Abstract
Chitosan (CH) is a biopolymer derived from chitin, which is the second most abundant polysaccharide in nature, after cellulose. Their functional groups -NH2 and -OH can form intermolecular interactions with water and other molecules, enabling a variety of applications for CH. -NH2 groups become protonated in acidic solutions, causing an increase in electrostatic repulsion between CH chains, which facilitates their dispersion in aqueous media. Aqueous solutions of acetic acid and/or acetates buffers have been used to disperse CH, but may not be adequate for technological applications, espeacially because of the strong flavor this acid confers to formulations. In this study, 0.125; 0.250; 0.500; 0.750 and 1.000 g (100 g)−1 CH dispersions were prepared in acidic aqueous media (50 mmol L−1), not only with acetic (AA), but also with glycolic (GA), propionic (PA), or lactic (LA), acid aiming to evaluate the effects of biopolymer concentration and type of organic acid on: electrical conductivity, pH, density and rheological characteristics of dispersions. Moreover, ζ potential values of CH chains dispersed in these acidic aqueous media were assessed. pH, density and consistency index were influenced by the biopolymer concentration, but not by the acid type. At a given biopolymer concentration, ζ potential signs (+) and values suggested that electrostatic interactions between CH chains and counter-anions occurred, regardless of the type of the organic acid. Thus, at least from a physicochemical point of view, GA, PA or LA showed to be suitable to replace AA when preparing dispersions containing from 0.125 to 1.000 g (100 g)−1 CH for technological purposes, such as thickening or stabilizer in formulated food products.
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Abbreviations
- a :
-
First constant of Mark–Houwink–Sakurada relationship (dimensionless)
- AA:
-
Acetic acid
- A 1320 :
-
Normalized absorbance of the peak at wavenumbers 1320 cm−1 (norm. arb. u.)
- A 1420 :
-
Normalized absorbance of the peak at wavenumbers 1420 cm−1 (norm. arb. u.)
- CDD:
-
Chitosan diluted-dispersions
- CH:
-
Chitosan
- CS:
-
Control systems
- CSD:
-
Chitosan stock-dispersions
- DA:
-
Degree of acetylation (%)
- DD:
-
Degree of deacetylation (%)
- GA:
-
Glycolic acid
- K :
-
Consistency index (Pa sn)
- K MHS :
-
Second constant of Mark–Houwink–Sakurada relationship (dL g−1)
- LA:
-
Lactic acid
- MAPE:
-
Mean absolute percentage error (%)
- \(\overline{M}_{V}\) :
-
Viscometric-average molar mass (kDa)
- n :
-
Flow behavior index (dimensionless)
- PA:
-
Propionic acid
- pH:
-
Hydrogenionic potential (dimensionless)
- R 2 :
-
Coefficient of determination
- ζ:
-
Zeta potential (mV)
- μ :
-
Viscosity (Pa s)
- μ e :
-
Electrophoretic mobility (m2 (V s)−1)
- ν :
-
Speed of particles (m s−1)
- τ :
-
Shear stress (Pa)
- \(\dot{\gamma }\) :
-
Shear rate (s−1)
- \({\vec{\text{E}}}\) :
-
Electric field (N C−1)
- [η]H :
-
Huggins intrinsic viscosity (dL g−1)
- [η]K :
-
Kraemer intrinsic viscosity (dL g−1)
- \(\left[ {\overline{\eta }} \right]\) :
-
Average intrinsic viscosity (dL g−1
References
Amorim ML, Ferreira GMD, Soares LS et al (2016) Physicochemical aspects of chitosan dispersibility in acidic aqueous media: effects of the food acid counter-anion. Food Biophys 11:388–399. https://doi.org/10.1007/s11483-016-9453-4
Badawy MEI, Rabea EI (2009) Potential of the biopolymer chitosan with different molecular weights to control postharvest gray mold of tomato fruit. Postharvest Biol Technol 51:110–117. https://doi.org/10.1016/j.postharvbio.2008.05.018
