlycodendrimersICMR UMR CNRSS. Bouquillon
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
11
J. Org. Chem. 2009, in press.
Extension to 2nd and 3rd generations
Si O
OO
O
Si
Si
O
O
O
O
OO
O
O
OO
Ph
3
NNN
O S"
NNN
OS"
N NN
OS"
NN
NO
S"
NN
NO S"
NN
NO S"
N NN
O S"
N NN
OS"
NN
NO
S"
S' (2 eq. / branch)
O
OAcO
AcO
OAc
N3
O
HO
HO
OH
Cu(SO4)2 . 5H2O ( 4 eq. / branch)
Sodium ascorbate (8 eq. / branch)Si O
OO
OO
Si
Si
O
O
O
O
OO
O
O
OO
Ph
3
OH
5 steps (40 %)
S'
S" =O
AcO
AcO
OAc
THF / water, RT, 12 h
59%
"Click" Chemistry
Synthesis of Silicium-based GlycodendrimersICMR UMR CNRSS. Bouquillon
J. Org. Chem. 2009, 74, 5071
Applications :CatalysisNanoencapsulation
N NN
OO
O
N NN
N NN
O
O
Si
N NN
OO
O
N NNN N
N
O
O
Si
N NN OO
O
N NNN N
N
O
O
Si
OSi
N NN O
O
O
N NN
N NN
O
O
Si
N NN
OO
O
N NN
N NN
O
OSi
NN
N
O
O
O
NN N
NN
N
OO Si
O Si
NN N
O
O
O
NN N
NN N
O O Si
NN N
O
OO
NN N
NN N
O
OSi
NN N
O
OO
NN N
NN N
O
OSi
OSi
NN N
O
O ONN N
NN N
O
O
Si
NN
N
O
O ON
NN
NN
N
O
O
Si
NN
N
O
O O
NN
N
NN
N
O
O
Si
O
Si
NN
N
O
OO
NN
N
NN
N
O
O
Si
NNN
OO
O
NNN
NNN
O
O
Si
NNN
OO
O
NNN
NNN
O
O
Si
O
Si
NNN
O O
O
NNN NN
N
O
O
Si
NNNO O
O
NNN
NNN
O
O
Si
NNN
OO
O
NNN
NNN
O
OSi
OSi
NN
N
O
O
O
NN
N
NN
N
OOSi
NNN
O
O
O
NNN
NNN
OOSi
NNN
O
O
O
NNN
NNNO
OSi
OSi
NNN
O
O
O
NNN
NNNO
OSi
NNN
O
OO
NNN
NNN
O
OSi
NNN
O
OO
NNN
NNN
O
O
Si
O
Si
NN
N
O
OONN
N
NN
N
O
O
Si
NN
N
O
OO
NN
N
NN
N
O
O
Si
NN
N
OO
O
NN
N
NN
N
O
O
Si
O
Si
RO
RO
RO
RO
RORO
RORO
RO
RORO
RORO RO RO RO RO RO
OROR
OROR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OR
OROR
OROR
OROROROR
RORO
RORO
RORO RO RO RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
RO
O
OAcO
AcO
OAc
RO
Generation 3
Synthesis of Silicium-based GlycodendrimersICMR UMR CNRSS. Bouquillon
Pr. Sandrine BOUQUILLON, Université de Reims6èmes Rencontres de la Biomasse
Gembloux – 21 octobre 2009
12
Conclusions
Wheat bran
Pentoses :D-xylose
L-arabinose
Arabino-xylo-oligosaccharides
Pentoses syrup « Fine chemicals »
Pentosides
Surfactants
ICMR UMR CNRSARD WheatoleoUMR FARE INRA
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