chemical modification of non-cellulosic polysaccharides
TRANSCRIPT
Dr. Katrin Schwikal 1Thuringian Institute of Textile and Plastics Research, Rudolstadt
Chemical modification of non-cellulosic polysaccharides
Katrin Schwikal1, Katrin Petzold-Welcke1, Thomas Heinze1, Bodo Saake2
1 Centre of Competence for Polysaccharide Research, Friedrich Schiller University Jena / TITK- Rudolstadt
2 Institute of Wood Technology and Wood Biology, Johann Heinrich von Thuenen Institute, Hamburg
Dr. Katrin Schwikal 2Thuringian Institute of Textile and Plastics Research, Rudolstadt
! For example: acidic, alkaline, hydrophilic, hydrophobic, optical active.
With one matrix – various properties can be obtained
Polymer matrix with functional groups.
Modification with functional groups
Improved... • solubility.
• specific interaction with other polymers and particles (flocculation agents, surface active agents, phase separation agents, viscosity control agents, agents for improving the mechanical properties).
Specific biological activities, sensor functions.
Dr. Katrin Schwikal 3Thuringian Institute of Textile and Plastics Research, Rudolstadt
DS = 0.5
DS = 1.0
DS = 2.0
• Mixed substituted derivatives (amphiphile, hybrid ionic, combination of a functional group with a intermediary dilution group ...)
• Degree of the modification and distribution of the functional groups can be adjusted.
Advantages of a polymer analog reaction:
Furthermore, a selective reaction on a specific hydroxyl group is possible, too.
statistical
Distribution of the substituents along the polymer chain
non-statistical
Degree of substitution (DS)(example: two hydroxyl groups)
substituted unit
non-substituted unit
individual hydroxyl functions
Modification with functional groups
Dr. Katrin Schwikal 4Thuringian Institute of Textile and Plastics Research, Rudolstadt
Non-cellulosic polysaccharides
O
HOOH
OH
O
OOHO
OOH
OH
O
HOOH
OH
O
OO
HOOH
OH
OOHO
OH
OH
OO
OHO
OH
OH
Amylose
Cellulose
β-D-polyglucose
α-D-polyglucose
fiber forming structure polymer
non-fibre forming storage polymer
O
HOOH
OH
O
OOHO
OOH
O
n
OOHO
OH
OH
Amylopectine
Starch vs. cellulose
Dr. Katrin Schwikal 5Thuringian Institute of Textile and Plastics Research, Rudolstadt
OOHO
OHO
O
HOO
OO
HOOH O
OHO
OO
OH3CO
HOOH
COOHOH3CO
HOOH
COOH
n
" Isolation from various resources" Cereal-by-products: wheat and oat spelts, corn spindles, barley
husks (arabinoxylanes) – depending on location up to 50%.
" Pulping-by-products (hard woods – 4-O-methyl glucuronoxylanes).
Xylan" Is one of the polyoses. " To be found in the supporting connective tissue
of plant cells.
41,627.3
27.1
cellulose
polyoses
lignin
accessory component
Birch:
*Grammel, R., Forstbenutzung. Verlag Paul Parey, Hamburg und Berlin, 1989.
Non-cellulosic polysaccharides
Dr. Katrin Schwikal 6Thuringian Institute of Textile and Plastics Research, Rudolstadt
Non-cellulosic polysaccharides
Cellulose
Xylan
OOHO
OHO
O
HOO
OO
HOOH O
OHO
OO
RR
OOHO
OHO
O
HOOH
OO
HOOH O
OHO
OHO
OH
OH
OH
OH
O
HOOH
OOO
HOOH
OO
OHβ-D-Polyglucose
β-D-Polyxylose
similar stereochemical configuration
Supporting connective tissue of plant cells- supports plant water circulation- connect cellulose and lignin
With the exception:pentose hexose
R: polysaccharide substituents
Dr. Katrin Schwikal 7Thuringian Institute of Textile and Plastics Research, Rudolstadt
Adjustable degree of substitution (DS)
Adjustable distribution of the substituents along the polymer chain
OOHO
OH
Functional polymers
PolysacchridePolysacchride esteresterPolysacchridePolysacchride etherether
OxidatedOxidatedproductsproducts
O
HOOH
OH
O
O
Reactive OH-groups
COOH
CH3C
O
O-Na+
N CH3
CH3OH H3C
Cl
CH3
O n
Xyl-O-SO3-Na+
O
Hydrophilic Hydrophobic Other special functionalities
O
O
O
OOO
O
NO
O
H
OO
Cross-linkable
Physiological active
Complexing Chiral
Dr. Katrin Schwikal 8Thuringian Institute of Textile and Plastics Research, Rudolstadt
OORO
O
OHNCl
OOHO
OH
NO
Cl
2-Hydroxypropyltrimethylammonium xylan (HPMA xylan)
R = H; CH2CHOHCH2N(CH3)3+Cl-
Schwikal K., Heinze Th., Ebringerová A., Petzold K. Macromol. Symp. 2006, 232, 49-56.