Bano I, Arshad M, Yasin T et al (2017) Chitosan: a potential biopolymer for wound management. Int J Biol Macromol 102:380–383. https://doi.org/10.1016/j.ijbiomac.2017.04.047
Brugnerotto J, Lizardi J, Goycoolea FM et al (2001) An infrared investigation in relation with chitin and chitosan characterization. Polymer 42:3569–3580
Calero N, Muñoz J, Ramírez P, Guerrero A (2010) Flow behaviour, linear viscoelasticity and surface properties of chitosan aqueous solutions. Food Hydrocoll 24:659–666. https://doi.org/10.1016/j.foodhyd.2010.03.009
Calero N, Muñoz J, Cox PW et al (2013) Influence of chitosan concentration on the stability, microstructure and rheological properties of O/W emulsions formulated with high-oleic sunflower oil and potato protein. Food Hydrocoll 30:152–162. https://doi.org/10.1016/j.foodhyd.2012.05.004
Campos RP, Kwiatkowski A, Clemente E (2011) Post-harvest conservation of organic strawberries coated with cassava starch and chitosan. Ceres 58:554–560
Costa MPM, Delpech MC, Ferreira IM et al (2017) Evaluation of single-point equations to determine intrinsic viscosity of sodium alginate and chitosan with high deacetylation degree. Polym Test 63:427–433. https://doi.org/10.1016/j.polymertesting.2017.09.003
Dash M, Chiellini F, Ottenbrite RM, Chiellini E (2011) Chitosan—a versatile semi-synthetic polymer in biomedical applications. Prog Polym Sci 36:981–1014. https://doi.org/10.1016/j.progpolymsci.2011.02.001
Dhumal CV, Sarkar P (2018) Composite edible films and coatings from food-grade biopolymers. J Food Sci Technol 55:4369–4383. https://doi.org/10.1007/s13197-018-3402-9
FDA (2019) Title 21 food and drugs parts 170 to 199, Special edn. Government Publishing Office, Washington
Ferreira DCM, de Souza AL, da Silveira JVW et al (2020) Chitosan nanocomposites for food packaging applications. In: Abd-Elsalam KA (ed) Multifunctional hybrid nanomaterials for sustainable agri-food and ecosystems, 1st edn. Elsevier, Cambridge, p 732
Fischer P, Pollard M, Erni P et al (2009) Rheological approaches to food systems. Comptes Rendus Phys 10:740–750. https://doi.org/10.1016/j.crhy.2009.10.016
Gaurav GK, Panjagari NR, Alam T (2019) An overview of paper and paper based food packaging materials: health safety and environmental concerns. J Food Sci Technol 56:4391–4403. https://doi.org/10.1007/s13197-019-03950-z
Goñi MG, Tomadoni B, Roura SI, Moreira MR (2017) Lactic acid as potential substitute of acetic acid for dissolution of chitosan : preharvest application to Butterhead lettuce. J Food Sci Technol 54:620–626. https://doi.org/10.1007/s13197-016-2484-5
Hamed I, Ozogul F, Regenstein JM (2016) Industrial applications of crustacean by-products (chitin, chitosan, and chitooligosaccharides): a review. Trends Food Sci Technol 48:40–50. https://doi.org/10.1016/j.tifs.2015.11.007
Hosseinnejad M, Jafari SM (2016) Evaluation of different factors affecting antimicrobial properties of chitosan. Int J Biol Macromol 85:467–475. https://doi.org/10.1016/j.ijbiomac.2016.01.022
Islam S, Bhuiyan MA, Islam MN (2017) Chitin and chitosan: structure, properties and applications in biomedical engineering. J Polym Environ 25:854–866. https://doi.org/10.1007/s10924-016-0865-5
Kaisler M, Van Den BLAM, Boeriu CG (2020) Chitin and chitosan as sources of bio-based building blocks and chemicals. In: van den Broek LAM, Boeriu CG, Stevens CV (eds) Chitin and chitosan: properties and applications, 1st edn. Wiley, Hoboken, p 536
Kasaai MR (2007) Calculation of Mark–Houwink–Sakurada (MHS) equation viscometric constants for chitosan in any solvent–temperature system using experimental reported viscometric constants data. Carbohyd Polym 68:477–488. https://doi.org/10.1016/j.carbpol.2006.11.006
