Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging
Sorbitol derivatives and other additives are commonly used in various products, such as packaging or food packaging, to improve their mechanical, physical, and optical properties. To accurately and precisely evaluate the efficacy of adding sorbitol-type nucleating agents to these articles, their qua...
- Autores:
-
Hernández Fernández, Joaquín
Martinez Trespalacios, Jose
Marquez, Edgar
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2024
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/13826
- Acceso en línea:
- https://hdl.handle.net/11323/13826
https://repositorio.cuc.edu.co/
- Palabra clave:
- Sorbitol
Nucleating agent
Infrared spectroscopy machine learning
RMSE
SVR
- Rights
- openAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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| dc.title.eng.fl_str_mv |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| title |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| spellingShingle |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging Sorbitol Nucleating agent Infrared spectroscopy machine learning RMSE SVR |
| title_short |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| title_full |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| title_fullStr |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| title_full_unstemmed |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| title_sort |
Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packaging |
| dc.creator.fl_str_mv |
Hernández Fernández, Joaquín Martinez Trespalacios, Jose Marquez, Edgar |
| dc.contributor.author.none.fl_str_mv |
Hernández Fernández, Joaquín Martinez Trespalacios, Jose Marquez, Edgar |
| dc.subject.proposal.eng.fl_str_mv |
Sorbitol Nucleating agent Infrared spectroscopy machine learning RMSE SVR |
| topic |
Sorbitol Nucleating agent Infrared spectroscopy machine learning RMSE SVR |
| description |
Sorbitol derivatives and other additives are commonly used in various products, such as packaging or food packaging, to improve their mechanical, physical, and optical properties. To accurately and precisely evaluate the efficacy of adding sorbitol-type nucleating agents to these articles, their quantitative determination is essential. This study systematically investigated the quantification of sorbitol-type nucleating agents in food packaging made from impact copolymers of polypropylene (PP) and polyethylene (PE) using attenuated total reflectance infrared spectroscopy (ATR-FTIR) together with analysis of principal components (PCA) and machine learning algorithms. The absorption spectra revealed characteristic bands corresponding to the C–O–C bond and hydroxyl groups attached to the cyclohexane ring of the molecular structure of sorbitol, providing crucial information for identifying and quantifying sorbitol derivatives. PCA analysis showed that with the selected FTIR spectrum range and only the first two components, 99.5% of the variance could be explained. The resulting score plot showed a clear pattern distinguishing different concentrations of the nucleating agent, affirming the predictability of concentrations based on an impact copolymer. The study then employed machine learning algorithms (NN, SVR) to establish prediction models, evaluating their quality using metrics such as RMSE, R2, and RMSECV. Hyperparameter optimization was performed, and SVR showed superior performance, achieving near-perfect predictions (R2 = 0.9999) with an RMSE of 0.100 for both calibration and prediction. The chosen SVR model features two hidden layers with 15 neurons each and uses the Adam algorithm, balanced precision, and computational efficiency. The innovative ATR-FTIR coupled SVR model presented a novel and rapid approach to accurately quantify sorbitol-type nucleating agents in polymer production processes for polymer research and in the analysis of nucleating agent derivatives. The analytical performance of this method surpassed traditional methods (PCR, NN). |
| publishDate |
2024 |
| dc.date.accessioned.none.fl_str_mv |
2024-11-25T18:02:56Z |
| dc.date.available.none.fl_str_mv |
2024-11-25T18:02:56Z |
| dc.date.issued.none.fl_str_mv |
2024-04-15 |
| dc.type.none.fl_str_mv |
Artículo de revista |
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http://purl.org/coar/resource_type/c_2df8fbb1 |
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Text |
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info:eu-repo/semantics/article |
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http://purl.org/redcol/resource_type/ART |
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info:eu-repo/semantics/publishedVersion |
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http://purl.org/coar/version/c_970fb48d4fbd8a85 |
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Hernández-Fernández, J.; Martinez-Trespalacios, J.; Marquez, E. Development of a Measurement System Using Infrared Spectroscopy-Attenuated Total Reflectance, Principal Component Analysis and Artificial Intelligence for the Safe Quantification of the Nucleating Agent Sorbitol in Food Packaging. Foods 2024, 13, 1200. https://doi.org/10.3390/foods13081200 |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/13826 |
| dc.identifier.doi.none.fl_str_mv |
10.3390/foods13081200 |
| dc.identifier.eissn.none.fl_str_mv |
2304-8158 |
| dc.identifier.instname.none.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.none.fl_str_mv |
REDICUC - Repositorio CUC |
| dc.identifier.repourl.none.fl_str_mv |
https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Hernández-Fernández, J.; Martinez-Trespalacios, J.; Marquez, E. Development of a Measurement System Using Infrared Spectroscopy-Attenuated Total Reflectance, Principal Component Analysis and Artificial Intelligence for the Safe Quantification of the Nucleating Agent Sorbitol in Food Packaging. Foods 2024, 13, 1200. https://doi.org/10.3390/foods13081200 10.3390/foods13081200 2304-8158 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
| url |
https://hdl.handle.net/11323/13826 https://repositorio.cuc.edu.co/ |
| dc.language.iso.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.ispartofjournal.none.fl_str_mv |
Foods |
| dc.relation.references.none.fl_str_mv |