Activation with NaOH
4-O-methyl-glucurono xylan from birch wood
The degree of substitution
0.06
0.10
0.14
0.19
0.00
0.05
0.10
0.15
0.20
0.15 0.25 0.35 0.50
EPTA/AXU
DS The molar degree of substitution
(MS) is easily adjustable to values between 0.06 and 0.19.
MS
Dr. Katrin Schwikal 9Thuringian Institute of Textile and Plastics Research, Rudolstadt
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0 2 4 6 8 10 12 14
pH-value
Cha
rge
[equ
/mol
]
" The all in all surface charges of GX and the HPMAGX with a MS of 0.06 in water at pH 6-8 is negative.
" Surface charge of cationic modified birch xylans in water:
0.19
0.14
0.1
0.06
birch xylan
HPMA 4-O-methylglu-curono xylanswith MS =
-0.07
-0.02
0.030.07
0.14
SurfacechargebetweenpH 6-8
≡
O
HOO
OO
HOO
O
N
OH
OH3CO
HOOH
O O
O
HOOH
O
Cl
Na
+-
+
-
-
+-
Due to the methylglucuronicside chains in the polymer, the resulted structure have a zwitterionic character.
The degree of substitution
Dr. Katrin Schwikal 10Thuringian Institute of Textile and Plastics Research, Rudolstadt
Practical example: xylan as paper strength additive
Strong association of xylan to the cellulose microfibrilles in the natural environment.1
After removing xylan - stability decreased. 2
The pulp surface is weakly anionic charged.
" New biopolymer-based products are suitable by modification of the xylan.
" Cationic xylan derivatives should be able to increase the paper strength properties.
" They should be capable to improve the fine and filler retention.
+
OH
HO
HOOH
OH
OH
-OOCCOO-
HO
HO
--+
1Chanzy H., Dube, M., Marchessault R. H., Tappi 1978, 61(7), 81.2Laine, J., Pap. Puu 1997, 79(8), 551, Mobarak F., El-Ashmawy, A.E. Fahmy, Y. Cell. Chem. Technol. 1973, 7, 325Mobarak F., El-Ashmawy, A.E. Augustin, H. Cell. Chem. Technol. 1973, 11, 109.
The degree of substitution
Dr. Katrin Schwikal 11Thuringian Institute of Textile and Plastics Research, Rudolstadt
Adsorption behaviour on model surfaces via SPR*
prismpolarized light reflected light
adsorbed HPMA xylanHPMA xylan
sensor surfacewith gold film andsurface coating
• At a specific angle - the free electrons in the metal (gold) couple resonant with the incident photons – and induce a plasma wave that extends out in the interface.# surface plasmon
• Any change in the interface (thickness, refraction index) lead to a change of the resonant frequency.
• The angle there the minimum intensity was detected shift.
*surface plasmon resonance spectroscopyKaya A., Drazenovich D. A.; Glasser W. G., Schwikal K., Heinze Th., Esker A. R. The 235th ACS National Meeting, New Orleans, LA, United States, April 6-10, 2008.
