agrofood research madeira

José S. Câmara Centro de Química da Madeira,

Universidade da Madeira

FÓRUM AGRO-ALIMENTAR

july 9th , 2015

AGROFOOD RESEARCH IN CQM

2http://cqm.uma.pt

MATERIALS GROUP

NATURAL PRODUCTS

GROUP CQM

Research in the field of new materials §  In par4cular molecular and nanomaterials §  Specific applica4ons: nanomedicine and optoelectronics

Characteriza4on and evalua4on of core components of foodstuffs

§  evaluation and identification of bioactive components of aromatic/medicinal plants and foods; § used as food constituents; search for new therapeutic molecules

Overview

NATLab

ACECQM Lab

3http://cqm.uma.pt

Bioactivity of Hydroxycinnamic Acids and derivatives from edible

and medicinal plants

Chemotaxonomy of Macaronesian endemic species (plants and fungi)

Extraction of added value substances from Beer Spent Grain

Ø  Hydroxycinnamic Acids Ø  Proteins Ø  enzymes

S t a b i l i z a t i o n o f l a b i l e componentes isolated from plant extracts

Ø  Adsorption in porous materials

Ø  Microencapsulation

Ø  Incorporation in microfibers

Ø  Identification of marker compounds

Ø  Evaluation of genetic variability

Ø  Identification by MSn Ø  enzymatic inhibition – in silico and in vitro studies Ø  Antioxidant, antibacterial and antifungal activities Ø  disgestion simulation

IMPACT ON QUALITY AND FOOD SECURITY

Overview

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MEDICINAL CHEMISTRY

FOOD CHEMISTRY

§  Chemical characterization – VOMs; TAC §  Valorization of regional food products

Public health promotion and well being

§  Biomarkers detection in several patologies –Cancer, CVD and Asthma

ACECQMLab

Projects and Partners

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AntiVin MAC

VINSAUDE MAC

AVC-CV MAC

OTHERS

•  ULL •  CVIP •  HUC (La Laguna) •  CSIC (Canárias)

• IVBAM • Madeira Wine Company • HMBorges • Henriques & Henriques •  Vinhos Barbeito

• Insular Moinhos • ECM • Hospital Dr. Nélio Mendonça • LRVSA

UNIÃO EUROPEIA Fundo Europeu

de Desenvolvimento Regional

6http://cqm.uma.pt

Madeira wines

RAM typical fruits

Vegetables

Chemical characterization as a powerful

approach to determine and establish the

genuinity and typicity of RAM agro foods

Ensure DOC quality

Useful tool on support to fraud detec4on

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Madeira Wine Studies

Grapes chemical

composi4on Grape

matura4on markers

Vola4le wine composi4on

Ageing markers

Bioac4ve polyphenols

TAC

Aroma network Madeira wines

EC SOTOLON FURANICS

TCA

Contribu4on for deeper insights into Madeira wines

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Distribution of grape cultivars used to produce Madeira wine

Malvazia Bual

Verdelho Sercial

Tinta Negra

Grapes and Madeira Wine Research

Véraison

2ndD

imen

sion

(s)

0.17

0.67

1.17

1.67

MaturityMalvasia Cândida

2ndD

imen

sion

(s)

0.17

0.67

1.17

1

.67

Véraison MaturitySercial

Véraison

2ndD

imen

sion

(s)

0.17

0.67

1.17

1.67

338 538 738 938

1st Dimension (s)

Maturity

338 538 738 938

1st Dimension (s)

Tinta Negra

C10 C13 C15

Hydrocarbons

Oxygen containing

2ndD

imen

sion

(s)

0.17

0.67

1.17

1.67

Véraison

Hydrocarbons

Oxygen containing

Maturity

C10 C13 C15

Bual

C10 C13 C15

Hydrocarbons

Oxygen containing

Hydrocarbons

Oxygen containingC10 C13 C15

C10 C13 C15

Hydrocarbons

Oxygen containing

Hydrocarbons


C10 C13 C15

Hydrocarbons

Oxygen containing

Hydrocarbons


Grape maturity markers

114 VOMs 71 monoterpenic

25 sesquiterpenic

18 norisoprenoids

44 were reported 1st

4me 11 are

predominant


High source of sesquiterpenics

Bual grapes High source of monoterpenics

Malvazia grapes

8 monoterpenic 2 sesquiterpenic 7 norisoprenoids


common to all classification models, and they could be used as potential grape maturity markers.

