Hort Connections

Adelaide Convention Centre

17 May 2017

ARC Centre of Excellence in Plant Cell WallsAdelaide Glycomics

The University of AdelaideAustralia

&

Division of GlycoscienceRoyal Institute of Technology (KTH)

Stockholm, Sweden

vincent.bulone@adelaide.edu.au

Value adding to agricultural biomass waste

Glycoscience

Turning agricultural waste into new high-value products

Cost of agricultural waste in Australia

$20 billion per annum across the value chain

40% of all food produced for human consumption is lost during primary

production

20% primary horticultural production is lost pre-farm gate representing

$1.72 billion loss per annum

Dif

fere

nce

co

mp

ared

to

19

96

(%

)

Financial year

Waste biomass generation in South Australia

Around 27 million tonnes per annum (t/p.a.) of total waste biomass generated of which 5.5 million t/p.a. (around 21%) is considered accessible waste biomass.

Around 5.2 million t/p.a. or 95% of the estimated accessible waste biomass is associated with crop residues.

Accessible waste biomass generated by type and Council region

Crop residues are essentially from cereals, potatoes and other horticultural cropsWineries contribute less than 10% biomass waste – efficient waste management with 95-100% recovery

7

Three current major uses of agricultural waste from crops

Energy: direct combustion systems and cogeneration

Compost

Feed for animals

8

Example (1) of major low-value agricultural streams in South Australia

Between 20-40% of the fresh potato harvest falls below supermarket specifications for shape, size and appearance

This represents 85,000 tonnes wasted annually or AUD$850k in South Australia only

(total waste in Australia of 130,000 tonnes)

Paradoxically Australia imports around 20,000 tonnes of potato starch per year

Product Yield Price/t (USD) Price /t (AUD) AUD/t raw material

Juice 75% 0 0

Starch 19% 400–600 532–798 101–152

Fibre 4% 1500–2200 1995–2926 80–117

Protein 2% 1200–1700 1596–2261 31–45

212–314

There is clearly potential for import substitution and establishment of a starch

industry

Energy storage: starch in plants (glycogen in animals)

• Amylose

– -1,4-glucan

– ~1000 glucose units

• Starch grain

– Water insoluble,

– size & shape is species specific

• Amylopectin– -1,4 & -1,6-glucan– 10,000 - 100,000 glucose units– highly branched, 20 - 25

glucoses/branch

potato: oval,

100 µm in diameter

rice: angular,

10 µm in diameter

acceptors

for addition

of further

glucose unitsstart

(reducing end)

polymer of glucose units

Exploitation of waste streams from potato primary production

- Our aim is to start the first starch industry in Australia taking advantage of the local production

- Potential to amplify 60-200 fold the value of the (current) 85,000 tonnes of annual ‘waste’

Amylose for

and many more, e.g., non-food fillers, composite materials, textiles, packaging materials, emulsion stabilizers, cosmetics and paints (after modification)

South Australia: competitive advantages

Security of supply (year-round production of fresh potatoes)

Additional land available to increase potato production for starch business

Range of established potato production districts close to Adelaide markets and suppliers

Varying climates between production districts allows production over extended periods

Source: Investment Attraction Agency, SA Government; Potatoes South Australia; University of Adelaide

Biomass

Integrated extraction process

Production in South Australia: around 220 tonnes/week by 2018

Example (2) of major low-value agricultural streams in South Australia

Good source of B & D vitamins, including riboflavin, niacin, and pantothenic acid, which help to provide energy by breaking down proteins, fats and carbohydrates. Source of important minerals: selenium and ergothioneine (antioxidants), copper and potassium Chitin/chitosan: structural fibre and bioactive carbohydrate polymer Beta-glucans: immunomodulating properties, resistance against allergies (Bulone et al., patented)

- Beta-glucan can be used as nutraceutical and in functional food, worth over $70M per year in Australia only- Use of chitin for ‘green’ functional materials (e.g., UV-protective materials)

- Global market for products containing chitin and chitosan: 21,000M tonnes worth an estimated $80 billion

- The global market for chitosan only is expected to reach $2 billion by 2022, with a CAGR of 17%+

Structure, sources and applications of chitin/chitosan

Shrimp-based bandage

26

Increasing application as an environmentally friendly option in textile and agrochemical

industries, specifically as a chelating agent in waste water treatment.

Increasing demand for natural skin care products, specifically hair care and cosmetics.

Increasing use as a safe, bio-compatible product in pharmaceutical and food applications.

US chitosan market by applications

chitin

chitosan

16

Health effects of ultraviolet radiationsBenefits:

- they can be used to kill germs

- they can help treating some skin conditions (e.g., rickets, psoriasis, eczema,

jaundice, lupus vulgaris, vitiligo)

- they help the formation of vitamin D in our bodies (Ca and P absorption for

bone development)

Risks involved with overexposure: acute or chronic- sunburns (erythema)

- premature skin aging [e.g., wrinkling, hardening (leathery skin)

blotchiness, loss of elasticity, dark patches ("age spots" or "liver spots"),

precancerous skin changes (actinic keratoses)

- skin cancer

- eye damage (e.g., photokeratitis and photoconjunctivitis)

- weakening of the immune system

The risks outweigh the benefits.

Keep UVA and UVB exposure as low as possible.