Surface coating with self-assembled monolayers (SAMs) and cellulose
The degree of substitution
HPMA xylan
SAM-COOHHS(CH2)10COO-
=HS
Au Au
S S S S
Au
S S S S
Dr. Katrin Schwikal 12Thuringian Institute of Textile and Plastics Research, Rudolstadt
SPR-measurements*
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
0.4
0.3
0.2
0.1
0
Γ/m
g•m
-2
16012080400
Concentration /mg•L-1
A3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
0.4
0.3
0.2
0.1
0
Γ/m
g•m
-2
16012080400
Concentration /mg•L-1
A
16012080400
Concentration /mg•L-1
16012080400
Concentration /mg•L-1
0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
16012080400
Concentration /mg•L-1
0.3
0.2
0.1
0
Γ/m
g•m
-2
16012080400
Concentration /mg•L-1
B0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
16012080400
Concentration /mg•L-1
0.3
0.2
0.1
0
Γ/m
g•m
-2
16012080400
Concentration /mg•L-1
B
Γ/m
g•m
-2Γ/
mg•
m-2
Γ/m
g•m
-2Γ/
mg•
m-2
model cellulose surface SAM-OH surface
" Generally, all samples have low affinity to the model cellulose and SAM-OH surfaces.
" Hydrophilic interactions do not play any significant role in the adsorption.* in cooperation with Abdulaziz Kaya, Alan R. Esker, Viginia-Tech-University, USA
The degree of substitution
Dr. Katrin Schwikal 13Thuringian Institute of Textile and Plastics Research, Rudolstadt
0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
16012080400
Concentration /mg•L-1
D0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
16012080400
Concentration /mg•L-1
D
Γ/m
g•m
-2Γ/
mg•
m-2
MS = 0.06 (●), MS = 0.10 (▼), MS = 0.14 (►), MS = 0.19 (■), MS = 0.34 (▲),4-O-methyl-glucurono xylan from birch wood (◄).
SAM-COO- surface
electrostatic interactions
HPMA-4-O-methylglucuronoxylans with:
" Absence of adsorption for birch xylan indicates the importance of electrostatic interactions in the adsorption process.
" The decrease in adsorption at higher DS values are most probably caused by flat conformation of HPMA chains on the SAM-COOH surface.
" Adsorption has a maximum at HPMAGX MS = 0.10.
" Adsorption has a maximum at HPMAGX MS = 0.10.
MS = 0.1
The degree of substitution
SPR-measurements
Heinze T., Hornig S., Michaelis N., Schwikal K., ACS Symposium Series, 2010, 1019(9), 195–221.
Dr. Katrin Schwikal 14Thuringian Institute of Textile and Plastics Research, Rudolstadt
2025303540455055
0 3 6 9c [g*10*kg-1]
Tens
ile-In
dex
[Nm
*g-1
]
0.19
0.14
0.1
0.06
Birch xylan
" HPMA xylan increased the tensile strength of spruce sulfite pulp and birch kraftpulp.
" Spruce sulfite pulp up to 50%; birch kraft pulp up to 60%." Optimum at MS = 0.1.
Tensile strength after adding xylan and xylan derivatives:
HPMA-4-O-methylglucuronoxylans with:
MS = 0.19MS = 0.14MS = 0.10MS = 0.064-O-methyl-glucurono xylan from birch wood
2025303540455055
0 3 6 9
c [g*10*kg-1]
Tens
ile-In
dex
[Nm
*g-1
]
Spruce sulfite pulp Birch kraft pulp
Adjustable degree of cationic groups – optimized product.
The degree of substitution
Dr. Katrin Schwikal 15Thuringian Institute of Textile and Plastics Research, Rudolstadt
6
23
O
+Na-OOCH2COO
OH
O
OOHO
OOH
OCH2COO-Na+
+Na-OOCH2C
Statistical distribution:
Non-statistical distribution:HPLC5
" Distribution of the functional groups within the repeating unit Can be calculated from the 1H-NMR-spectra (hydrolyzed sample).1
" Distribution of the functional groups along the polymer chain.
The substituent distribution
Analytical tools:
Capillary Electrophoresis4
Enzymatic Degradation3
GC/FID2
1 Reuben J., Conner H.T. Carbohydr. Res. 1983, 115, 1–13.2 Zeller S. G., Griesgraber G. W., Gray G. R. Carbohydr. Res. 1991, 211, 41–45.3 Horner S., Puls J., Saake B., Klohr E.-A., Thielking H. Carbohydr. Polym. 1999, 40, 1–7.4 Tüting W., Albrecht G., Volkert B., Mischnick P. Starch/Stärke 2004, 56, 315–3215 Lazik W., Heinze Th., Pfeiffer K., Albrecht G., Mischnick P. J. Appl. Polym. Sci. 2002, 86,
743–752.
