DEPARTMENT OF GLYCOMATERIALS:

Department of glycomaterials studies:

- the occurrence and structural features of polysaccharides from plant residues, medicinal plants and pseudocereals,

- their functional and rheological properties and intermolecular interactions, - biological activity of the polysaccharides, - modification of the polysaccharides.

Main topics of the projects are:

1) Polysaccharides from economically important plants and plant

residues

Selection of economically important plants (amaranth, buckwheat, plant residues).

Utilization of new extraction methods (ultrasound) and their comparison to classical methods. Evaluation of the chemical composition, molecular and rheological properties of the obtained polysaccharide preparations.

Study of application polysaccharides as additives in food, pharmacy, or cosmetics - preparation of new functional polysaccharides.

Application possibilities of the isolated hemicelluloses -xylansApplication possibilities of the isolated hemicelluloses -xylans

Wet-end additive in papermaking AGX from corn cobs (2 %) improved substantially the mechanical properties of printing and wrapping paper .

Pharmaceutical aid GX and AGX are useful as disintegrating and wetting agents (tablet and powder forms).

Textile printing aidGX and AGX improved the printing behaviour of textile and can substitute in part

alginates using alginate/xylan blends

* Emulsifying agent for oil/water emulsions

* Stabilising agent Protein foam stabilizing effect of various xylans

* Food hydrocolloid Rheological behaviour of xylan/starch blends

Xylans in breadmaking. The addition of GX from buckwheat hulls increased quality of dough and baker’s products.

0 10 20 30

Stimulatory index, SI

AG

AGX

GX

AX

AG

AGX

GX

AX

1000

100

10

SIm it

SIcom it

Dose, g/ml

Water-solubole heteroxylans:

AX (rye bran)

GX (beech wood meal)

AGX (corn cob)

AG- Arabinogalactan- control

Mitogenic activity of xylan from economically important plants and plant residues

The disaccharide side chain -Xylp-(1→2)--Araf seems to be important for the expression of the immunological activity. AGX>>GX>AX

Xylp1-2Araf1 Araf1 Araf1

3 3 3 __

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

4Xylp1__

3 2 2

Araf1 Araf1 4MeGlcpA1

acid hydrolysis endo--1,4-xylanase AGX-3, AGX-48

a-L-arabinofuranosidase ultrasonication

AGX (corn cob)

0

9

18

27

36

45

54

Sti

mu

lato

ry in

de

x, S

I

ws-AGX AGX-Usw AGX-Usa AGX-E3 AGX-E48

10 100

1000

10 100

1000

2) Polysaccharides from selected herbs and other medicinal plants

Isolation of the water-soluble polysaccharides from selected herbs and other plants.

The crude polysacharides are tested for biological activity - mitogenic and comitogenic activity

- antitusic activity and- antioxidant activity.

Preparation of the homogeneous polysaccharide fractions from the crude biological active polysaccharides. The biological activity of the homogeneous fractions is compared with the activity of the crude polysaccharide.

Determination of the primary structure of most biologically active fractions by means

of chemical and spectral methods of structural analysis.

Scientific goal:

To determine relationship between structure and the biological activity of the polysaccharides.

0

10

20

30

40

50

60

AO

A (

%)

L+Hemi-5 L+Hemi-6 L+Hemi-7 L+T

Antioxidant aktivity

Buckwheat hulls

Methods:a) measurement of chemiluminiscence (CL)Antioxidant activity of polysaccharides was determined by comparison of CL signal which was obtained by reaction of luminol and different radicals and of CL signal in presence of the polysaccharides- antioxidants.

b) measurement of absorption spectraof conjugated dienes (215-320 nm) of peroxidized liposomes.. Antioxidant activity of samples was compared with reference inhibitor α-tocopherol.

0

2000

4000

6000

8000

10000

TR

AP

( m

ol/

ml)

EE/L EEPS/L WEPS/L EE/R EEPS/R EEPS/R

3 1.5 0.3 0.15

Leaves RootsBurdock

Antioxidant activity (TRAP) of all polysaccharides was very high, significantly higher for water-ethanol extract from the leaves.

The antioxidant activity of all polysaccharide fractions of the buckwheat was higher in comparison to that of -tocopherol (T), which is used as a reference inhibitor of peroxidation.

Althea Malva Plantago

Antitusic activity (ATus) of water extracts from the medicinal plant

Roots, Leaves Flowers LeavesG; RG G; RG G; RGHighly branched arabinan AG AGGlucuronorhamno- Acid heteropolysaccharide galacuronan

G- α -1,6-Glucan ; RG- Ramnoarabinogalaktan; AG- Arabino-3,6-galactan

0

20

40

60

80

100

M RG C D P

Act

ivit

y, %

Althea

Water extracts (mucilagenous and non-mucilagenous) have high antitusic activity. Rhamnoarabinogalactans are more active than glucans. Extracted components have no negative effect on expectoration.