• Anti-inflammatory • Anti-bacterial including enhancement of bacterial susceptibility to antibiotics

• Anti-carcinogenic • Antioxidant, hepatoprotection

Present in several fruits where they have been reported as potential contributors to the aroma characteristics and health benefits of wine

• Suitable tool to support winemaker decision based on grape potentialities

• improving the excellence of Madeira wine – fruity, floral and citric notes

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Wine composi4on

v  0,5% sulphites v  1,5% acids (tartaric, malic, citric, succinic, acetic,

lactic, gallic) v  1% sugars v  1% proteins and aminoacids v  1% vitamins (A, B, K and G, thiamin, riboflavin,

niacin, folate, choline, betaine, lutein, zeaxanthin) v  1% minerals (Na, Ca, Fe, Mg, P, K, Zn, Cu, Mn, F,

Se) v  1% bioactive compounds (polyphenols like

catechins ,quercetin, resveratrol, tannins, etc) v  Volatile organic compounds - aroma

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Wine Research

Comprehensive Insights into Madeira Wine Aroma

Furans2-Furfural

2-Furanmethanol

2-Acetylfuran

5-Methyl-2-furfural

2-Pentylfuran

Ethyl 2-furoate

1-(2-Furyl)-1-propanone

2-Acetyl-5-methylfuran

2-Diethoxymethylfuran

3-Acetyl-2,5-dimethylfuran

Methyl 2-furoate

Furaneol

Maltol

5-Ethoxymethyl-2-furfural

5-Hydroxymethylfurfural

Sulphur compounds2-Thiophenecarboxaldehyde

2-Thiophenemethanol

2-Formyl-5-methylthiophene

Ethyl 3-(methylthio)propionate

BenzothiazoleEstersEthyl acetate

Ethyl propanoate

Ethyl isobutyrate

Isobutyl acetate

Ethyl formate

Ethyl butyrate

Ethyl lactate

Ethyl 2-butenoate

Ethyl isovalerate

Isoamyl acetate

Ethyl pentanoate

Pentyl acetate

Ethyl 3-hydroxybutanoate

Ethyl 2-hydroxyisovalerate

Isoamyl propionate

cis-3-Hexenyl acetate

Ethyl 3-hexanoate

Hexyl acetate

Ethyl 2-hexenoate

Isoamyl butanoate

Ethyl 2-hydroxy-4-methylpentanoate

Ethyl levulate

Diethyl malonate

Ethyl 6-heptenoate

Methyl benzoate

Ethyl heptanoate

Ethyl sorbate

Diethyl methylmalonate

Isopentyl 2-methylbutanoate

Isopentyl isovalerate

Ethyl 3-hydroxyhexanoate

Ethyl benzoate

2-Phenethyl formate

Methyl benzeneacetate

Diethyl succinate

Ethyl octanoate

Ethyl phenylacetate

2-Phenethyl acetate

Ethyl dl-malate

Ethyl salicylate

Ethyl nonanoate

Ethyl hydrocinnamate

Methyl cinnamate

Butyl benzoate

Diethyl hexanedioate

Ethyl decanoate

2-Phenylethyl isobutanoate

2-Phenylethyl butanoate

Isoamyl octanoate

Ethyl cinnamate

2-Phenylethyl benzoate

Propyl decanoate

Ethyl citrate

Hexyl salicylate

Ethyl hexadecanoate

Pyrazines2-Methylpyrazine

2,3-Dimethyl-pyrazine


5-Methy-2-ethylpyrazine

3-Methyl-2-ethylpyrazine

Norisoprenoids2,2,6-Trimethylcyclohexanone

α-Isophoron

4-Oxoisophorone

Safranal

β-Cyclocitral

Vitispirane

1,2-Dihydro-1,1,6-trimethylnaphthalene

cis-β-Damascenone

α-Ionol

trans-β-Damascenone

α-Ionone

Geranyl acetone

β-Ionone

Monoterpenic compoundsα-Pineneα-Phellandrenep-CymeneLimoneneOcimene quintoxide cis-Linalool oxide Terpinolene γ-Terpinene trans-Linalool oxide Linalooltrans-Rose oxide Fenchol cis-Rose oxide α-Terpinol Nerol oxide Ocimenoltrans-Borneol Myrtenol p-Cymen-8-ol α-TerpineolL-Verbenone p-Menth-1-en-9-al NerolCitronellolGeraniolPerilla alcoholp-Cymen-7-ol α-Cedrene Lilyal Methyl dihydrojasmonate