Dr. Katrin Schwikal 16Thuringian Institute of Textile and Plastics Research, Rudolstadt
Values from HPLC analysis of carboxymethylcelluloses after hydrolysis with HClO4
Synthesis procedure for e.g. a carboxymethylation1. Dissolving the polymer (e.g. in
Dimethylacetamide/LiCl for cellulose; Dimethylsulfoxide for starch and xylan)
2. Solid NaOH particles3. ClCH2COO-Na+
A selective activationof the polymer fiberresulted
Non-statistical distribution
For example non-statistical distributed CMC1: " Tends to the formation of small, more compact
complex aggregates." Specific adsorption - multiple reloading of colloidal
BaSO4-particles.
Synthesis via forming a reactive microstructure � state of the art
Different properties despite the same degree of substitution:
The substituent distribution
1Kötz J., Bogen I., Heinze U., Heinze T., Klemm D., Lange S., Kulicke W.-M. Das Papier 1998, 52(12) 704-712.
Dr. Katrin Schwikal 17Thuringian Institute of Textile and Plastics Research, Rudolstadt
CMS from Hylon VII, DS = 1.02via reactive microstructure
0
0.1
0.2
0.3
0.4
0.5
0.6
Glc Mono-CMGlc Di-CMGlc Tri-CMGlc
Mol
e fra
ctio
n Statistical values for linear polymers (Spurlin) for DS = 1.02
Hylon VII (amylose content: 70%)
Synthesis via forming a reactive microstructure*
DSCM NMR O-2 O-3 O-6 Σ 0.53 0.11 0.42 1.05 0.64 0.11 0.26 1.01
Via reactive microstructureVia conventional heterogeneous synthesis
Increased reactivity on position O-6 compared to heterogeneous methods.
The substituent distribution
OORO
OCH2COO-Na+
OR
R = H, CH2COO-Na+
*Dissolution in DMSO, NaOH-particlesAGU:NaOH:ClCH2COO-Na+ zu 1:17:10
Dr. Katrin Schwikal 18Thuringian Institute of Textile and Plastics Research, Rudolstadt
Potato starch (amylose content: 28%)
Synthesis via forming a reactive microstructure
0
0.1
0.2
0.3
0.4
0.5
0.6
Glc Mono-CMGlc
Di-CMGlc Tri-CMGlc
Tetra-CMGlc
Mol
e fra
ctio
n
CMS from potato starch, DS = 1.10via reactive microstructure
Statistical values for linear polymers(Spurlin) for DS = 1.10
For starches with a higher amylopectine content an additional tetra-substitution was detected.1
The substituent distribution
1Heinze T. , Liebert T., Heinze U., Schwikal K. Cellulose, 2004, 11(2) 239-245
AGU:NaOH:ClCH2COO-Na+ zu 1:17:10
Dr. Katrin Schwikal 19Thuringian Institute of Textile and Plastics Research, Rudolstadt
0.00.20.40.60.81.01.2
0.5 1 2 3 4 10Molares Verhältnis
ClCH2COONa:Anhydroxyloseeinheit
DS
Xylan dissolved in aqueous NaOH -subsequent addition of Propan-2-ol
Anhydroxylose unit (AXU):NaOH 1:4,1, 70 min, 65°C, 25% NaOH
OORO
OCH2COO-Na+
R = H, CH2COO-Na+
Activation of the xylan in solution*
Xylan suspended in Propan-2-ol -subsequent addition of aqueous NaOH
Anhydroxylose unit (AXU):NaOH - 1:ClCH2COONa, 5 h, 55°C, 15% NaOH
Activation of the xylan in suspension
*multiple synthesis steps (2 X) CMX (DS = 1.09) - product with a DS = 1.91 results.
The substituent distribution
Alternative routes for non-cellulosic polysaccharides:
Molar ratioClCH2COONa: anhydroxylose unit
Petzold K., Schwikal K., Heinze T. Carbohyd. Polym., 2006, 64, 292–298.
