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1 Claudia Sorlini Già professore ordinario di Microbiologia Agraria Università degli Studi di Milano Presidente del Comitato Scientifico per EXPO Comune di Milano Past full professor of Agricultural Microbiology - University of Milan President of the Scientific Committee for EXPO - Municipality of Milan Via S. Tommaso Milano Tel Mob comitatoscientifico.expo@comune.milano.it 1
2 L approccio AQUAPHOTOMICS: metodologia e case studies Tiziana M.P. Cattaneo Consiglio per la Ricerca in Agricoltura e l analisi dell economia agraria; CRA-IAA, Milan Italy Winter school, gennaio 2015, Milano
3 OUTLINE Introduction Applications in food science: Scattering and absorption Just water Metal ions Fermentation Food quality and packaging Conclusions Acknowledgements
4 AQUAPHOTOMICS CONCEPT
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14 The Aquaphotomics concept helps to positively evaluate the water changes occurring, after physical or chemical perturbations, in different and several bio-systems. The direct monitoring of food processes or/and chemical and physical changes in biological matrices is not often possible. These information can be collected through the study of water patterns in NIR region.
15 Water in extreme conditions (Lawrence Livermore National Laboratory, S&TR October 2005, )
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17 WATER CLUSTER Nemethy and Scheraga, 1962 The changes in the water spectrum are comparable to variations due to changes in temperature, probably associated with a different H-bond content. The substances inducing a change in the spectrum comparable to an increase in temperature are termed structure-breakers. The substances inducing a change comparable to a decrease of temperature are termed structure-makers. R. Giangiacomo, 2006, Food Chemistry, 96 (3),
18 Extracting scattering information and identify the wavelength ranges mainly influenced by particles distribution and size. VIP coefficients for casein calibration on milk spectral data. Before (brillant blu line) and after ( sweet blue line) EMSC correction C C C8! Cattaneo, T.M.P.; Cabassi, G.; Profaizer, M.; Giangiacomo, R., 2009, JNIRS, 17 (6)
19 SPECTRUM OF DIFFERENCES AMONG WATER SAMPLES (Giangiacomo R. et al., 2010, 14 th ICNIRS Proc., Thailand, )
20 Not only the mineral concentration, but also the types of minerals and their hydration capacities can affect water spectral response in the NIR range. MSC pre-treated spectra
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23 AQUAPHOTOMICS: WAVELENGTHS INVOLVED IN THE STUDY OF THE SPECIATION OF METAL IONS (Zn 2+, Pb 2+, Ag + ) IN AQUEOUS SOLUTIONS. (Vero S. et al., 2010, NIRNews, 21 (8), 11-13) The main differences among spectra are detectable in the range , confirming the possibility to indirectly study cation solutions and their speciation by using water spectral modifications. [20mM], ph 1.50 First derivative 4.50E E E E E E Wavelength (nm) Zn2+, Ag+, Pb2+ Zn2+ Ag+ Pb2+
24 The study of the evolution of the spectra of individual ions at increasing ph values (Pb 2+ ) First derivative 6.00E E E E E E E Wavelength (nm) ph = 2.00 ph = 3.00 ph = 4.11 ph = 5.15 ph = 5.45 The spectral changes corresponding to ph variations are clearly visible in the selected NIR range. The water absorption bands seemed to be involved as possible descriptors of the presence of different cation species at each selected ph.
25 For increasing ph values from 3.00 to 5.15, it is possible to notice that the changes in the first derivative flexes and maxima can be interpreted as a function of the increased concentration of the species PbOH + to 10-5 M. A further change was observed at ph 5.45, at which the presence of hydroxocomplex Pb 4 (OH) 4 4+ with a final concentration of 10-4 M becomes important. The determination of the predominant components in spectra allowed the distinction between the different ways in which the water matrix is influenced by the presence of different cations at the different ph values. These data can contribute to update the Aquaphotomics library in order to better understand which and what kinds of molecular bonds can modify water spectra, modifications that can also occur for the presence of natural or added compounds in very low concentrations.