Plastics-the Facts 2019 An Analysis of European Plastics Production, Demand and Waste Data. Available online: https:// plasticseurope.org/wp-content/uploads/2021/10/2019-Plastics-the-facts.pdf (accessed on 24 November 2023). Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Development and validation of a methodology for quantifying partsper-billion levels of arsine and phosphine in nitrogen, hydrogen and liquefied petroleum gas using a variable pressure sampler coupled to gas chromatography-mass spectrometry. J. Chromatogr. A 2021, 1637, 461833. [CrossRef] Hernández-Fernández, J.; Castro-Suarez, J.R.; Toloza, C.A.T. Iron Oxide Powder as Responsible for the Generation of Industrial Polypropylene Waste and as a Co-Catalyst for the Pyrolysis of Non-Additive Resins. Int. J. Mol. Sci. 2022, 23, 11708. [CrossRef] Kabir, E.; Kaur, R.; Lee, J.; Kim, K.H.; Kwon, E.E. Prospects of biopolymer technology as an alternative option for non-degradable plastics and sustainable management of plastic wastes. J. Clean. Prod. 2020, 258, 120536. [CrossRef] Rendón-Villalobos, R.; Ortíz-Sánchez, A.; Tovar-Sánchez, E.; Flores-Huicochea, E. The role of biopolymers in obtaining environmentally friendly materials. Compos. Renew. Sustain. Mater. 2016, 151. Chacon, H.; Cano, H.; Fernández, J.H.; Guerra, Y.; Puello-Polo, E.; Ríos-Rojas, J.F.; Ruiz, Y. Effect of Addition of Polyurea as an Aggregate in Mortars: Analysis of Microstructure and Strength. Polymers 2022, 14, 1753. [CrossRef] [PubMed] Davis, G.; Song, J.H. Biodegradable packaging based on raw materials from crops and their impact on waste management. Ind. Crops Prod. 2006, 23, 147–161. [CrossRef] Raheem, D. Application of plastics and paper as food packaging materials—An overview. Emir. J. Food Agric. 2013, 25, 177–188. [CrossRef] Shaaban, H.A.; Farouk, A. Preservation and Packaging Food Recent Methods and Techniques: A Review. Biomed. J. Sci. Tech. Res. 2022, 46, 37680–37695. [CrossRef] Pavon, C.; Aldas, M.; Hernández-Fernández, J.; López-Martínez, J. Comparative characterization of gum rosins for their use as sustainable additives in polymeric matrices. J. Appl. Polym. Sci. 2022, 139, 51734. [CrossRef] Urzendowski, I.R.; Pechak, D.G.; Pechak, D.G. Characterization of Food Packaging Materials by Microscopic, Spectrophotometric, Thermal and Dynamic Mechanical Analysis. Food Struct. 1992, 11, 301–314. Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A.T. Experimental Study of the Impact of Trace Amounts of Acetylene and Methylacetylene on the Synthesis, Mechanical and Thermal Properties of Polypropylene. Int. J. Mol. Sci. 2022, 23, 12148. [CrossRef] [PubMed] Kristiansen, P.M. Nucleation and clarification of semi-crystalline polymers. 2004. Available online: https://www.researchcollection.ethz.ch/bitstream/handle/20.500.11850/148326/eth-27485-01.pdf (accessed on 24 November 2023). Eliaerts, J.; Dardenne, P.; Meert, N.; Van Durme, F.; Samyn, N.; Janssens, K.; De Wael, K. Rapid classification and quantification of cocaine in seized powders with ATR-FTIR and chemometrics. Drug Test Anal. 2017, 9, 1480–1489. [CrossRef] [PubMed] Hernández-Fernández, J.; Cano, H.; Aldas, M. Impact of Traces of Hydrogen Sulfide on the Efficiency of Ziegler–Natta Catalyst on the Final Properties of Polypropylene. Polymers 2022, 14, 3910. [CrossRef] [PubMed] Nucleating and Clarifying Agents for Polyolefins—Hoffmann—2001—Macromolecular Symposia—Wiley Online Library. Available online: https://onlinelibrary.wiley.com/doi/10.1002/1521-3900(200112)176:1%3C83::AID-MASY83%3E3.0.CO;2-N (accessed on 17 November 2023). Gahleitner, M.; Grein, C.; Kheirandish, S.; Wolfschwenger, J. Nucleation of polypropylene homo- and copolymers. Int. Polym. Process. 2011, 26, 2–20. [CrossRef] Menyhárd, A.; Bredács, M.; Simon, G.; Horváth, Z. Determination of nucleus density in semicrystalline polymers from nonisothermal crystallization curves. Macromolecules 2015, 48, 2561–2569. [CrossRef] Zhuravlev, E.; Wurm, A.; Pötschke, P.; Androsch, R.; Schmelzer, J.W.P.; Schick, C. Kinetics of nucleation and crystallization of poly(ε-caprolactone)—Multiwalled carbon nanotube composites. Eur. Polym. J. 2014, 52, 1–11. [CrossRef] Schawe, J.E.K.; Budde, F.; Alig, I. Non-isothermal crystallization of polypropylene with sorbitol-type nucleating agents at cooling rates used in processing. Polym. Int. 2019, 68, 240–247. [CrossRef] Fillon, B.; Lotz, B.; Thierry, A.; Wittmann, J.C. Self-nucleation and enhanced nucleation of polymers. Definition of a convenient calorimetric ‘efficiency scale’ and evaluation of nucleating additives in isotactic polypropylene (α phase). J. Polym. Sci. B Polym. Phys. 1993, 31, 1395–1405. [CrossRef] Smith, T.L.; Masilamani, D.; Bui, L.K.; Khanna, Y.P.; Bray, R.G.; Hammond, W.B.; Binder-Castelli, S. The Mechanism of Action of Sugar Acetals as Nucleating Agents for Polypropylene. Macromolecules 1994, 27, 3147–3155. [CrossRef] Nagarajan, K.; Myerson, A.S. Molecular Dynamics of Nucleation and Crystallization of Polymers. Cryst. Growth Des. 2001, 1, 131–142. [CrossRef] Marco, C.; Ellis, G.; Gómez, M.A.; Arribas, J.M. Comparative study of the nucleation activity of third-generation sorbitol-based nucleating agents for isotactic polypropylene. J. Appl. Polym. Sci. 2002, 84, 2440–2450. [CrossRef] Kristiansen, M.; Werner, M.; Tervoort, T.; Smith, P.; Blomenhofer, M.; Schmidt, H.W. The Binary System Isotactic Polypropylene/Bis(3,4-dimethylbenzylidene)sorbitol: Phase Behavior, Nucleation, and Optical Properties. Macromolecules 2003, 36, 5150–5156. [CrossRef] Marco, C.; Ellis, G.; Gómez, M.A.; Arribas, J.M. Analysis of the isothermal crystallization of isotactic polypropylene nucleated with sorbitol derivatives. J. Appl. Polym. Sci. 2003, 88, 2261–2274. [CrossRef] Microstructural Characterization of Plasticized Starch-Based Films—García—2000—Starch—Stärke—Wiley Online Library. Available online: https://onlinelibrary.wiley.com/doi/abs/10.1002/1521-379X%28200006%2952%3A4%3C118%3A%3AAIDSTAR118%3E3.0.CO%3B2-0 (accessed on 17 November 2023). Tian, H.; Liu, D.; Yao, Y.; Ma, S.; Zhang, X.; Xiang, A. Effect of Sorbitol Plasticizer on the Structure and Properties of Melt Processed Polyvinyl Alcohol Films. J. Food Sci. 2017, 82, 2926–2932. [CrossRef] [PubMed] Wang, J.; Dou, Q.; Wu, S.; Chen, X. Influence of the amount of salts of rosin acid on the nonisothermal crystallization, morphology, and properties of isotactic polypropylene. Polym. Eng. Sci. 2007, 47, 889–897. [CrossRef] Huo, H.; Jiang, S.; An, L.; Feng, J. Influence of Shear on Crystallization Behavior of the β Phase in Isotactic Polypropylene with β-Nucleating Agent. Macromolecules 2004, 37, 2478–2483. [CrossRef] Ullmann’s Polymers and Plastics: Products and Processes. Available online: https://books.google.com/books/about/Ullmann_ s_Polymers_and_Plastics_4_Volume.html?hl=es&id=MuLNwQEACAAJ (accessed on 17 November 2023). Tsochatzis, E.D.; Theodoridis, G.; Gika, H.G. Development and validation of a uhplc-qtof ms method for the determination of sorbitol-based nuclear clarifying agents in food simulants after migration from food contact materials. Appl. Sci. 2021, 11, 3789. [CrossRef] Lenhart, A.; Chey, W.D. A Systematic Review of the Effects of Polyols on Gastrointestinal Health and Irritable Bowel Syndrome. Adv. Nutr. 2017, 8, 587–596. [CrossRef] Sternbauer, L.; Dieplinger, J.; Buchberger, W.; Marosits, E. Determination of nucleating agents in plastic materials by GC/MS after microwave-assisted extraction with in situ microwave-assisted derivatization. Talanta 2014, 128, 63–68. [CrossRef] McDonald, J.G.; Cummins, C.L.; Barkley, R.M.; Thompson, B.M.; Lincoln, H.A. Identification and quantitation of sorbitol-based nuclear clarifying agents extracted from common laboratory and consumer plasticware made of polypropylene. Anal. Chem. 2008, 80, 5532–5541. [CrossRef] Grembecka, M.; Lebiedzi ´nska, A.; Szefer, P. Simultaneous separation and determination of erythritol, xylitol, sorbitol, mannitol, maltitol, fructose, glucose, sucrose and maltose in food products by high performance liquid chromatography coupled to charged aerosol detector. Microchem. J. 2014, 117, 77–82. [CrossRef] Tsochatzis, E.D.; Lopes, J.A.; Kappenstein, O.; Tietz, T.; Hoekstra, E.J. Quantification of PET cyclic and linear oligomers in teabags by a validated