Nuevos Envases Activos Para Cosmética
Cris%na Nerín Universidad de Zaragoza
I3A, Dept. Anal. Chem. Campus Rio Ebro María de Luna 3, 50018 Zaragoza, Spain
2
GUIA GROUP (GRUPO UNIVERSITARIO DE INVESTIGACIÓN ANALÍTICA)
Torres Quevedo building (Campus Rio Ebro)
Ø Department of analytical chemistry University of Zaragoza
Ø I3A –Aragón Institute of engineering research
Research we do • Food-‐Packaging Interac1ons • Food safety related to packaging:
– specific migra1on analysis – NIAS studies: Iden1fica1on and quan1fica1on
• Quality related parameters: odor, off-‐odors iden1fica1on, …
• Development of ac1ve packaging materials • Development of intelligent materials • Development of analy1cal procedures for all the
studies
3
Outline
• The concept • The measurement • The development • Case study 1 • Case study 2 • Conclusions
The “ideal” Packaging
Active Packaging Intelligent Packaging
Absorbers
Radicals Oxygen Humidity Colestherol Odors CO2…
Releasers Biocides, AnBmicrobials Aromas Insect repellents
Indicators
TIme-‐temperature Freshness Microorganisms Off-‐odors Deadline
WHAT IS ACTIVE PACKAGING
Mode of action
An1oxidants Free Radical Scavengers Oxygen scavengers u No direct contact needed u Free radical scavengers
act in presence of oxygen
An1microbials Released from the packaging u A protec1ve atmosphere is
created around the product to inhibit miroorganisms growth
u Organolep1c issues have
to be tested.
ACTIVE PACKAGING
(–CH=CH–CH2–CH=CH–) O2 R·
If one of the three components is removed the process cannot go on
OXIDATION of ORGANIC SUBSTRATES
The concept
Radical scavengers
Determina1on of the an1oxidant capacity of ac1ve food packagings by in situ gas-‐phase hydroxyl radical genera1on and high-‐performance liquid chromatography–fluorescence detec1on. Pezo, D., et al. (2008). J Chromat A 1178(1–2): 126-‐133.
Radical forma1on H2O2 à OH. (ultraviolet radia1on)
SeNP solu1ons Free radicals react with SeNPs
Salicilic acid will react with the free radicals remaining
Salicylic acid + OH. à 2,5-‐DHB +2,3-‐DHB + catechol
Determina1on of an1oxidant capacity. Free radical method
% HydroxilaBon AnBoxidant
What kind of an1oxidants/an1radicals
• Essen1al oils • Plant extracts • Nanopar1cles
• Inside the polymer
(extrusion) (polyethylene, polypropylene)
• Inside the adhesive (not in direct contact with food)
• In a lacquer/varnish in the internal layer of the packaging
The best solu1on
Why? Because free radicals can cross the polymer!
extrusion coa1ng mul1layer
AnBoxidant packaging based on SeNPs
Laminated PET-‐adhesive-‐PE
AcBve substance
SeNPs (radical scavenger)
Material
Se0
Adhesive PET
PE
Case study 1
Produc1on of nanoSe
• Stable nanoSe were produced: generated in situ and encapsulated.
• Round nanoparBcles beeer than nano-‐rods • Size range: 50-‐60 nm diameter
Se0
Case study 1
0
200
400
600
800
1000
1200
1400
1600
adhesivo puro
adhesivo + 5%
blanco 4
4m35 + 5% nanos tanda 4 (5ppm)
adhesivo + 10 % blanco 4
4m35 + 10% nanos tanda 4 (10ppm)
adhesivo + 5 %
blanco 5
4m35 + 5% nanos tanda 5 (5ppm)
adhesivo + 10%
blanco 5
4m35 + 10% nanos tanda 5 (10ppm)
adhesivo + 5 %
blanco 6
4m35 + 5% nanos tanda 6 (5ppm)
adhesivo + 10%
blanco 6
4m35 + 10% nanos tanda 6 (10ppm)
CAOX (ugT/gadh)
CAOX del adhesivo con para las disoluciones con distintos estabilizantes
Selec1on of stabilizing agent and experimental condi1ons
An1oxidant performance of adhesive containing the nanoSe
Case study 1
Maximum: 10% SeNPs soluBon
Prepara1on of an1oxidant mul1layer with nanoSe
PET 12µm
PE
Adhesive + SeNPs
Free radicals: • Oxo • Hydroxo • peroxo
Different thickness
Case study 1
NanoSe
Se NP in disolución
SeNP in mul1layer
An1oxidant capacity of the new ac1ve mul1layer in vitro
0
10
20
30
40
50
60
70
80
90
100
Reference Laminate with PE 35μm
Laminate with PE 60μm
Laminate with PE 90μm
%Hy
droxyla1
on
• 35 µm • 60 µm • 90 µm