Volatile compounds (283) that explain the Madeira wine aroma notes

Aromatic alcoholsBenzenemethanol

2-Phenylethyl alcohol

Furans2-Furfural

2-Furanmethanol

2-Acetylfuran

5-Methyl-2-furfural

2-Pentylfuran

Ethyl 2-furoate

1-(2-Furyl)-1-propanone

2-Acetyl-5-methylfuran

2-Diethoxymethylfuran

3-Acetyl-2,5-dimethylfuran

Methyl 2-furoate

Furaneol

Maltol

5-Ethoxymethyl-2-furfural

5-Hydroxymethylfurfural

EstersEthyl acetate

Ethyl propanoate

Ethyl isobutyrate

Isobutyl acetate

Ethyl formate

Ethyl butyrate

Ethyl lactate

Ethyl 2-butenoate

Ethyl isovalerate

Isoamyl acetate

Ethyl pentanoate

Pentyl acetate

Ethyl 3-hydroxybutanoate

Ethyl 2-hydroxyisovalerate

Isoamyl propionate

cis-3-Hexenyl acetate

Ethyl 3-hexanoate

Hexyl acetate

Ethyl 2-hexenoate

Isoamyl butanoate

Ethyl 2-hydroxy-4-methylpentanoate

Ethyl levulate

Diethyl malonate

Ethyl 6-heptenoate

Methyl benzoate

Ethyl heptanoate

Ethyl sorbate

Diethyl methylmalonate

Isopentyl 2-methylbutanoate

Isopentyl isovalerate

Ethyl 3-hydroxyhexanoate

Ethyl benzoate

2-Phenethyl formate

Methyl benzeneacetate

Diethyl succinate

Ethyl octanoate

Ethyl phenylacetate

2-Phenethyl acetate

Ethyl dl-malate

Ethyl salicylate

Ethyl nonanoate

Ethyl hydrocinnamate

Methyl cinnamate

Butyl benzoate

Diethyl hexanedioate

Ethyl decanoate

2-Phenylethyl isobutanoate

2-Phenylethyl butanoate

Isoamyl octanoate

Ethyl cinnamate

2-Phenylethyl benzoate

Propyl decanoate

Ethyl citrate

Hexyl salicylate

Ethyl hexadecanoate

Volatile Phenolso-Methylanisole

o-Cresol

p-Methylguaiacol

2-Phenoxyethanol

p-Vinylguaiacol

Eugenol

Methyl eugenol

Vanillin

Ethyl vanillate

Lactonesγ-Butyrolactone

α-Angelicalactone

Lavander lactone

Pantolactone

γ-Hexalactone

Solerone

γ-Heptalactone

γ-Octalactone

trans-oak-lactone

cis-oak-lactone

γ-Nonalactone

γ-Decalactone

Massoia lactone

γ-Dodecalactone

δ-Dodecalactone

Pyrazines2-Methylpyrazine



5-Methy-2-ethylpyrazine

3-Methyl-2-ethylpyrazine

Sesquiterpenic compoundsβ-Caryophylleneα-trans-bergamoteneCalareneAromadendrene oxideα-Patchouleneα-Muuroleneδ-Cadineneβ-Sesquiphellandreneα-Calacoreneβ-Calacorene(-)-Caryophyllene oxideγ-EudesmolCedrolι-Cadinolα-BisabololFarnesyl acetateα-Cadinol

Acetals1,1-Diethoxyethane

1,1-Diethoxy-2-methyl-propane

1,1-Diethoxy-3-methylbutane

1,3,3-Triethoxypropane

1,1-Diethoxyhexane

1-(1-Ethoxyethoxy)-hexane

1,1-Diethoxyoctane

1,1-Diethoxynonane

1,1-Diethoxydecane

