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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 ([email protected])
Hörður G. Kristinsson ([email protected]) Rósa Jónsdóttir ([email protected])