26 THE USE OF NEAR INFRARED SPECTROSCOPY FOR MONITORING MILK- WHEY BIOTRANSFORMATION PROCESSES USING Lactobacillus plantarum Remagni M.C. et al., 2012, (2012), 15th ICNIRS Proc., Cape Town, South Africa, Strain log CFU/mL t0 t6 t8 t11 t15 t18 t24 t28 t32 t ph Tim e (hours) Relationship between microbial growth and fermentation trend: Adaptability of Lactobacillus plantarum on the substrate tested: within 48 hours strains reached growth values of order 9 log CFU/mL demostrating how this species is able to multiply even in non-optimal growth conditions.
27 Lactose - validation and calibration curves Pretreatment R cal SEC (g/100g) Offset Slope R val SEP (g/100g) Offset Slope RER RPD CV% reference method Lactose SNV 0,985 0,197 0,1 0,97 0,98 0,18 0,12 0,97 24,4 6,05 3%
28 Lactic Acid - calibration and validation curves Pretreatment R cal SEC (g/100g) Offset Slope R val SEP (g/100g) Offset Slope RER RPD CV% referemce method Lactic SNV, acid 2^ derivative 0,980 0,164 0,04 0,95 0,986 0,154 0,06 0,91 23,15 4,87 3%
29 t0 t15 t28 AQUAGRAM OF FERMENTATION PROCESS t03 t06 t08 t11 t18 t20 t22 t24 t32 t42 t , ,00-1, O-H Stretch C-H stretch. and bend.
30 Relationship between bands intensity and analyte concentration Increasing of the water absorption bands with the incubation time
31 NUTRACEUTICAL PROPERTIES OF ITALIAN RICE Barzaghi S. et al., 2014, NIRItalia2014 Proceedings, Total tocopherols content (RPD = 3,47; screening method)
32 <0.5 >0.5 <4 >4 <6 >6 <10 (ppm) , ,00-1, Increase in tocopherols content corresponded to a decrease in water absorption
33 1518 fat-water interactions AQUAGRAM Storage days dehydration Cattaneo T.M.P. et al., 2014, SciX 2014, 09/28 10/03, Reno (NV), US
34 Natural dehydration during storage influenced Aquagram on the basis of an increased number of water-bonded molecules and a decreasing of free water molecules. At 21 days, no linear relationship with storage was detected. The maximum of variability was associated to this sampling point for weight loss calibration (Cattaneo T.M.P. et al., 2014, NIRItalia2014 Proceedings, ), supporting Aquagram s results.
35 WAPS The specific Water Spectral Absorbance Patterns illustrated phase transitions in the system over the time on the basis of the increasing absorption intensity over the time, detected at 950, 970, 1200 nm.
36 INFLUENCE OF PACKAGING (MSC pretreated spectra) C11 C12 Pack 1 Pack 2 C1 C2 C3 C4 C5
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38 SHELF LIFE OF WHITE MELON: INFLUENCE OF COATING (Cattaneo T.M.P. et al., 2014, NIRItalia2014 Proceedings, )
39 SKIN (surface) PULP (inside) Aquagrams showed differences ascribable to different coating permeability. Each coating generates a specific fingerprint for the same product.
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47 CONCLUSIONS The chemical or physical perturbations applied to water (solution, suspension) disrupt the flickering cluster of water, breaking some water H-bonds and generating some new H-bonds, both in the non-solvent water and in the water involved as solvent. This higher number of water H-bonds, compared to those in the pure water, is more stable and with higher energy, giving rise to a new water spectrum. The information provided support the use of Aquaphotomics as suitable tool in explaining and monitoring the evolution of biosystems through the study of water absorption pattern.
48 CONCLUSIONS The Aquaphotomics approach was found to be highly informative when applied in various fields, such as medical, food and pharmaceutical. Future work will involve dissemination of this knowledge and developing the entire aquaphotome, i.e. collective characterization of all possible windows of electromagnetic spectrum where water molecular system could be observed. In the future, we expect to be able to explain how the water spectral pattern is related to food characteristics and functionalities, such as freshness. Another important future direction is to understand how water, as the matrix of life, changes with time and environmental changes like temperature, humidity, atmospheric pressure.
49 AKNOWLEDGEMENTS This review collected results obtained during the last 10 years MAINLY by the NIR team of CRA-FLC, Lodi, Italy. The chemometrics expertise of Dr.ssa Stefania Barzaghi, CRA-FLC researcher, has been crucial to obtain suitable and useful information.
50 Thank you for your attention!
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