Burdock Rudbekia Mahony

Non- Mucilageneous

Roots Roots, Aerial part StemsFructan P- complex Glucuronoxylan(inulin-type) Glucuronoxylan Glukuronoxylan-

-pectin complex

0

20

40

60

80

100

M RG G C D P

Activ

ity, %

Mucilageneous

Malva

0

20

40

60

80

100

C D P AL-F RR RL RX MahX MAP

Drugs Burdock Rudbeckia Mahony

An

ti-t

uss

ive

acti

vity

, %

0 20 40 60 80 100 120

Zymosan

Pl-P

Va-PC

Sa-PC

SO-P

RSc-PC

RSn-PC

Stimulatory index, SI

1000

100

101

SImit

Dose, g/ml

0 20 40 60 80 100 120

Zymosan

Va-PC

SO-P

RSn-PC

SIcomit

Rudbeckia fulgida, var. Sullivantii (aerial part) – DEAE-Seph A50/waterSalvia officinalis (aerial part)-US Valeriana officinalis (roots) Plantago lanceolata (leaves) Symphytum officinalis (roots)

RSc-PC Crude polysaccharide RSn-PC -1,6-D-Glucan, Arabinogalactan, Sa-PC Pectic arabinogalactan, Glucan, Xylan Va-PC Arabinogalactan, Pectin, Glucan PL-P Rhamnoarabino-1,6-D-galactan SO-P Low-Mw glucofructan

Mitogenic activity of polysaccharide fractions from medical plantsCrude fractions

Mahony (stems) A- pectin, MahX- xylan MahX>>APSalvia (aerial part) A- Arabinogalactan A << B ~ C

BB- Pectin/Arabinan C- Glucuronoxylan Burdock ((leaves, roots) EELL-2P, LL-PS –from leaves EELL-2P, LL-PS <AL-C, AL-R

AL-C, AL-R – from rootsBuckwheat (hulls) BW 6 - xylan, BW 5 - starch-xylan BW5 < BW6

Fractions after purification

ATus: Antitussive; Mit: Mitogenic/comitogenic; AO: AntioxidantTests were performed on extracts and isolated polysaccharides

Plant

Althea officinalis L., var. Robusta Malva mauritiana L. Plantago lanceolata L., var. Libor Rudbeckia fulgida L., var. Sullivanti Mahony - Mahonia aquifolium Pursh (Nutt.) Valerian - Valeriana officinalis L. Sage - Salvia officinalis L. Burdock - Arctium lappa, var. Herkules Comfrey – Symphytum officinalis L.Aloe - Aloe barbadensis L.Cistanche deserticola Y.C. Ma. Aloe Vera –Aloe barbadensis L.Tamarind – Tamarindus indica L.

Corn - Zea mays L.Buckwheat – Fagopyrum esculentum L.

Tissue

Roots, leaves Flowers Leaves Stem, leaves, roots Aerial part RootsAerial partRoots. leavesRoots Leaves Underground partLeavesSeed coat

Cobs, hulls Seed coat

Biological activity

ATus, Mit ATus, Mit ATus, Mit ATus, Mit ATus, Mit Mit Mit ATus, Mit, AO Mit, AO Mit, AO Mit Mit, AOA AO Mit Mit, AO

Biological activity of polysaccharides isolated from the plants

3) Hydrophobization of chosen commercial and non-commercial polysaccharides

A: Partial hydrophobization of chosen commercial polysaccharides by application of conventional and unconventional esterification procedures. Determination of the degree of substitution and some functional properties of the derivatives. Determination of emulsifying and foaming activities of the prepared derivatives.

SCIENTIFIC GOAL:

To achieve more effective utilization of plant raw material. To prepare novel, highly valuable materials for cosmetics and pharmaceutical industry.

B: Partial hydrophobization of commercial pectin and alginate by alkylation of the carboxyl groups. Amidation of highly methoxylated pectin by reaction with alkyl amines. Determination of the degree of substitution and  some functional properties of the derivatives.

SCIENTIFIC GOAL:

Preparation of the hydrocolloids with improved or novel functional properties for application as additives in food, cosmetics, pharmacy and other industrial branches.

Hydrofobic modification of the polysaccharides

Polysaccharide sources

HEC, CMC, CMS Citrus pectin and pectate

Xylan from  beech wood mealXylan from  beech wood sulfit cellulose (Institute of Chemistry)Xylan from alkali effluents of the viscose process (Lenzing AG)

Introduction of long alkyl substituents (C4-18)

Water-solubleWater-soluble deriv derivativesatives, , lowlow DS DS Amphiphilic derivatives ( surface active properties)

Water-insolubleWater-insoluble deriv derivativesatives, , highhigh DS DS Hydrophobic materials (films, textile printing aid,

composites, special materials)

DEPARTMENT OF GLYCOMATERIALS:

Hromádková Zdenka Malovíková Anna Kardošová Alžbeta Ebringerová Anna Capek Peter Košťálová Zuzana

Technicians: Bordáčová A., Šporánková N., Marková E.

Domestic and international projects

VEGA č. 2/3162/23, 2003 - 05 : Bioactive and functional plant polysaccharides for applications in food, pharmacy and cosmetics. ( J. Hirsch )APVT project č. APVT-51-015802, 2002–05: :Hydrophobized polysaccharide derivatives for various industrial applications. ( A. Ebringerová )Project VTP-SP-2003-01-U-00-01, 2003-04: Preparation of the polysaccharide from buckwheat bran and their application in bread making technology as a new functional food. ( J. Hirsch )

COST D28, WG D28/006/03), 2004–08: Therapeutic Polysaccharides II: Bioactive Polysaccharides and theirStructure-Function relationships. ( Z. Hromádková)COST D29, WG D29/0008/03, 2003–2007: Production and Functionalization of Hemicelluloses for Sustainable Advanced Products. ( A. Ebringerová )

Scientific co-operation

Faculty of Industrial Technologies, TrU, Púchov: I. Sroková Jesenius Medical School, UC, Martin : G. Nosáľová Faculty of Pharmacy, UC, Bratislava: D. Košťálová National Institute of Health, Praha: V. HříbalováInstitute of Biophysics, ASC, Brno: L. Kubala Friedrich-Schiller University, Jena: T. HeinzeNCMH University of Nottingham: S. Harding