Kasaai MR (2008) A review of several reported procedures to determine the degree of N-acetylation for chitin and chitosan using infrared spectroscopy. Carbohyd Polym 71:497–508. https://doi.org/10.1016/j.carbpol.2007.07.009
Kim KM, Son JH, Kim S-K et al (2006) Properties of chitosan films as a function of pH and solvent type. J Food Sci 71:119–124
Klinkesorn U (2013) The role of chitosan in emulsion formation and stabilization the role of chitosan in emulsion formation and stabilization. Food Rev Int 29:371–393. https://doi.org/10.1080/87559129.2013.818013
Knidri H, Belaabed R, Addaou A et al (2018) Extraction, chemical modi fi cation and characterization of chitin and chitosan. Int J Biol Macromol 120:1181–1189. https://doi.org/10.1016/j.ijbiomac.2018.08.139
Laplante S, Turgeon SL, Paquin P (2005) Emulsion stabilizing properties of various chitosans in the presence of whey protein isolate. Carbohyd Polym 59:425–434. https://doi.org/10.1016/j.carbpol.2004.08.031
Liu H, Yu H, Xia J et al (2020) Topical azelaic acid, salicylic acid, nicotinamide, sulphur, zinc and fruit acid (alpha-hydroxy acid) for acne (Review). Cochrane Database Syst Rev 1:CD011368. https://doi.org/10.1002/14651858.CD011368.pub2.www.cochranelibrary.com
Martínez A, Chornet E, Rodrigue D (2004) Steady-shear rheology of concentrated chitosan solutions. J Texture Stud 35:53–74. https://doi.org/10.1111/j.1745-4603.2004.tb00822.x
Mckesey J, Tovar-Garza A, Pandya AG (2019) Melasma treatment: an evidenc-based review. Am J Clin Dermatol 23:173–225. https://doi.org/10.1007/s40257-019-00488-w
Nidheesh T, Suresh PV (2015) Optimization of conditions for isolation of high quality chitin from shrimp processing raw byproducts using response surface methodology and its characterization. J Food Sci Technol 52:3812–3823. https://doi.org/10.1007/s13197-014-1446-z
Nieto Galván ZR, Soares LS, Medeiros EAA et al (2018) Rheological properties of aqueous dispersions of xanthan gum containing different chloride salts are impacted by both sizes and net electric charges of the cations. Food Biophys 13:186–197. https://doi.org/10.1007/11483-018-9524-9
Oryan A, Sahvieh S (2017) Effectiveness of chitosan scaffold in skin, bone and cartilage healing. Int J Biol Macromol 104:1003–1011. https://doi.org/10.1016/j.ijbiomac.2017.06.124
Ouattara B, Simard RE, Piette G et al (2000) Inhibition of surface spoilage bacteria in processed meats by application of antimicrobial films prepared with chitosan. Int J Microbiol 62:139–148
Park SY, Marsh KS, Rhim JW (2002) Characteristics of different molecular weight chitosan films affected by the type of organic solvents. J Food Sci 67:194–197
Rao MA (2013) Rheology of fluid, semisolid, and solid foods, 3rd edn. Springer, New York
Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31:603–632. https://doi.org/10.1016/j.progpolymsci.2006.06.001
Romanazzi G, Gabler FM, Margosan D et al (2009) Effect of chitosan dissolved in different acids on its ability to control postharvest gray mold of table grape. Phytopathology 99:1028–1036
Sarbon NM, Sandanamsamy S, Kamaruzaman SFS, Ahmad F (2015) Chitosan extracted from mud crab (Scylla olivicea) shells: physicochemical and antioxidant properties. J Food Sci Technol 52:4266–4275. https://doi.org/10.1007/s13197-014-1522-4
Shukla SK, Mishra AK, Arotiba OA, Mamba BB (2013) Chitosan-based nanomaterials: a state-of-the-art review. Int J Biol Macromol 59:46–58. https://doi.org/10.1016/j.ijbiomac.2013.04.043
Siggel TTD (1986) Why are organic acids stronger acids than organic alcohols? J Am Chem Soc 1:4360–4363
Siggel SA, Thomas TD (1988) The role of resonance and inductive effects in the acidity of carboxylic acids. J Am Chem Soc 1:8022–8028