LC-MS method—In silico toxicity assessment and consumer’s exposure. Food Chem. 2020, 317, 2020. [CrossRef] [PubMed] Nerin, C.; Alfaro, P.; Aznar, M.; Domeño, C. The challenge of identifying non-intentionally added substances from food packaging materials: A review. Anal. Chim. Acta 2013, 775, 14–24. [CrossRef] Pitsch, J.; Weghuber, J. Hydrophilic Interaction Chromatography Coupled with Charged Aerosol Detection for Simultaneous Quantitation of Carbohydrates, Polyols and Ions in Food and Beverages. Molecules 2019, 24, 4333. [CrossRef] [PubMed] Köster, D.; Wolbert, J.B.; Schulte, M.S.; Jochmann, M.A.; Schmidt, T.C. Origin of Xylitol in Chewing Gum: A Compound-Specific Isotope Technique for the Differentiation of Corn- and Wood-Based Xylitol by LC-IRMS. J. Agric. Food Chem. 2018, 66, 2015–2020. [CrossRef] [PubMed] Hadjikinova, R.; Petkova, N.; Hadjikinov, D.; Denev, P.; Hrusavov, D. Development and Validation of HPLC-RID method for Determination of Sugars and Polyols. J. Pharm. Sci. Res. 2017, 9, 1263. Molnár-Perl, I. Simultaneous quantitation of acids and sugars by chromatography: Gas or high-performance liquid chromatography? J. Chromatogr. A 1999, 845, 181–195. [CrossRef] Medeiros, P.M.; Simoneit, B.R.T. Analysis of sugars in environmental samples by gas chromatography–mass spectrometry. J. Chromatogr. A 2007, 1141, 271–278. [CrossRef] De Castro, E.D.S.G.; Cassella, R.J. Direct determination of sorbitol and sodium glutamate by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) in the thermostabilizer employed in the production of yellow-fever vaccine. Talanta 2016, 152, 33–38. [CrossRef] Cassella, A.R.; Cassella, R.J.; Garrigues, S.; Santelli, R.E.; De Campos, R.C.; De la Guardia, M. Flow injection-FTIR determination of dithiocarbamatepesticides. Analyst 2000, 125, 1829–1833. [CrossRef] Armenta, S.; Quintás, G.; Moros, J.; Garrigues, S.; De La Guardia, M. Fourier transform infrared spectrometric strategies for the determination of Buprofezin in pesticide formulations. Anal. Chim. Acta 2002, 468, 81–90. [CrossRef] Quintás, G.; Armenta, S.; Morales-Noé, A.; Garrigues, S.; De La Guardia, M. Simultaneous determination of Folpet and Metalaxyl in pesticide formulations by flow injection Fourier transform infrared spectrometry. Anal. Chim. Acta 2003, 480, 11–21. [CrossRef] Khanmohammadi, M.; Armenta, S.; Garrigues, S.; de la Guardia, M. Mid- and near-infrared determination of metribuzin in agrochemicals. Vib. Spectrosc. 2008, 46, 82–88. [CrossRef] Moros, J.; Armenta, S.; Garrigues, S.; de la Guardia, M. Quality control of Metamitron in agrochemicals using Fourier transform infrared spectroscopy in the middle and near range. Anal. Chim. Acta 2006, 565, 255–260. [CrossRef] Garrigues, J.M.; Akssira, M.; Rambla, F.J.; Garrigues, S.; De La Guardia, M. Direct ATR-FTIR determination of sucrose in beet root. Talanta 2000, 51, 247–255. [CrossRef] Ruíz, A.; Cañada, M.J.A.; Lendl, B. A rapid method for peroxide value determination in edible oils based on flow analysis with Fourier transform infrared spectroscopic detection. Analyst 2001, 126, 242–246. [CrossRef] Ohnsmann, J.; Quintás, G.; Garrigues, S.; De la Guardia, M. Determination of caffeine in tea samples by Fourier transform infrared spectrometry. Anal. Bioanal. Chem. 2002, 374, 561–565. [CrossRef] [PubMed] Otte, X.; Eurard, B.; Oelattre, L.; Thunus, L. Development and validation of a new Fourier transform infrared spectrometric method for the quantification of urea in creams and ointments. Anal. Chim. Acta 2002, 451, 323–328. [CrossRef] Salvador, A.; Peña, M.C.; De la Guardia, M. Stopped-flow Fourier-transform infra-red spectrometric speciation of glycolic and lactic acids in cosmetic formulations. Analyst 2001, 126, 1428–1431. [CrossRef] Robaina, N.F.; de Paula, C.E.R.; Brum, D.M.; de la Guardia, M.; Garrigues, S.; Cassella, R.J. Novel approach for the determination of azithromycin in pharmaceutical formulations by Fourier transform infrared spectroscopy in film-through transmission mode. Microchem. J. 2013, 110, 301–307. [CrossRef] Garrigues, S.; Gallignani, M.; de la Guardia, M. FIA—FT—IR determination of ibuprofen in pharmaceuticals. Talanta 1993, 40, 89–93. [CrossRef] [PubMed] Sánchez-Dasi, M.J.; Garrigues, S.; Cervera, M.L.; De La Guardia, M. On-line solvent recycling: A tool for the development of clean analytical chemistry in flow injection Fourier transform infrared spectrometry. Determination of ketoprofen. Anal. Chim. Acta 1998, 361, 253–260. [CrossRef] Bouhsain, Z.; Garrigues, S.; De La Guardia, M. Flow injection–Fourier transform infrared spectrometric determination of paracetamol in pharmaceuticals. Analyst 1996, 121, 635–639. [CrossRef] Moros, J.; Garrigues, S.; de la Guardia, M. Quality control Fourier transform infrared determination of diazepam in pharmaceuticals. J. Pharm. Biomed. Anal. 2007, 43, 1277–1282. [CrossRef] [PubMed] Griffiths, P.R.; De Haseth, J.A. Oicentennial. In Fourier Transform Infrared Spectrometry, 2nd ed.; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2007. Cheng, J.H.; Sun, D.W. Rapid and non-invasive detection of fish microbial spoilage by visible and near infrared hyperspectral imaging and multivariate analysis. LWT—Food Sci. Technol. 2015, 62, 1060–1068. [CrossRef] Vasconcelos, H.; Saraiva, C.; de Almeida, J.M.M.M. Evaluation of the Spoilage of Raw Chicken Breast Fillets Using Fourier Transform Infrared Spectroscopy in Tandem with Chemometrics. Food Bioproc. Tech. 2014, 7, 2330–2341. [CrossRef] Moreira, M.J.P.; Silva, A.C.; de Almeida, J.M.M.M.; Saraiva, C. Characterization of deterioration of fallow deer and goat meat using microbial and mid infrared spectroscopy in tandem with chemometrics. Food Packag. Shelf Life 2018, 15, 169–180. [CrossRef] Lohumi, S.; Lee, S.; Lee, H.; Cho, B.K. A review of vibrational spectroscopic techniques for the detection of food authenticity and adulteration. Trends Food Sci. Technol. 2015, 46, 85–98. [CrossRef] Kamruzzaman, M.; Makino, Y.; Oshita, S. Non-invasive analytical technology for the detection of contamination, adulteration, and authenticity of meat, poultry, and fish: A review. Anal. Chim. Acta 2015, 853, 19–29. [CrossRef] Kim, D.; Hwang, J. Preparation and Characterization of Sodium Caseinate-Coated Papers Based on Glycerol and Sorbitol Contents for Packaging Application. Foods 2023, 12, 940. [CrossRef] Paudel, S.; Regmi, S.; Janaswamy, S. Effect of glycerol and sorbitol on cellulose-based biodegradable films. Food Packag. Shelf Life 2023, 37, 101090. [CrossRef] Yoplac, I.; Hidalgo, A.; Vargas, L. Characterization, microstructure, and spectroscopic study of optimized sodium caseinatesorbitol active biofilms with citral microencapsulate. Polym. Bull. 2022, 80, 5447–5468. [CrossRef] Pandey, V.K.; Srivastava, S.; Dash, K.K.; Singh, R.; Mukarram, S.A.; Kovács, B.; Harsányi, E. Machine Learning Algorithms and Fundamentals as Emerging Safety Tools in Preservation of Fruits and Vegetables: A Review. Processes 2023, 11, 1720. [CrossRef] Hernández-Fernández, J.; Guerra, Y.; Espinosa, E. Development and Application of a Principal Component Analysis Model to Quantify the Green Ethylene Content in Virgin Impact Copolymer Resins During Their Synthesis on an Industrial Scale. J. Polym. Environ. 