Sun care global market (skin care / beauty): $454 billion Sun care market in Australia: $290M

17

Examples of most common commercial UV filters

18

Examples of most common commercial UV filters

19

Violetline Maori Wrasse

Mycosporines & mycosporine-like amino acids

(MAA)

20

Mycosporines and mycosporine-like amino acids (MAA)

λmax = 334 nmε = 43 200 M-1 cm-1

Gelidium corneum

λmax = 334 nmε = 44 700 M-1 cm-1

Porphyra rosengurttii

λmax = 307 nmε = 28 700 M-1 cm-1

Lichina pygmaea

CyclohexenoneCycloheximine

Porphyra 334 Shinorine Mycosporine-Glycine

21

CS-MAA conjugates produced

Fernandes et al. (2015) ACS Appl Mater Interfaces 7: 16558–16564Patented Bulone & Fernandes

22

UV-visible spectra of CS-MAA films

250 to 800 nmFilm thickness 27 μm Fernandes et al. (2015) ACS Appl

Mater Interfaces 7: 16558–16564

UV-visible spectra of CS-MAA films (10% MAA)

24

Photostability of CS-MAA films

UV dose 40 times the dose of 1 month uninterrupted direct exposure to sunlight 3.3 years of uninterrupted exposure to sunlight 6.6 years in areas with the highest number of sunshine hours in the world 9.8 years in Brisbane, Perth and Sydney – 14.5 years in Melbourne and Adelaide

Map of yearly sunshine hours in the world

Fernandes et al. (2015) ACS Appl Mater Interfaces 7: 16558–16564

25

Thermoresistance of CS-MAA films

Fernandes et al. (2015) ACS Appl Mater Interfaces 7: 16558–16564

26

Biocompatibility of CS-MAA films

Fernandes et al. (2015) ACS Appl Mater Interfaces 7: 16558–16564

27

Biocompatibility of CS-MAA films

Fernandes et al. (2015) ACS Appl Mater Interfaces 7: 16558–16564

Vitamin D: Australian market US$164M by 2020 (worldwide market $3 billion)

normal growth and development of bones and teeth protects against muscle weakness helps prevent hypocalcemia, osteomalacia, rickets, and

osteoporosis enhances immunity required for proper thyroid function and blood clotting assists with recovery from mental illnesses, particularly depression

Powder kg Current value ($) Vitamin-D value ($) Increase ($)

Current

Daily waste 3 429 1 000 571

Yearly waste (×300) 857 128 571 300 000 171 429

Projected (2020)

Daily waste* 8 1 179 2 750 1 571

Yearly waste (×300) 2 357 353 571 825 000 471 429

Increased proportion to vitamin D production

Daily** 17 2 529 5 900 3 371

Yearly (×300) 5 057 758 571 1 770 000 1 011 429

* 10% of 55 tonnes per week generated as waste.

Mushroom powder

Vitamin D

** 40% of 55 tonnes per week production.

Powder kg Current value ($) Vitamin-D value ($) Increase ($)

Current

Daily waste 3 429 1 000 571

Yearly waste (×300) 857 128 571 300 000 171 429

Projected (2020)

Daily waste* 8 1 179 2 750 1 571

Yearly waste (×300) 2 357 353 571 825 000 471 429

Increased proportion to vitamin D production

Daily** 17 2 529 5 900 3 371

Yearly (×300) 5 057 758 571 1 770 000 1 011 429

Exploitation of Vitamin D from mushrooms

+ UV irradiation

X 100

Exploiting cellulose properties…

31

cellulose

Structural role and mechanical support

32

Bioinspired materials: nanocellulose building blocks

200 mm

1 wt% 2 wt%

33

Cellulose nanopaper

Nanopaper

Paper

Sehaqui et al. (2010) Biomacromolecules, 11, 2195-2198

34

Microfibrillated cellulose foams and their potential applications

Sehaqui et al. (2010) Soft Matter 6, 1824-1832

35

Cellulose from plant (crop!) cell walls

Acid treated"Native"

Negative staining

36

Chiral nematic suspensions of cellulose crystallites

A suspension of cellulose nanocrystals in pure water at low concentrations forms a clear stable isotropic fluid.

At higher concentrations, the nanocrystals self-align to form a ‘chiralnematic’ liquid crystalline phase.

Biphasic cellulose nanocrystal

suspension (crossed polars)

Revol, et al. (1992) Int. J. Biol. Macromol., 14, 170-172

37

The ordered structure of the suspensions can be preserved after drying

38

Iridescent films

Natural Structural Colors

Zhao et al Chem. Soc. Rev. (2012) 41: 3297-3317

20

Paracheirodon innesi

Tortoise beetleCharidotella egregia

Structural colours of cellulose nanocrystals in polymer composite films

21

Zhou & Bulone et al. (2017) Advanced Materials, in press

Reversible moisture-responsive colour change

22

42

Reversible moisture-responsive colour change

24

A competitive agricultural sector can drive Australia's global competitiveness…

…but the entire sector needs support for R&D and innovation.

Thanks to the students, post-docs & researchers in my past and current research groups…

Christian BROWN Felicia LEIJON Xiaohui XING

Ela RZESZUTEK Sujit KOTALA Qi ZHOU

Vaibhav SRIVASTAVA Thomas CROUZIER Kun YAO

Stefan KLINTER Annie AINMAN Yves HSIEH

Osei AMPOMAH Sophia EKENGREN Paul DAHLIN

Zhili PANG Francisco VILAPLANA Andrea RUTHES

Lauren McKEE Antonio ABAD Lana REZINCIUC

Sara DIAZ-MORENO Susana FERNANDES

… and to many national and international collaborators