Reference: laminate prepared with adhesive without SeNPs
PE thicknesses:
Case study 1
Industrial roll
Scale up AcBve Material
Industrial produc1on of the new an1oxidant mul1layer
Case study 1
Stability of the new an1oxidant material with nanoSe
Storage for 3 months
Reference: laminate prepared with adhesive without SeNPs
Case study 1
Bags with hazelnuts or walnuts
An1oxidant capacity of the new an1oxidant mu1layer in vivo
TBARS method
!"#$%
!"#&%
!"'$%
!"'&%
!"$$%
!"$&%
!"($%
!"(&%
!% (% )!% )(% #!% #(% '!% '(% $!% $(%
!"#$%&'
()"#
*+()*,
-.*,
&/01231
4&
5+0,&/*(.64&
7(8,)#9:6&
*+,+-+./+%
0123%4+567%
!"#$
!"%$
&$
&"&$
&"'$
&"#$
&"%$
($
)$ *$ !)$ !*$ &)$ &*$ ()$ (*$ ')$ '*$
!"#$%&'
()"#
*+()*,
-.*,
&/01231
4&
5+0,&/*(.64&
7()#896&
+,-,.,/0,$
1234$5,678$
Accelerated oxida1on test
Case study 1
Migra1on
78Se < 2.32 ng/g (LOD) in food simulants 77Se < 0.46 ng/ml (LOD) in hazelnuts 77Se/78Se similar in blanks and acBve samples
10 days at 40ºC of exposure 77SeNP were used for in vivo studies (hazelnuts)
21
An ac1ve formula of green tea extract (GTE) has been developed and integrated in bio-‐packaging at
industrial level
NEW ACTIVE PACKAGING
ANTIRADICAL-‐ANTIOXIDANT
Case study 2
AnBoxidant packaging based on Green Tea
Laminated PET-‐adhesive-‐PE
AcBve substance
Green Tea (radical scavenger)
Material Adhesive PET
PE
• Strong an1oxidant proper1es: polyphenols (Catechins, Gallic a., Caffeine)
Case study 2
• An1oxidant material produced – At lab scale – At industrial scale
• The Efficiency of the new Material tested – in vitro – in vivo: Coffee industry; Chocolate Company
• Migra1on tests done • Organolep1c tests done
GREEN TEA in a MULTILAYER
Case study 2
PRODUCTS
CHOCOLATES LACASA GROUP
Sugar coated dragees Choco coated dragees
24
Praline Nougats Candies
Chocolate Bars Chocolate bombon&truffles
A CASE STUDY IN A CHOCOLATE COMPANY
Case study 2
Chocolate coated peanuts
Evaluation during 16 months
Chocolate coated cereals Star1ng day 24/02/2013
Conguitos (peanuts)
Cereals
Sample size 1 Kg bags each 1 Kg trays each
Sample Nº 36 36
Sample type 18 bags with acBve material
18 trays with acBve material
18 bags of usual material
18 trays of usual material
Evalua1on of An1oxidant capacity on food
Fahy acids
Hexanal (rancidity)
Organolep1c tests
Parameters
pyrazines
Case study 2
Cereals (blue line acBve material, red NON-‐ acBve material)
Conguitos (blue line acBve material, red NON-‐acBve material)
Shelf life Shelf life
0,000
0,100
0,200
0,300
0,400
0,500
0,600
0,700
0,800
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T14 T16
Serie1
Serie2
0,000
0,500
1,000
1,500
2,000
2,500
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T14 T16
Serie1
Serie2
ü NO migration ü NO organoleptic issues ü NO changes in packaging line
Evalua1on in real food. RESULTS (Hexanal)
Case study 2
Pyrazines profile for ac1ve (blue bars) and non-‐ac1ve (red bars) packaging systems in dark chocolate peanuts
Evalua1on in real food:RESULTS (pyrazines)
Case study 2
• AnBoxidant mulBlayer packaging with radical scavengers is an efficient approach and easier to produce and use
• Free radicals of oxo, hydroxo and peroxo can diffuse throughout the LDPE layer.
• NanoSe and green tea behave as efficient an1radicals even without being in direct contact with the packaged product (food, cosme1cs,etc..)
• The material behaves in the packaging lines exactly the same as the convenBonal
packaging materials.
• Each product requires an specific acBve material and appropriate opBmizaBon • Material with nanoSe can be also applied in any mulBlayer behind PE. ThinPE
layers are preferred
Concluding Remarks
• NANOFLEXIPACK (Spanish Ministry MINECO) – GUIA group Universidad de Zaragoza – AnalyBcal Traces group, Universidad
Complutense, Madrid – SAMTACK – MAGAPOR
• SAFEMTECH (EU Project) – GUIA group University of Zaragoza – GOGLIO
Acknowledgements