153 volatile compounds are reported for the first time in Madeira wine

Each color represents an aroma note. The width line corresponds to the number of shared aroma compounds

Young Madeira wines Old Madeira wines

CaramelDried fruitsDried orange peelSpiceTeaToastWood

Alm

ond

Citr

usC

ocoa

Flor

alFr

uity

Toba

cco

Woo

d

Almond

Caramel

Dried fruits

Dried orange pell

Toast

Vanilla

Spice

Wood

Tobacco

AlmondCitrusCocoaFloralFruityTobaccoWood

HoneyCitrusWaxyMushroomCitrusRipe fruitTeaWood




AlmondCitrusCocoaFloralFruityTobaccoWoodHoneyCitrusWaxyMushroom

Dried fruitsHoneySpiceToastEtherealWood

Almond

Caramel

Dried fruits

Dried orange pell

Toast

Vanilla

Spice

Wood

Tobacco

Younger

Madeira wines

Older

Madeira wines

Malvasia Bual

AlmondCocoaFloralFruityTea

HoneyCitrusWaxyMushroom

SpiceHoneyFloralFruityMushroom

Citrus

Ripe fruit

TeaWood

Tinta Negra

Malvasia Bual

Verdelho

Shared Compounds

VerdelhoSercial

Sercial

Tinta Negra

40 - 7020 - 4010 - 200 - 10

Malvasia Bual

Sercial Verdelho Sercial Verdelho

Madeira Wine Aroma network

AlmondCocoaFloralFruityTea

SpiceHoneyFloralFruityMushroom

CitrusRipe fruitTeaWood



HoneyCitrusWaxyMushroom

Almond

Caramel

Dried fruits

Dried orange pell

Toast

Vanilla

Spice

Wood

Tobacco

Almond

Caramel

Dried fruits

Dried orange pell

Toast

Vanilla

Spice

Wood

Tobacco

Younger

Madeira wines

Older

Madeira wines

Malvasia Bual

Tinta Negra

Malvasia BualAlmond

Caramel

Dried fruits

Dried orange pell

Toast

Vanilla

Spice

Wood

Tobacco

Almond

Caramel

Dried fruits

Tea

Toast

Spice

Wood

Dried orange pellHoneyDried fruitsToastVanillaSpiceWood

Dried fruitsHoneySpiceToastEtherealWood

CaramelDried fruitsDried orange pellSpiceTeaToastWood

Verdelho

Shared Compounds

VerdelhoSercial

Sercial

Tinta Negra

40 - 7020 - 4010 - 200 - 10

Malvasia Bual

Sercial Verdelho Sercial Verdelho

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Wine polyphenol characterization by UPLC

3 5 6

10

1 white wine

1 - Gallic acid;

2 - Protocatechuic

acid;

3 - Catechin;

4 - Gentisic acid;

5 - Epicatechin;

6 - Syringic acid;

7 - p-coumaric acid;

8 - Ferulic acid;

9 - m-coumaric acid;

10 - Rutin;

11 - Resveratrol;

12 - Myricetin;

13 - Quercitin;

14 - Cinnamic acid;

15 - Kaempferol.

red wine 3

5 6

7 1

1 2

3

4

5 6

7

8

9 10

11

12 13

14

15

polyphenols standards mixture

15 polyphenols identified in just 5min!

