Rósa Jónsdóttir

Antioxidant extraction from seaweed

Seaweed Industry Workshop Tuesday 27th June 2017

Marinox (Matis spin-off) founded in 2011

Built on extensive research on bioactives

in marine algae

UNA skincare launched in 2012

UNA skincare now separate company

Marinox developing and producing

seaweed extracts

Growing trend toward application of natural

antioxidants as functional and bioactive

ingredients

• Enhance oxidation stability

• Maintain/improve the intrinsic quality and

nutritional value

• Health promoting benefits

Antioxidants in seaweed

Antioxidants in seaweed

• Phlorotannins Polymers of phloroglucinol units

Restricted to brown seaweed

Free radical scavengers, reducing agents and metal chelators

• Fucoidans Sulphated polysaccharides

Cell wall of brown algae

Fucose

• Carotenoids, e.g. fucoxanthin

http://www.staff.dtu.dk/mata/Fucoidan/Structures

Antioxidant extraction

Antioxidant assays • Total Polyphenol Content

(TPC) • Oxygen radical

absorbance capacity (ORAC)

• DPPH radical scavenging • Fe2+ chelating ability (MC) • Reducing power (RP) • Cellular antioxidant

activity (CAA) • Model systems (food,

cosmetics, etc.) • Intervention studies

Extraction methods

• Solvent extraction

• Thermal and/or physical

methods

• Enzymatic hydrolysis

• Microwave

• Ultrasound

• Supercritical fluid

• Pressurized liquid

Seaweed

Preprocessing

Antioxidant extraction

Fractionation and characterization

Functional ingredient

Potential Impact

• Supplement:

• Positive health impact Anti-oxidative

Anti-diabetic

Anti-inflammatory

Anti-bacterial/viral

Anti-aging

• Large and growing market

• Food ingredient: • Improved food shelf-life

Antioxidant

Anti-microbial

• Sodium reduction

• Flavour enhancement

• High demand for new natural ingredients

0 10 20 30

Fucus vesiculosus

Ascophyllum nodosum

Laminaria hyperborea-old blade

Laminaria hyperborea-new blade

Alaria esculenta

Saccharina latissima-old blade

Saccharina latissima-new blade

Laminaria digitata

Ulva lactuca

Palmaria palmata

Chondrus crispus

Total phenolic content (g PGE/100 g extract)

(a)

0 500 1000 1500 2000 2500 3000

Fucus vesiculosus

Ascophyllum nodosum

Laminaria hyperborea-old blade

Laminaria hyperborea-new blade

Alaria esculenta

Saccharina latissima-old blade

Saccharina latissima-new blade

Laminaria digitata

Ulva lactuca

Palmaria palmata

Chondrus crispus

ORAC value (Trolox equivalent, µmol/g extract)

(b)

0 20 40 60 80 100

Fucus vesiculosus

Ascophyllum nodosum

Laminaria hyperborea-old blade

Laminaria hyperborea-new…

Alaria esculenta

Saccharina latissima-old blade

Saccharina latissima-new blade

Laminaria digitata

Ulva lactuca

Palmaria palmata

Chondrus crispus

Antiradical power (1/EC50)

(c)

Antioxidant activity of 9 species of Icelandic macro algae

Wang et al. 2009. Total phenolic compounds, radical scavenging and metal

chelation of extracts from Icelandic seaweeds, Food Chemistry, 116, 240-248.

TPC

ORAC

DPPH

Fucus vesiculosus with highest antioxidant capacity

Seasonal variation

Species • Alaria esculenta

• Ascophyllum nodosum

• Fucus vesiculosus

• Saccharina latissima

Locations • Sandgerdi (south-west)

• Stykkisholmur (west)

• Eskifjordur (east)

Time • March, April, May, July, August, October

70% acetone extract

0

5

10

15

20

25

SA ST ES SA ST ES SA ST ES SA ST ES

A. esculenta A. nodosum F. vesiculosus S. latissima

TPC

(g

PG

E/ 1

00

g e

xtra

ct)

March

April

May

June

August

October

Total Polyphenol Content

SA: Sandgerdi ST: Stykkisholmur ES: Eskifjordur

Io

din

e (

mg

/kg

dry w

eig

ht

Iodine content

0200400600800

100012001400160018002000

Sandgerdi

Stykkisholmur

Eskifjordur

Total arsenic content A

s (

mg

/kg

dry

weig

ht)

High content of total arsenic, highest during winter time

Inorganic arsenic iA

s (

mg

/kg

dry w

eig

ht)

Low levels of inorganic arsenic, less than 1% of the total arsenic

Major product categories from biorefining of brown macroalgal biomass

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8

Od

or s

co

re (

ran

cid

ity)

Days on ice

Seaweed antioxidant

Propyl gallate

Seaweed phlorotannin antioxidants

No antioxidant

Lipid oxidation in fish mince

OH

O

O

OH

OH

O

HO OH

HO

O

OH

O

O

OH

OH

O

OH

OH

Wang et al. 2009. Inhibition of haemoglobin-mediated lipid oxidation in washed cod muscle and cod protein

isolates by Fucus vesiculosus extract and fractions. Food Chemistry. 123, 321-330.

Seaweed phlorotannin antioxidants

0

5

10

15

20

25

30

35

0 4 8 12 16 20

TB

AR

S (

µm

ol/

kg

)

Degree of Hydrolysis (%)

No antioxidant

Seaweed antioxidant

Lipid oxidation during hydrolysis of fish byproducts

Halldórsdóttir et al. 2014. Oxidative processes during enzymatic hydrolysis of cod protein and their influence

on antioxidant and immunomodulating ability. Food Chemistry. 142, 201-209.

Mayonnaise enriched with 5% fish oil Secondary volatile oxidation products

EA 1.5 g/kg WE 2.0 g/kg

• Water extract in highest concentration most efficient • Similar results were seen in milk emulsion enriched

with 5% fish oil

Hermund et al. 2015. Characterization and antioxidant evaluation of Icelandic F. vesiculosus extracts in

vitro and in fish-oil-enriched milk and mayonnaise. J Functional Foods.

Granola bars enriched with 5% fish oil Secondary volatile oxidation products

0

200

400

600

800

1000

1200

1400

1600

0 1 2 3 4 5 6 7 8 9 10

1-P

en

ten

-3-o

l [n

g/g

]

Week

Control

Ac2

Ac1

Ec2

• Water, aceton or ethanol extracts (0.5 or 1 g extract/100 g emulsion) • Addition of seaweed extracts increases the lag phase of 1-penten-3-ol • At week 9 Control and Wc1 had the highest concentration of 1-penten-3-ol

Wc1

Wc2

Ec1

Biomolecule spin-off companies: Marinox and UNA skincare

Marina Mayo

EPA & DPA omega-3 enriched mayonnaise

with MarinoxTM extract presented at

Nordtic in Selfoss June 2014

Seaweed barley pasta

Icelandic barley with Alaria esculenta

Seaweed based dairy product (skyr)

Seaweed food ingredient – products developed at Matís

Icelandic skyr with Alaria esculenta

Seaweed ingredients in cosmetic

Contact: Biljana Ilievska (biljana@marinox.is)

Hörður G. Kristinsson (hordur@marinox.is) Rósa Jónsdóttir (rosa@marinox.is)