1234, 30, 4800–4808. [CrossRef] Morita, S. Chemometrics and related fields in python. Anal. Sci. 2020, 36, 107–112. [CrossRef] [PubMed] Cited, L.; Bates, H.; Hiittenrauch, J.; Pitter, R. Smoothing and Differentiation of Data by Simplified Least Squares Procedures. Am. Pharm. Assoc. Sci. Ed. 1951, 40, 1832. Candolfi, A.; De Maesschalck, R.; Jouan-Rimbaud, D.; Hailey, P.A.; Massart, D.L. The influence of data pre-processing in the pattern recognition of excipients near-infrared spectra. J. Pharm. Biomed. Anal. 1999, 21, 115–132. [CrossRef] [PubMed] Kumar, N.; Panchariya, P.C.; Patel, S.S.; Kiranmayee, A.H.; Ranjan, R. Application of Various Pre-Processing Techniques on Infrared (IR) Spectroscopy Data for Classification of Different Ghee Samples. In Proceedings of the 2018 Fourth International Conference on Computing Communication Control and Automation (ICCUBEA), Pune, India, 16–18 August 2018. [CrossRef] Quinquenet, S.; Ollivon, M.; Grabielle-Madelmont, C.; Serpelloni, M. Polimorphism of hydrated sorbitol. Thermochim. Acta 1988, 125, 125–140. [CrossRef] Larkin, P.J. Infrared and Raman Spectroscopy: Principles and Spectral Interpretation; Elsevier: Amsterdam, The Netherlands, 2017. Lu, H.S.; Xu, H.R.; Ying, Y.B.; Fu, X.P.; Yu, H.Y.; Tian, H.Q. Application Fourier transform near infrared spectrometer in rapid estimation of soluble solids content of intact citrus fruits. J. Zhejiang Univ. Sci. B 2006, 7, 794–799. [CrossRef] Kharbach, M.; Mansouri, M.A.; Taabouz, M.; Yu, H. Current Application of Advancing Spectroscopy Techniques in Food Analysis: Data Handling with Chemometric Approaches. Foods 2023, 12, 2753. [CrossRef] Rijavec, T.; Ribar, D.; Markelj, J.; Strliˇc, M.; Cigi´c, I.K. Machine learning-assisted non-destructive plasticizer identification and quantification in historical PVC objects based on IR spectroscopy. Sci. Rep. 2022, 12, 1–11. [CrossRef] [PubMed] Siegler, B.C. Food Engineering. Available online: https://www.researchgate.net/publication/281732691_Potential_uses_of_ fourier_transform_infrared_spectroscopy_FTIR_in_food_processing_and_engineering (accessed on 17 November 2023). Pandiselvam, R.; Prithviraj, V.; Manikantan, M.R.; Kothakota, A.; Rusu, A.V.; Trif, M.; Mousavi Khaneghah, A. Recent advancements in NIR spectroscopy for assessing the quality and safety of horticultural products: A comprehensive review. Front. Nutr. 2022, 9, 973457. [CrossRef] Neo, E.R.K.; Yeo, Z.; Low, J.S.C.; Goodship, V.; Debattista, K. A review on chemometric techniques with infrared, Raman and laser-induced breakdown spectroscopy for sorting plastic waste in the recycling industry. Resour. Conserv. Recycl. 2022, 180, 106217. [CrossRef] Rodriguez-Saona, L.E.; Allendorf, M.E. Use of FTIR for rapid authentication and detection of adulteration of food. Annu. Rev. Food Sci. Technol. 2011, 2, 467–483. [CrossRef] [PubMed] Barczewski, M.; Dobrzy ´nska-Mizera, M.; Dudziec, B.; Sterzy ´nski, T. Influence of a sorbitol-based nucleating agent modified with silsesquioxanes on the non-isothermal crystallization of isotactic polypropylene. J. Appl. Polym. Sci. 2014, 131. [CrossRef] Dobrzy ´nska-Mizera, M.; Dutkiewicz, M.; Sterzy´nski, T.; Di Lorenzo, M.L. Polypropylene-based composites containing sorbitolbased nucleating agent and siloxane-silsesquioxane resin. J. Appl. Polym. Sci. 2016, 133. [CrossRef] Katsuno, S.; Yoshinaga, M.; Kitade, S.; Sanada, Y.; Akiba, I.; Sakurai, K.; Masunaga, H. Crystallization kinetics of polypropylene containing a sorbitol nucleating agent. Polymer 2012, 45, 87–93. [CrossRef] Nagarajan, K.; Levon, K.; Myerson, A.S. Nucleating agents in polypropylene. J. Therm. Anal. Calorim. 2000, 59, 497–508. [CrossRef] Lopes, J.A.; Tsochatzis, E.D.; Robouch, P.; Hoekstra, E. Influence of pre-heating of food contact polypropylene cups on its physical structure and on the migration of additives. Food Packag. Shelf Life 2019, 20, 100305. [CrossRef] |
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Atribución 4.0 Internacional (CC BY 4.0) |
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openAccess |
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18 páginas |
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Multidisciplinary Digital Publishing Institute (MDPI) |
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Switzerland |
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Multidisciplinary Digital Publishing Institute (MDPI) |
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Atribución 4.0 Internacional (CC BY 4.0)© 2024 by the authors.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Hernández Fernández, JoaquínMartinez Trespalacios, JoseMarquez, Edgar2024-11-25T18:02:56Z2024-11-25T18:02:56Z2024-04-15Hernández-Fernández, J.; Martinez-Trespalacios, J.; Marquez, E. Development of a Measurement System Using Infrared Spectroscopy-Attenuated Total Reflectance, Principal Component Analysis and Artificial Intelligence for the Safe Quantification of the Nucleating Agent Sorbitol in Food Packaging. Foods 2024, 13, 1200. https://doi.org/10.3390/foods13081200https://hdl.handle.net/11323/1382610.3390/foods130812002304-8158Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/Sorbitol derivatives and other additives are commonly used in various products, such as packaging or food packaging, to improve their mechanical, physical, and optical properties. To accurately and precisely evaluate the efficacy of adding sorbitol-type nucleating agents to these articles, their quantitative determination is essential. This study systematically investigated the quantification of sorbitol-type nucleating agents in food packaging made from impact copolymers of polypropylene (PP) and polyethylene (PE) using attenuated total reflectance infrared spectroscopy (ATR-FTIR) together with analysis of principal components (PCA) and machine learning algorithms. The absorption spectra revealed characteristic bands corresponding to the C–O–C bond and hydroxyl groups attached to the cyclohexane ring of the molecular structure of sorbitol, providing crucial information for identifying and quantifying sorbitol derivatives. PCA analysis showed that with the selected FTIR spectrum range and only the first two components, 99.5% of the variance could be explained. The resulting score plot showed a clear pattern distinguishing different concentrations of the nucleating agent, affirming the predictability of concentrations based on an impact copolymer. The study then employed machine learning algorithms (NN, SVR) to establish prediction models, evaluating their quality using metrics such as RMSE, R2, and RMSECV. Hyperparameter optimization was performed, and SVR showed superior performance, achieving near-perfect predictions (R2 = 0.9999) with an RMSE of 0.100 for both calibration and prediction. The chosen SVR model features two hidden layers with 15 neurons each and uses the Adam algorithm, balanced precision, and computational efficiency. The innovative ATR-FTIR coupled SVR model presented a novel and rapid approach to accurately quantify sorbitol-type nucleating agents in polymer production processes for polymer research and in the analysis of nucleating agent derivatives. The analytical performance of this method surpassed traditional methods (PCR, NN).18 páginasapplication/pdfengMultidisciplinary Digital Publishing Institute (MDPI)Switzerlandhttps://www.mdpi.com/2304-8158/13/8/1200Development of a measurement system using infrared spectroscopy-attenuated total reflectance, principal component analysis and artificial intelligence for the safe quantification of the nucleating agent sorbitol in food packagingArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85FoodsPlastics-the Facts 2019 An Analysis of European Plastics Production, Demand and Waste Data. Available online: https:// plasticseurope.org/wp-content/uploads/2021/10/2019-Plastics-the-facts.pdf (accessed on 24 November 2023).Hernández-Fernández, J.; Lopez-Martinez, J.; Barceló, D. Development and validation of a methodology for quantifying partsper-billion levels of arsine and phosphine in nitrogen, hydrogen and liquefied petroleum gas using a variable pressure sampler coupled to gas chromatography-mass spectrometry. J. Chromatogr. A 2021, 1637, 461833. [CrossRef]Hernández-Fernández, J.; Castro-Suarez, J.R.; Toloza, C.A.T. Iron Oxide Powder as Responsible for the Generation of Industrial Polypropylene Waste and as a Co-Catalyst for the Pyrolysis of Non-Additive Resins. Int. J. Mol. Sci. 2022, 23, 11708. [CrossRef]Kabir, E.; Kaur, R.; Lee, J.; Kim, K.H.; Kwon, E.E. Prospects of biopolymer technology as an alternative option for non-degradable plastics and sustainable management of plastic wastes. J. Clean. Prod. 2020, 258, 120536. [CrossRef]Rendón-Villalobos, R.; Ortíz-Sánchez, A.; Tovar-Sánchez, E.; Flores-Huicochea, E. The role of biopolymers in obtaining environmentally friendly materials. Compos. Renew. Sustain. Mater. 2016, 151.Chacon, H.; Cano, H.; Fernández, J.H.; Guerra, Y.; Puello-Polo, E.; Ríos-Rojas, J.F.; Ruiz, Y. Effect of Addition of Polyurea as an Aggregate in Mortars: Analysis of Microstructure and Strength. Polymers 2022, 14, 1753. [CrossRef] [PubMed]Davis, G.; Song, J.H. Biodegradable packaging based on raw materials from crops and their impact on waste management. Ind. Crops Prod. 2006, 23, 147–161. [CrossRef]Raheem, D. Application of plastics and paper as food packaging materials—An overview. Emir. J. Food Agric. 2013, 25, 177–188. [CrossRef]Shaaban, H.A.; Farouk, A. Preservation and Packaging Food Recent Methods and Techniques: A Review. Biomed. J. Sci. Tech. Res. 2022, 46, 37680–37695. [CrossRef]Pavon, C.; Aldas, M.; Hernández-Fernández, J.; López-Martínez, J. Comparative characterization of gum rosins for their use as sustainable additives in polymeric matrices. J. Appl. Polym. Sci. 2022, 139, 51734. [CrossRef]Urzendowski, I.R.; Pechak, D.G.; Pechak, D.G. Characterization of Food Packaging Materials by Microscopic, Spectrophotometric, Thermal and Dynamic Mechanical Analysis. Food Struct. 1992, 11, 301–314.Hernández-Fernández, J.; Vivas-Reyes, R.; Toloza, C.A.T. Experimental Study of the Impact of Trace Amounts of Acetylene and Methylacetylene on the Synthesis, Mechanical and Thermal Properties of Polypropylene. Int. J. Mol. Sci. 2022, 23, 12148. [CrossRef] [PubMed]Kristiansen, P.M. Nucleation and clarification of semi-crystalline polymers. 2004. Available online: https://www.researchcollection.ethz.ch/bitstream/handle/20.500.11850/148326/eth-27485-01.pdf (accessed on 24 November 2023).Eliaerts, J.; Dardenne, P.; Meert, N.; Van Durme, F.; Samyn, N.; Janssens, K.; De Wael, K. Rapid classification and quantification of cocaine in seized powders with ATR-FTIR and chemometrics. Drug Test Anal. 2017, 9, 1480–1489. [CrossRef] [PubMed]Hernández-Fernández, J.; Cano, H.; Aldas, M. Impact of Traces of Hydrogen Sulfide on the Efficiency of Ziegler–Natta Catalyst on the Final Properties of Polypropylene. Polymers 2022, 14, 3910. [CrossRef] [PubMed]Nucleating and Clarifying Agents for Polyolefins—Hoffmann—2001—Macromolecular Symposia—Wiley Online Library. Available online: https://onlinelibrary.wiley.com/doi/10.1002/1521-3900(200112)176:1%3C83::AID-MASY83%3E3.0.CO;2-N (accessed on 17 November 2023).Gahleitner, M.; Grein, C.; Kheirandish, S.; Wolfschwenger, J. Nucleation of polypropylene homo- and copolymers. Int. Polym. Process. 2011, 26, 2–20. [CrossRef]Menyhárd, A.; Bredács, M.; Simon, G.; Horváth, Z. Determination of nucleus density in semicrystalline polymers from nonisothermal crystallization curves. Macromolecules 2015, 48, 2561–2569. [CrossRef]Zhuravlev, E.; Wurm, A.; Pötschke, P.; Androsch, R.; Schmelzer, J.W.P.; Schick, C. Kinetics of nucleation and crystallization of poly(ε-caprolactone)—Multiwalled carbon nanotube composites. Eur. Polym. J. 2014, 52, 1–11. [CrossRef]Schawe, J.E.K.; Budde, F.; Alig, I. Non-isothermal crystallization of polypropylene with sorbitol-type nucleating agents at cooling rates used in processing. Polym. Int. 2019, 68, 240–247. [CrossRef]Fillon, B.; Lotz, B.; Thierry, A.; Wittmann, J.C. Self-nucleation and enhanced nucleation of polymers. Definition of a convenient calorimetric ‘efficiency scale’ and evaluation of nucleating additives in isotactic polypropylene (α phase). J. Polym. Sci. B Polym. Phys. 1993, 31, 1395–1405. [CrossRef]Smith, T.L.; Masilamani, D.; Bui, L.K.; Khanna, Y.P.; Bray, R.G.; Hammond, W.B.; Binder-Castelli, S. The Mechanism of Action of Sugar Acetals as Nucleating Agents for Polypropylene. Macromolecules 1994, 27, 3147–3155. [CrossRef]Nagarajan, K.; Myerson, A.S. Molecular Dynamics of Nucleation and Crystallization of Polymers. Cryst. Growth Des. 2001, 1, 131–142. [CrossRef]Marco, C.; Ellis, G.; Gómez, M.A.; Arribas, J.M. Comparative study of the nucleation activity of third-generation sorbitol-based nucleating agents for isotactic polypropylene. J. Appl. Polym. Sci. 2002, 84, 2440–2450. [CrossRef]Kristiansen, M.; Werner, M.; Tervoort, T.; Smith, P.; Blomenhofer, M.; Schmidt, H.W. The Binary System Isotactic Polypropylene/Bis(3,4-dimethylbenzylidene)sorbitol: Phase Behavior, Nucleation, and Optical Properties. Macromolecules 2003, 36, 5150–5156. [CrossRef]Marco, C.; Ellis, G.; Gómez, M.A.; Arribas, J.M. Analysis of the isothermal crystallization of isotactic polypropylene nucleated with sorbitol derivatives. J. Appl. Polym. Sci. 2003, 88, 2261–2274. [CrossRef]Microstructural Characterization of Plasticized Starch-Based Films—García—2000—Starch—Stärke—Wiley Online Library. Available online: https://onlinelibrary.wiley.com/doi/abs/10.1002/1521-379X%28200006%2952%3A4%3C118%3A%3AAIDSTAR118%3E3.0.CO%3B2-0 (accessed on 17 November 2023).Tian, H.; Liu, D.; Yao, Y.; Ma, S.; Zhang, X.; Xiang, A. Effect of Sorbitol Plasticizer on the Structure and Properties of Melt Processed Polyvinyl Alcohol Films. J. Food Sci. 2017, 82, 2926–2932. [CrossRef] [PubMed]Wang, J.; Dou, Q.; Wu, S.; Chen, X. Influence of the amount of salts of rosin acid on the nonisothermal crystallization, morphology, and properties of isotactic polypropylene. Polym. Eng. Sci. 2007, 47, 889–897. [CrossRef]Huo, H.; Jiang, S.; An, L.; Feng, J. Influence of Shear on Crystallization Behavior of the β Phase in Isotactic Polypropylene with β-Nucleating Agent. Macromolecules 2004, 37, 2478–2483. [CrossRef]Ullmann’s Polymers and Plastics: Products and Processes. Available online: https://books.google.com/books/about/Ullmann_ s_Polymers_and_Plastics_4_Volume.html?hl=es&id=MuLNwQEACAAJ (accessed on 17 November 2023).Tsochatzis, E.D.; Theodoridis, G.; Gika, H.G. Development and validation of a uhplc-qtof ms method for the determination