18http://cqm.uma.pt

Polyphenols

Sensorial -

Color Taste

Antihypertensive

Antimicro-bial

Antioxidant effects

Enzymatic modulatio

n

Anti-inflammator

y effects

CVD Cancer

Neurodegene-rative

Disease protectio

n

Why Polyphenols?

19http://cqm.uma.pt

BEER

VOLATILE COMPOSITION

Raw Materials

Different stages of BEER produc4on

BEER POLYPHENOLS

20http://cqm.uma.pt

BANANA

ANONA

APPLE “PEROS TRADICIONAIS”

PASSION FRUITS

PITANGA

ENDEMIC BLACKBERRY

(uveira)

DELICIOUS FRUIT

RAM tropical and endemic fruits

Valoriza4on of regional products; Evalua4on of genuinity/typicity

BANANA

21http://cqm.uma.pt

Dwarf Cavendish Prata Maçã

Platano Ouro

ANNONA

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Perry Vidal Funchal

Madeira Mateus

Apple “Pêro Regional”

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Ponta do Pargo Santo Serra

Camacha Porto Santo

PASSION FRUIT

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PurpleYellow

OrangeLemon

Banana

Tomato

Melon

PeachPineapple

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VEGETABLES

Tomato VOMs, TAC; vitamines; ripening

An4oxidant poten4al; vola4le metabolites-‐ Carrot

Brocolli – polyphenolic profile, VOMs

Valoriza4on of regional products; Evalua4on of genuinity/typicity

26http://cqm.uma.pt

SECONDARY METABOLITES PRODUCED BY FUNGI

Food ContaminaNons PotenNal hazard for humans and animals

Neurotoxic Mutagenic Carcinogenic

...

Different types of Toxicity Considered by European Food Safety Authority

(EFSA) as a specific hazard category

Where they can be found? Produced by different Fungi:

ü  Fusarium sp. ü  Aspergillus sp. ü  Penicillium sp.

FOOD SAFETY - Mycotoxins

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Evaluation of the occurrence of mycotoxins in cereals

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UNIVERSITY of MADEIRA Portugal

AGRO FOOD ENTERPRISES

PARTNERS FROM DIFFERENT FIELDS

CQM ACE Lab

Network to promote the transfer of knowledge from institutions for the business sector in order to improve its competitiveness

30http://cqm.uma.pt

REDE/1517/RMN/2005 REDE/1508/RNEM/2005

THANK YOU FOR YOUR ATTENTION …

UNIÃO EUROPEIA Fundo Europeu

de Desenvolvimento Regional

31

INTERESTS

METHODOLOGIES

APPLICATIONS

Oxida4ve damage and Diseases

Biomarkers

Bioac4ve compounds

Microextrac4on

SPME, NTME

MEPS, µSPE, µQuEChERS Liquid

Chromatography

Gas Chromatography

Wine Tea Coffee

Plasma Exhaled Breath

Fruits Vegetables

Urine

Beer SAMPLES

Bioac4ves in food matrices and beverages (phenolics, carotenoids, tocopherols, terpenoids)

Madeira WINES

Food safety (mycotoxins)

Drug abuse (an4psycho4cs , an4depressants)

Cancer volatomics

ACECQM Lab

Endemic and typical fruits

Vegetables VOMs

agrofood research madeira

Food

vraison hydrocarbons

dimension s maturity

madeira frum agroalimentar

food security overview

t i o n o f

food constituents search

predominant grape ma

studies antioxidant