Dr. Katrin Schwikal 20Thuringian Institute of Textile and Plastics Research, Rudolstadt
0,0
0,2
0,4
0,6
0,8
1,0
0,0 0,5 1,0 1,5 2,0
Mol
frakt
ione
n
DSHPLC
Xylose Mono-O-CMX Di-O-CMX
HPLC-data analysis1,2 of the carboxymethyl xylans:
0,0
0,2
0,4
0,6
0,8
1,0
0,0 0,5 1,0 1,5 2,0M
olfra
ktio
nen
DSHPLC
Xylose Mono-O-CMX Di-O-CMX
Activation of the xylan in suspensionActivation of the xylan in solution
ci = Mole fraction of xylose (i = 0); mono- (i = 1); di- (i = 2) carboxymethyl xylose
k = carboxymethyl group content per AXU (k = 0;1;2)DS = degree of substitution
( ) ( ) k2ki DS/21DS/2
k2
c −−⎟⎟⎠
⎞⎜⎜⎝
⎛=
1Spurlin H.M. J. Am. Chem. Soc. 1939, 61, 2222-2227.2 Heinze U., Heinze Th., Klemm D. Macromol. Chem. Phys. 1999, 200, 896-902.
Petzold K., Schwikal K., Günther W., Heinze Th. Macromol. Symp. 2006, 232, 27-36.
Structural characterization
The substituent distribution
Dr. Katrin Schwikal 21Thuringian Institute of Textile and Plastics Research, Rudolstadt
Synthesis conditions: Anhydroxylose unit:ClCH2COO-Na+:NaOH - 1:2:2, 5 h, 55°C, propan-2-olproducts: DS = 0.81 (4% NaOH), DS = 0.82 (6% NaOH), DS = 0.84 (10% NaOH), DS = 1.01 (15% NaOH), DS = 0.60 (20% NaOH).
Di-O-carboxymethyl xylose
Mono-O-carboxymethyl xylose
Xylose
4% 6% 10% 15% 20%
-0,30
-0,20
-0,10
0,00
0,10
0,20
Δ ci(s
purli
n)
NaOH
Activation of the xylan in suspension
1. xylan/propan-2-ol. 2. aqueous NaOH.
050
100150200250300350400
2 3 4 5 6 7 8 9 10 15% NaOH
NT
U
1% Xylan3% Xylan
Non-statisticaldistribution
The substituent distribution
Dr. Katrin Schwikal 22Thuringian Institute of Textile and Plastics Research, Rudolstadt
The substituent distribution
... and in starch chemistry?
" It is a well known fact that reaction conditions can be influence sample properties
• Even at low degrees of substitution (MS = 0.03-0.11)1 different properties (swelling, solubility and viscosity) of HPMA- starches varied, despite the same MS when different reaction conditions were used (Slurry process, Paste process, Semi-dry process, Extrusion process).
• Vihervaara et al.:2 different distributions of cationic groups throughout the granule depending on process.
" In starch chemistry the method �first slurry and then activation� is very common.
• Tüting et al.3 discuss the distribution pattern along the polymer chain of different carboxymethyl starches (Waxy mais, potato and High amylose) prepared with a slurry method (isopropanol/NaOH).
• Waxy maize CMS– best agreement with the statistic calculated patterns (Spurlin, Reuben).
• potato and high amylose CMS – more differences.
1S. Radosta, W. Vorwerg, A. Ebert, A.H. Begli, D. Grülc, M. Wastyn Starch/Stärke 2004, 56, 277–287.2T. Vihervaara, H. H. Bruun, R. Backman, M. Paakkanen Starch/Stärke 1990, 42, 64-68.3Tüting W., Albrecht G., Volkert B., Mischnick P. Starch/Stärke 2004, 56, 315–32.
Dr. Katrin Schwikal 23Thuringian Institute of Textile and Plastics Research, Rudolstadt
" In general:• Type of starch
• Water/slurry ratio
• Slurry medium
• NaOH concentration
• Reaction temperature...
...are influence swelling of the starch - and may have an influence on the distribution pattern along the polymer chain.
The substituent distribution
More detailed studies can be a helpful tool to design starch derivatives with a target adjusted distribution and
properties, too.
Dr. Katrin Schwikal 24Thuringian Institute of Textile and Plastics Research, Rudolstadt
Many thanks for�
Thank you for your attention!
Prof. Allan Esker and Dr. Abdulaziz Kaya