of sorbitol-based nuclear clarifying agents in food simulants after migration from food contact materials. Appl. Sci. 2021, 11, 3789. [CrossRef]Lenhart, A.; Chey, W.D. A Systematic Review of the Effects of Polyols on Gastrointestinal Health and Irritable Bowel Syndrome. Adv. Nutr. 2017, 8, 587–596. [CrossRef]Sternbauer, L.; Dieplinger, J.; Buchberger, W.; Marosits, E. Determination of nucleating agents in plastic materials by GC/MS after microwave-assisted extraction with in situ microwave-assisted derivatization. Talanta 2014, 128, 63–68. [CrossRef]McDonald, J.G.; Cummins, C.L.; Barkley, R.M.; Thompson, B.M.; Lincoln, H.A. Identification and quantitation of sorbitol-based nuclear clarifying agents extracted from common laboratory and consumer plasticware made of polypropylene. Anal. Chem. 2008, 80, 5532–5541. [CrossRef]Grembecka, M.; Lebiedzi ´nska, A.; Szefer, P. Simultaneous separation and determination of erythritol, xylitol, sorbitol, mannitol, maltitol, fructose, glucose, sucrose and maltose in food products by high performance liquid chromatography coupled to charged aerosol detector. Microchem. J. 2014, 117, 77–82. [CrossRef]Tsochatzis, E.D.; Lopes, J.A.; Kappenstein, O.; Tietz, T.; Hoekstra, E.J. Quantification of PET cyclic and linear oligomers in teabags by a validated LC-MS method—In silico toxicity assessment and consumer’s exposure. Food Chem. 2020, 317, 2020. [CrossRef] [PubMed]Nerin, C.; Alfaro, P.; Aznar, M.; Domeño, C. The challenge of identifying non-intentionally added substances from food packaging materials: A review. Anal. Chim. Acta 2013, 775, 14–24. [CrossRef]Pitsch, J.; Weghuber, J. Hydrophilic Interaction Chromatography Coupled with Charged Aerosol Detection for Simultaneous Quantitation of Carbohydrates, Polyols and Ions in Food and Beverages. Molecules 2019, 24, 4333. [CrossRef] [PubMed]Köster, D.; Wolbert, J.B.; Schulte, M.S.; Jochmann, M.A.; Schmidt, T.C. Origin of Xylitol in Chewing Gum: A Compound-Specific Isotope Technique for the Differentiation of Corn- and Wood-Based Xylitol by LC-IRMS. J. Agric. Food Chem. 2018, 66, 2015–2020. [CrossRef] [PubMed]Hadjikinova, R.; Petkova, N.; Hadjikinov, D.; Denev, P.; Hrusavov, D. Development and Validation of HPLC-RID method for Determination of Sugars and Polyols. J. Pharm. Sci. Res. 2017, 9, 1263.Molnár-Perl, I. Simultaneous quantitation of acids and sugars by chromatography: Gas or high-performance liquid chromatography? J. Chromatogr. A 1999, 845, 181–195. [CrossRef]Medeiros, P.M.; Simoneit, B.R.T. Analysis of sugars in environmental samples by gas chromatography–mass spectrometry. J. Chromatogr. A 2007, 1141, 271–278. [CrossRef]De Castro, E.D.S.G.; Cassella, R.J. Direct determination of sorbitol and sodium glutamate by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) in the thermostabilizer employed in the production of yellow-fever vaccine. Talanta 2016, 152, 33–38. [CrossRef]Cassella, A.R.; Cassella, R.J.; Garrigues, S.; Santelli, R.E.; De Campos, R.C.; De la Guardia, M. Flow injection-FTIR determination of dithiocarbamatepesticides. Analyst 2000, 125, 1829–1833. [CrossRef]Armenta, S.; Quintás, G.; Moros, J.; Garrigues, S.; De La Guardia, M. Fourier transform infrared spectrometric strategies for the determination of Buprofezin in pesticide formulations. Anal. Chim. Acta 2002, 468, 81–90. [CrossRef]Quintás, G.; Armenta, S.; Morales-Noé, A.; Garrigues, S.; De La Guardia, M. Simultaneous determination of Folpet and Metalaxyl in pesticide formulations by flow injection Fourier transform infrared spectrometry. Anal. Chim. Acta 2003, 480, 11–21. [CrossRef]Khanmohammadi, M.; Armenta, S.; Garrigues, S.; de la Guardia, M. Mid- and near-infrared determination of metribuzin in agrochemicals. Vib. Spectrosc. 2008, 46, 82–88. [CrossRef]Moros, J.; Armenta, S.; Garrigues, S.; de la Guardia, M. Quality control of Metamitron in agrochemicals using Fourier transform infrared spectroscopy in the middle and near range. Anal. Chim. Acta 2006, 565, 255–260. [CrossRef]Garrigues, J.M.; Akssira, M.; Rambla, F.J.; Garrigues, S.; De La Guardia, M. Direct ATR-FTIR determination of sucrose in beet root. Talanta 2000, 51, 247–255. [CrossRef]Ruíz, A.; Cañada, M.J.A.; Lendl, B. A rapid method for peroxide value determination in edible oils based on flow analysis with Fourier transform infrared spectroscopic detection. Analyst 2001, 126, 242–246. [CrossRef]Ohnsmann, J.; Quintás, G.; Garrigues, S.; De la Guardia, M. Determination of caffeine in tea samples by Fourier transform infrared spectrometry. Anal. Bioanal. Chem. 2002, 374, 561–565. [CrossRef] [PubMed]Otte, X.; Eurard, B.; Oelattre, L.; Thunus, L. Development and validation of a new Fourier transform infrared spectrometric method for the quantification of urea in creams and ointments. Anal. Chim. Acta 2002, 451, 323–328. [CrossRef]Salvador, A.; Peña, M.C.; De la Guardia, M. Stopped-flow Fourier-transform infra-red spectrometric speciation of glycolic and lactic acids in cosmetic formulations. Analyst 2001, 126, 1428–1431. [CrossRef]Robaina, N.F.; de Paula, C.E.R.; Brum, D.M.; de la Guardia, M.; Garrigues, S.; Cassella, R.J. Novel approach for the determination of azithromycin in pharmaceutical formulations by Fourier transform infrared spectroscopy in film-through transmission mode. Microchem. J. 2013, 110, 301–307. [CrossRef]Garrigues, S.; Gallignani, M.; de la Guardia, M. FIA—FT—IR determination of ibuprofen in pharmaceuticals. Talanta 1993, 40, 89–93. [CrossRef] [PubMed]Sánchez-Dasi, M.J.; Garrigues, S.; Cervera, M.L.; De La Guardia, M. On-line solvent recycling: A tool for the development of clean analytical chemistry in flow injection Fourier transform infrared spectrometry. Determination of ketoprofen. Anal. Chim. Acta 1998, 361, 253–260. [CrossRef]Bouhsain, Z.; Garrigues, S.; De La Guardia, M. Flow injection–Fourier transform infrared spectrometric determination of paracetamol in pharmaceuticals. Analyst 1996, 121, 635–639. [CrossRef]Moros, J.; Garrigues, S.; de la Guardia, M. Quality control Fourier transform infrared determination of diazepam in pharmaceuticals. J. Pharm. Biomed. Anal. 2007, 43, 1277–1282. [CrossRef] [PubMed]Griffiths, P.R.; De Haseth, J.A. Oicentennial. In Fourier Transform Infrared Spectrometry, 2nd ed.; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2007.Cheng, J.H.; Sun, D.W. Rapid and non-invasive detection of fish microbial spoilage by visible and near infrared hyperspectral imaging and multivariate analysis. LWT—Food Sci. Technol. 2015, 62, 1060–1068. [CrossRef]Vasconcelos, H.; Saraiva, C.; de Almeida, J.M.M.M. Evaluation of the Spoilage of Raw Chicken Breast Fillets Using Fourier Transform Infrared Spectroscopy in Tandem with Chemometrics. Food Bioproc. Tech. 2014, 7, 2330–2341. [CrossRef]Moreira, M.J.P.; Silva, A.C.; de Almeida, J.M.M.M.; Saraiva, C. Characterization of deterioration of fallow deer and goat meat using microbial and mid infrared spectroscopy in tandem with chemometrics. Food Packag. Shelf Life 2018, 15, 169–180. [CrossRef]Lohumi, S.; Lee, S.; Lee, H.; Cho, B.K. A review of vibrational spectroscopic techniques for the detection of food authenticity and adulteration. Trends Food Sci. Technol. 