agrofood research madeira
TRANSCRIPT
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
4http://cqm.uma.pt
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
5http://cqm.uma.pt
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
Oxygen containingC10 C13 C15
C10 C13 C15
Hydrocarbons
Oxygen containing
Hydrocarbons
Oxygen containingC10 C13 C15
Grape maturity markers
114 VOMs 71 monoterpenic
25 sesquiterpenic
18 norisoprenoids
44 were reported 1st
4me 11 are
predominant
Grape maturity markers
High source of sesquiterpenics
Bual grapes High source of monoterpenics
Malvazia grapes
8 monoterpenic 2 sesquiterpenic 7 norisoprenoids
Grape maturity markers
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
2,6-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
2,3-Dimethyl-pyrazine
2,6-Dimethyl-pyrazine
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
AlmondCitrusCocoaFloralFruityTobaccoWood
AlmondCitrusCocoaFloralFruityTobaccoWood
AlmondCitrusCocoaFloralFruityTobaccoWood
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
AlmondCitrusCocoaFloralFruityTobaccoWood
AlmondCitrusCocoaFloralFruityTobaccoWood
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
22http://cqm.uma.pt
Perry Vidal Funchal
Madeira Mateus
Apple “Pêro Regional”
23http://cqm.uma.pt
Ponta do Pargo Santo Serra
Camacha Porto Santo
PASSION FRUIT
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PurpleYellow
OrangeLemon
Banana
Tomato
Melon
PeachPineapple
25http://cqm.uma.pt
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
27http://cqm.uma.pt
Evaluation of the occurrence of mycotoxins in cereals
28http://cqm.uma.pt
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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