Sigma-Aldrich (2019) Chitosan medium molecular weight. https://www.sigmaaldrich.com/catalog/product/aldrich/448877?lang=pt®ion=BR
Soares LS, Milião GL, Tonole B et al (2019) Chitosan dispersed in aqueous solutions of acetic, glycolic, propionic or lactic acid as a thickener/stabilizer agent of O/W emulsions produced by ultrasonic homogenization. Ultrason Sonochem 59:104754. https://doi.org/10.1016/j.ultsonch.2019.104754
Soares LS, Faria JT, Amorim ML et al (2017) Rheological and physicochemical studies on emulsions formulated with chitosan previously dispersed in aqueous solutions of lactic acid. Food Biophys 12:109–118. https://doi.org/10.1007/s11483-017-9469-4
Soares LS, Perim RB, Alvarenga ES et al (2019b) Insights on physicochemical aspects of chitosan dispersion in aqueous solutions of acetic, glycolic, propionic or lactic acid. Int J Biol Macromol 128:140–148. https://doi.org/10.1016/j.ijbiomac.2019.01.106
Solomons TWG, Fryhle CB (2000) Organic chemistry, 7th edn. Wiley, New York
Souza MPC, Sábio RM, Ribeiro TDC et al (2020) Highlighting the impact of chitosan on the development of gastroretentive drug delivery systems. Int J Biol Macromol 159:804–822. https://doi.org/10.1016/j.ijbiomac.2020.05.104
Suleria HAR, Gobe G, Masci P, Osborne SA (2016) Marine bioactive compounds and health promoting perspectives; innovation pathways for drug discovery. Trends Food Sci Technol 50:44–55. https://doi.org/10.1016/j.tifs.2016.01.019
Villiers MM, Wurster DE, Narsai K (1997) Stability of lactic acid and glycolic acid in aqueous systems subjected to acid hydrolysis and thermal decomposition. J Cosmet Sci 48:165–174
Wang K, Du L, Zhang C et al (2019) Preparation of chitosan/curdlan/carboxymethyl cellulose blended film and its characterization. J Food Sci Technol. https://doi.org/10.1007/s13197-019-04010-2
Younes I, Rinaudo M (2015) Chitin and Chitosan preparation from marine sources. structure properties and applications. Mar Drugs 13:1133–1174. https://doi.org/10.3390/md13031133
Acknowledgements
The authors are thankful to: Brazilian research agencies CAPES (Finance Code 001), CNPq (PDJ - 156047/2018-7), FAPEMIG, FINEP, and FUNARBE, for their financial support; LABEM–UFV, for allowing us using some of their facilities to perform some experiments; Mrs. Angélica Ribeiro da Costa, for her technical support in the rheological analyses; Mr. Márcio Alvarenga, for his technical support in performing FT-IR analyses.
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Lucas de Souza SOARES: Conceptualization, Methodology, Investigation, Formal Analysis, Validation, Writing - Original Draft, Writing - Review & Editing. Bruna TONOLE: Conceptualization, Investigation, Writing - Original Draft. Gustavo Leite MILIÃO: Conceptualization, Investigation, Writing - Original Draft. Alvaro Vianna Novaes de Carvalho TEIXEIRA: Conceptualization, Writing - Review & Editing. Jane Sélia dos Reis COIMBRA: Conceptualization, Writing - Review & Editing, Resources, Funding acquisition. Eduardo Basílio de OLIVEIRA: Conceptualization, Validation, Writing - Original Draft, Writing - Review & Editing, Supervision, Project administration, Funding acquisition.
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Soares, L.S., Tonole, B., Milião, G.L. et al. Aqueous solutions of glycolic, propionic, or lactic acid in substitution of acetic acid to prepare chitosan dispersions: a study based on rheological and physicochemical properties. J Food Sci Technol 58, 1797–1807 (2021). https://doi.org/10.1007/s13197-020-04691-0
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DOI: https://doi.org/10.1007/s13197-020-04691-0