2015, 46, 85–98. [CrossRef]Kamruzzaman, M.; Makino, Y.; Oshita, S. Non-invasive analytical technology for the detection of contamination, adulteration, and authenticity of meat, poultry, and fish: A review. Anal. Chim. Acta 2015, 853, 19–29. [CrossRef]Kim, D.; Hwang, J. Preparation and Characterization of Sodium Caseinate-Coated Papers Based on Glycerol and Sorbitol Contents for Packaging Application. Foods 2023, 12, 940. [CrossRef]Paudel, S.; Regmi, S.; Janaswamy, S. Effect of glycerol and sorbitol on cellulose-based biodegradable films. Food Packag. Shelf Life 2023, 37, 101090. [CrossRef]Yoplac, I.; Hidalgo, A.; Vargas, L. Characterization, microstructure, and spectroscopic study of optimized sodium caseinatesorbitol active biofilms with citral microencapsulate. Polym. Bull. 2022, 80, 5447–5468. [CrossRef]Pandey, V.K.; Srivastava, S.; Dash, K.K.; Singh, R.; Mukarram, S.A.; Kovács, B.; Harsányi, E. Machine Learning Algorithms and Fundamentals as Emerging Safety Tools in Preservation of Fruits and Vegetables: A Review. Processes 2023, 11, 1720. [CrossRef]Hernández-Fernández, J.; Guerra, Y.; Espinosa, E. Development and Application of a Principal Component Analysis Model to Quantify the Green Ethylene Content in Virgin Impact Copolymer Resins During Their Synthesis on an Industrial Scale. J. Polym. Environ. 1234, 30, 4800–4808. [CrossRef]Morita, S. Chemometrics and related fields in python. Anal. Sci. 2020, 36, 107–112. [CrossRef] [PubMed]Cited, L.; Bates, H.; Hiittenrauch, J.; Pitter, R. Smoothing and Differentiation of Data by Simplified Least Squares Procedures. Am. Pharm. Assoc. Sci. Ed. 1951, 40, 1832.Candolfi, A.; De Maesschalck, R.; Jouan-Rimbaud, D.; Hailey, P.A.; Massart, D.L. The influence of data pre-processing in the pattern recognition of excipients near-infrared spectra. J. Pharm. Biomed. Anal. 1999, 21, 115–132. [CrossRef] [PubMed]Kumar, N.; Panchariya, P.C.; Patel, S.S.; Kiranmayee, A.H.; Ranjan, R. Application of Various Pre-Processing Techniques on Infrared (IR) Spectroscopy Data for Classification of Different Ghee Samples. In Proceedings of the 2018 Fourth International Conference on Computing Communication Control and Automation (ICCUBEA), Pune, India, 16–18 August 2018. [CrossRef]Quinquenet, S.; Ollivon, M.; Grabielle-Madelmont, C.; Serpelloni, M. Polimorphism of hydrated sorbitol. Thermochim. Acta 1988, 125, 125–140. [CrossRef]Larkin, P.J. Infrared and Raman Spectroscopy: Principles and Spectral Interpretation; Elsevier: Amsterdam, The Netherlands, 2017.Lu, H.S.; Xu, H.R.; Ying, Y.B.; Fu, X.P.; Yu, H.Y.; Tian, H.Q. Application Fourier transform near infrared spectrometer in rapid estimation of soluble solids content of intact citrus fruits. J. Zhejiang Univ. Sci. B 2006, 7, 794–799. [CrossRef]Kharbach, M.; Mansouri, M.A.; Taabouz, M.; Yu, H. Current Application of Advancing Spectroscopy Techniques in Food Analysis: Data Handling with Chemometric Approaches. Foods 2023, 12, 2753. [CrossRef]Rijavec, T.; Ribar, D.; Markelj, J.; Strliˇc, M.; Cigi´c, I.K. Machine learning-assisted non-destructive plasticizer identification and quantification in historical PVC objects based on IR spectroscopy. Sci. Rep. 2022, 12, 1–11. [CrossRef] [PubMed]Siegler, B.C. Food Engineering. Available online: https://www.researchgate.net/publication/281732691_Potential_uses_of_ fourier_transform_infrared_spectroscopy_FTIR_in_food_processing_and_engineering (accessed on 17 November 2023).Pandiselvam, R.; Prithviraj, V.; Manikantan, M.R.; Kothakota, A.; Rusu, A.V.; Trif, M.; Mousavi Khaneghah, A. Recent advancements in NIR spectroscopy for assessing the quality and safety of horticultural products: A comprehensive review. Front. Nutr. 2022, 9, 973457. [CrossRef]Neo, E.R.K.; Yeo, Z.; Low, J.S.C.; Goodship, V.; Debattista, K. A review on chemometric techniques with infrared, Raman and laser-induced breakdown spectroscopy for sorting plastic waste in the recycling industry. Resour. Conserv. Recycl. 2022, 180, 106217. [CrossRef]Rodriguez-Saona, L.E.; Allendorf, M.E. Use of FTIR for rapid authentication and detection of adulteration of food. Annu. Rev. Food Sci. Technol. 2011, 2, 467–483. [CrossRef] [PubMed]Barczewski, M.; Dobrzy ´nska-Mizera, M.; Dudziec, B.; Sterzy ´nski, T. Influence of a sorbitol-based nucleating agent modified with silsesquioxanes on the non-isothermal crystallization of isotactic polypropylene. J. Appl. Polym. Sci. 2014, 131. [CrossRef]Dobrzy ´nska-Mizera, M.; Dutkiewicz, M.; Sterzy´nski, T.; Di Lorenzo, M.L. Polypropylene-based composites containing sorbitolbased nucleating agent and siloxane-silsesquioxane resin. J. Appl. Polym. Sci. 2016, 133. [CrossRef]Katsuno, S.; Yoshinaga, M.; Kitade, S.; Sanada, Y.; Akiba, I.; Sakurai, K.; Masunaga, H. Crystallization kinetics of polypropylene containing a sorbitol nucleating agent. Polymer 2012, 45, 87–93. [CrossRef]Nagarajan, K.; Levon, K.; Myerson, A.S. Nucleating agents in polypropylene. J. Therm. Anal. Calorim. 2000, 59, 497–508. [CrossRef]Lopes, J.A.; Tsochatzis, E.D.; Robouch, P.; Hoekstra, E. Influence of pre-heating of food contact polypropylene cups on its physical structure and on the migration of additives. Food Packag. Shelf Life 2019, 20, 100305. [CrossRef]181813SorbitolNucleating agentInfrared spectroscopy machine learningRMSESVRPublicationORIGINALDevelopment of a Measurement System Using Infrared.pdfDevelopment of a Measurement System Using Infrared.pdfapplication/pdf3800866https://repositorio.cuc.edu.co/bitstreams/d7c79a23-2626-4dfe-8d96-3f20b2241329/download6b20d8ca40d753e1410f7c11d0069d2aMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-815543https://repositorio.cuc.edu.co/bitstreams/04a5c4db-13a5-4c34-b262-936c5918d6e2/download73a5432e0b76442b22b026844140d683MD52TEXTDevelopment of a Measurement System Using Infrared.pdf.txtDevelopment of a Measurement System Using Infrared.pdf.txtExtracted texttext/plain79229https://repositorio.cuc.edu.co/bitstreams/a076fcad-f63b-46cb-a65b-639b4b71a4d1/download7aedd137f8280543c393a9efa0d1d1c4MD53THUMBNAILDevelopment of a Measurement System Using Infrared.pdf.jpgDevelopment of a Measurement System Using Infrared.pdf.jpgGenerated 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ara ejercer estos derechos sobre la Obra tal y como se indica a continuación:</p>
    <ol type="a">
      <li>Reproducir la Obra, incorporar la Obra en una o más Obras Colectivas, y reproducir la Obra incorporada en las Obras Colectivas.</li>
      <li>Distribuir copias o fonogramas de las Obras, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública, incluyéndolas como incorporadas en Obras Colectivas, según corresponda.</li>
      <li>Distribuir copias de las Obras Derivadas que se generen, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública.</li>
    </ol>
    <p>Los derechos mencionados anteriormente pueden ser ejercidos en todos los medios y formatos, actualmente conocidos o que se inventen en el futuro. Los derechos antes mencionados incluyen el derecho a realizar dichas modificaciones en la medida que sean técnicamente necesarias para ejercer los derechos en otro medio o formatos, pero de otra manera usted no está autorizado para realizar obras derivadas. Todos los derechos no otorgados expresamente por el Licenciante quedan por este medio reservados, incluyendo pero sin limitarse a aquellos que se mencionan en las secciones 4(d) y 4(e).</p>
  </li>
  <br/>
  <li>
    Restricciones.
    <p>La licencia otorgada en la anterior Sección 3 está expresamente sujeta y limitada por las siguientes restricciones:</p>
    <ol type="a">
      <li>Usted puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra sólo bajo las condiciones de esta Licencia, y Usted debe incluir una copia de esta licencia o del Identificador Universal de Recursos de la misma con cada copia de la Obra que distribuya, exhiba públicamente, ejecute públicamente o ponga a disposición pública. No es posible ofrecer o imponer ninguna condición sobre la Obra que altere o limite las condiciones de esta Licencia o el ejercicio de los derechos de los destinatarios otorgados en este documento. No es posible sublicenciar la Obra. Usted debe mantener intactos todos los avisos que hagan referencia a esta Licencia y a la cláusula de limitación de garantías. Usted no puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra con alguna medida tecnológica que controle el acceso o la utilización de ella de una forma que sea inconsistente con las condiciones de esta Licencia. Lo anterior se aplica a la Obra incorporada a una Obra Colectiva, pero esto no exige que la Obra Colectiva aparte de la obra misma quede sujeta a las condiciones de esta Licencia. Si Usted crea una Obra Colectiva, previo aviso de cualquier Licenciante debe, en la medida de lo posible, eliminar de la Obra Colectiva cualquier referencia a dicho Licenciante o al Autor Original, según lo solicitado por el Licenciante y conforme lo exige la cláusula 4(c).</li>
      <li>Usted no puede ejercer ninguno de los derechos que le han sido otorgados en la Sección 3 precedente de modo que estén principalmente destinados o directamente dirigidos a conseguir un provecho comercial o una compensación monetaria privada. El intercambio de la Obra por otras obras protegidas por derechos de autor, ya sea a través de un sistema para compartir archivos digitales (digital file-sharing) o de cualquier otra manera no será considerado como estar destinado principalmente o dirigido directamente a conseguir un provecho comercial o una compensación monetaria privada, siempre que no se realice un pago mediante una compensación monetaria en relación con el intercambio de obras protegidas por el derecho de autor.</li>
      <li>Si usted distribuye, exhibe públicamente, ejecuta públicamente o ejecuta públicamente en forma digital la Obra o cualquier Obra Derivada u Obra Colectiva, Usted debe mantener intacta toda la información de derecho de autor de la Obra y proporcionar, de forma razonable según el medio o manera que Usted esté utilizando: (i) el nombre del Autor Original si está provisto (o seudónimo, si fuere aplicable), y/o (ii) el nombre de la parte o las partes que el Autor Original y/o el Licenciante hubieren designado para la atribución (v.g., un instituto patrocinador, editorial, publicación) en la información de los derechos de autor del Licenciante, términos de servicios o de otras formas razonables; el título de la Obra si está provisto; en la medida de lo razonablemente factible y, si está provisto, el Identificador Uniforme de Recursos (Uniform Resource Identifier) que el Licenciante especifica para ser asociado con la Obra, salvo que tal URI no se refiera a la nota sobre los derechos de autor o a la información sobre el licenciamiento de la Obra; y en el caso de una Obra Derivada, atribuir el crédito identificando el uso de la Obra en la Obra Derivada (v.g., "Traducción Francesa de la Obra del Autor Original," o "Guión Cinematográfico basado en la Obra original del Autor Original"). Tal crédito puede ser implementado de cualquier forma razonable; en el caso, sin embargo, de Obras Derivadas u Obras Colectivas, tal crédito aparecerá, como mínimo, donde aparece el crédito de cualquier otro autor comparable y de una manera, al menos, tan destacada como el crédito de otro autor comparable.</li>
      <li>
        Para evitar toda confusión, el Licenciante aclara que, cuando la obra es una composición musical:
        <ol type="i">
          <li>Regalías por interpretación y ejecución bajo licencias generales. El Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública o la ejecución pública digital de la obra y de recolectar, sea individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, SAYCO), las regalías por la ejecución pública o por la ejecución pública digital de la obra (por ejemplo Webcast) licenciada bajo licencias generales, si la interpretación o ejecución de la obra está primordialmente orientada por o dirigida a la obtención de una ventaja comercial o una compensación monetaria privada.</li>
          <li>Regalías por Fonogramas. El Licenciante se reserva el derecho exclusivo de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, los consagrados por la SAYCO), una agencia de derechos musicales o algún agente designado, las regalías por cualquier fonograma que Usted cree a partir de la obra (“versión cover”) y distribuya, en los términos del régimen de derechos de autor, si la creación o distribución de esa versión cover está primordialmente destinada o dirigida a obtener una ventaja comercial o una compensación monetaria privada.</li>
        </ol>
      </li>
      <li>Gestión de Derechos de Autor sobre Interpretaciones y Ejecuciones Digitales (WebCasting). Para evitar toda confusión, el Licenciante aclara que, cuando la obra sea un fonograma, el Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública digital de la obra (por ejemplo, webcast) y de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, ACINPRO), las regalías por la ejecución pública digital de la obra (por ejemplo, webcast), sujeta a las disposiciones aplicables del régimen de Derecho de Autor, si esta ejecución pública digital está primordialmente dirigida a obtener una ventaja comercial o una compensación monetaria privada.</li>
    </ol>
  </li>
  <br/>
  <li>
    Representaciones, Garantías y Limitaciones de Responsabilidad.
    <p>A MENOS QUE LAS PARTES LO ACORDARAN DE OTRA FORMA POR ESCRITO, EL LICENCIANTE OFRECE LA OBRA (EN EL ESTADO EN EL QUE SE ENCUENTRA) “TAL CUAL”, SIN BRINDAR GARANTÍAS DE CLASE ALGUNA RESPECTO DE LA OBRA, YA SEA EXPRESA, IMPLÍCITA, LEGAL O CUALQUIERA OTRA, INCLUYENDO, SIN LIMITARSE A ELLAS, GARANTÍAS DE TITULARIDAD, COMERCIABILIDAD, ADAPTABILIDAD O ADECUACIÓN A PROPÓSITO DETERMINADO, AUSENCIA DE INFRACCIÓN, DE AUSENCIA DE DEFECTOS LATENTES O DE OTRO TIPO, O LA PRESENCIA O AUSENCIA DE ERRORES, SEAN O NO DESCUBRIBLES (PUEDAN O NO SER ESTOS DESCUBIERTOS). ALGUNAS JURISDICCIONES NO PERMITEN LA EXCLUSIÓN DE GARANTÍAS IMPLÍCITAS, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.</p>
  </li>
  <br/>
  <li>
    Limitación de responsabilidad.
    <p>A MENOS QUE LO EXIJA EXPRESAMENTE LA LEY APLICABLE, EL LICENCIANTE NO SERÁ RESPONSABLE ANTE USTED POR DAÑO ALGUNO, SEA POR RESPONSABILIDAD EXTRACONTRACTUAL, PRECONTRACTUAL O CONTRACTUAL, OBJETIVA O SUBJETIVA, SE TRATE DE DAÑOS MORALES O PATRIMONIALES, DIRECTOS O INDIRECTOS, PREVISTOS O IMPREVISTOS PRODUCIDOS POR EL USO DE ESTA LICENCIA O DE LA OBRA, AUN CUANDO EL LICENCIANTE HAYA SIDO ADVERTIDO DE LA POSIBILIDAD DE DICHOS DAÑOS. ALGUNAS LEYES NO PERMITEN LA EXCLUSIÓN DE CIERTA RESPONSABILIDAD, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.</p>
  </li>
  <br/>
  <li>
    Término.
    <ol type="a">
      <li>Esta Licencia y los derechos otorgados en virtud de ella terminarán automáticamente si Usted infringe alguna condición establecida en ella. Sin embargo, los individuos o entidades que han recibido Obras Derivadas o Colectivas de Usted de conformidad con esta Licencia, no verán terminadas sus licencias, siempre que estos individuos o entidades sigan cumpliendo íntegramente las condiciones de estas licencias. Las Secciones 1, 2, 5, 6, 7, y 8 subsistirán a cualquier terminación de esta Licencia.</li>
      <li>Sujeta a las condiciones y términos anteriores, la licencia otorgada aquí es perpetua (durante el período de vigencia de los derechos de autor de la obra). No obstante lo anterior, el Licenciante se reserva el derecho a publicar y/o estrenar la Obra bajo condiciones de licencia diferentes o a dejar de distribuirla en los términos de esta Licencia en cualquier momento; en el entendido, sin embargo, que esa elección no servirá para revocar esta licencia o que deba ser otorgada , bajo los términos de esta licencia), y esta licencia continuará en pleno vigor y efecto a menos que sea terminada como se expresa atrás. La Licencia revocada continuará siendo plenamente vigente y efectiva si no se le da término en las condiciones indicadas anteriormente.</li>
    </ol>
  </li>
  <br/>
  <li>
    Varios.
    <ol type="a">
      <li>Cada vez que Usted distribuya o ponga a disposición pública la Obra o una Obra Colectiva, el Licenciante ofrecerá al destinatario una licencia en los mismos términos y condiciones que la licencia otorgada a Usted bajo esta Licencia.</li>
      <li>Si alguna disposición de esta Licencia resulta invalidada o no exigible, según la legislación vigente, esto no afectará ni la validez ni la aplicabilidad del resto de condiciones de esta Licencia y, sin acción adicional por parte de los sujetos de este acuerdo, aquélla se entenderá reformada lo mínimo necesario para hacer que dicha disposición sea válida y exigible.</li>
      <li>Ningún término o disposición de esta Licencia se estimará renunciada y ninguna violación de ella será consentida a menos que esa renuncia o consentimiento sea otorgado por escrito y firmado por la parte que renuncie o consienta.</li>
      <li>Esta Licencia refleja el acuerdo pleno entre las partes respecto a la Obra aquí licenciada. No hay arreglos, acuerdos o declaraciones respecto a la Obra que no estén especificados en este documento. El Licenciante no se verá limitado por ninguna disposición adicional que pueda surgir en alguna comunicación emanada de Usted. Esta Licencia no puede ser modificada sin el consentimiento mutuo por escrito del Licenciante y Usted.</li>
    </ol>
  </li>
  <br/>
</ol>
 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