journal article·2025-12Open access

Carvacrol-loaded montmorillonite–caseinate hybrids as active additives for the development of antimicrobial alginate-chitosan microcapsules

Mohamed Brahmi, Sara Moumnassi, Kamal Essifi, Emilie Dumas, Abdeslam Asehraou, Abdesselam Tahani, Adem Gharsallaoui

Abstract

This study presented a novel approach for encapsulating carvacrol, a volatile compound with antimicrobial properties, using montmorillonite-based hybrid materials prepared via an evaporation–adsorption process under vacuum at room temperature. These hybrids were incorporated as active additives into alginate-chitosan microcapsules. The effect of montmorillonite surface functionalization was examined by preparing two types of carvacrol-loaded composites: one with sodium caseinate intercalated within the clay layers, and another with caseinate adsorbed onto the external surface. Among these, the intercalated composite (Cas0.5@Mt-3) showed the highest carvacrol adsorption capacity, reaching 176.87 mg/g compared to 155.83 mg/g for the unmodified clay. This enhancement was attributed to the diffusion of carvacrol into the interlayer space, as supported by XRD analysis showing increased interlayer spacing. The carvacrol-loaded hybrids were incorporated into alginate matrices at three concentrations (1 %, 2 %, and 3 % w /w) using ionotropic gelation to form stable microcapsules. Higher encapsulation efficiency and loading capacity were achieved with the hybrid composites, likely due to the amphiphilic nature of caseinate, which improved compatibility between the additive and the polymeric matrix, as confirmed by FT-IR and TGA analysis. In vitro release studies in food-simulating media revealed more controlled carvacrol release in aqueous medium, while acidic and oily conditions led to faster diffusion. Antimicrobial tests against selected strains demonstrated enhanced inhibition, attributed to the synergistic effect of carvacrol and the polymeric components, particularly chitosan used for crosslinking. These results supported the effectiveness of this approach and its potential for developing active polymer-based systems to improve carvacrol bioavailability in food-related applications. • Carvacrol–montmorillonite hybrids formed via evaporation–adsorption. • Caseinate-modified montmorillonite enhanced carvacrol loading. • Hybrids successfully incorporated into alginate microcapsules. • Controlled release in water; faster diffusion in acid and oil media. • Improved antimicrobial activity against foodborne pathogens.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Nanocomposite Films for Food Packaging · Microencapsulation and Drying Processes · Polysaccharides Composition and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (60)

Show source-provided references
1. Chitosan: an overview of its properties and applications10.3390/polym13193256 ↗
2. Influence of process variables on essential oil microcapsule properties by carbohydrate polymer–protein blends10.1016/j.carbpol.2013.01.028 ↗
3. Encapsulation and release of Beauveria bassiana from alginate–bentonite nanocomposite10.1039/C7RA02185B ↗
4. Antimicrobial activity of carvacrol related to its chemical structure10.1111/j.1472-765X.2006.01938.x ↗
5. Development of alginate microspheres containing thyme essential oil using ionic gelation10.1016/j.foodchem.2016.02.104 ↗
6. The efficacy of essential oil components loaded into montmorillonite against Aspergillus Niger and Staphylococcus aureus10.1002/ffj.3488 ↗
7. Hybrid Microcapsules for Encapsulation and Controlled Release of Rosemary Essential Oil10.3390/polym15040823 ↗
8. Investigation into the role of layered nanoporous modified clays for adsorption/desorption of rosemary essential oil in the gas phase and the ability of this system as an antioxidant and preservation agent in food applications10.1186/s40643-025-00884-7 ↗
9. New insights into physicochemical aspects involved in the formation of chitosan@alginate biobased polyelectrolyte complexes on natural montmorillonite clay surface10.1016/j.molliq.2023.122635 ↗
10. Impact of pH on sodium caseinate binding and structural changes on montmorillonite surface
11. Synergistic stabilization of carvacrol emulsions using alginate, caseinate, and montmorillonite: enhancing encapsulation efficiency and controlled release10.1016/j.ijbiomac.2025.142957 ↗
12. Insight into the formation of layer-by-layer emulsions stabilized by sodium caseinate and montmorillonite studied with ITC for carvacrol retention and spray drying efficiency10.1016/j.foodchem.2025.144697 ↗
13. Competitive adsorption and displacement of anionic polysaccharides (fucoidan and gum arabic) on the surface of protein-coated lipid droplets10.1016/j.foodhyd.2015.08.023 ↗
14. Alginate gel particles–a review of production techniques and physical properties10.1080/10408398.2014.965773 ↗
15. Montmorillonite with essential oils as antimicrobial agents, packaging, repellents, and insecticides: an overview10.1016/j.colsurfb.2021.112186 ↗
16. Synergic antimicrobial properties of Carvacrol essential oil and montmorillonite in biodegradable starch films10.1016/j.ijbiomac.2020.07.226 ↗
17. Montmorillonite nanoclay based formulation for controlled and selective release of volatile essential oil compounds10.1016/j.matchemphys.2021.125569 ↗
18. Investigating the effect of clay content and type on the mechanical performance of calcium alginate-based hybrid bio-capsules10.1016/j.ijbiomac.2023.125011 ↗
19. Essifi, K., Brahmi ,Mohamed, Boussetta ,Abdelghani, Charii ,Hassan, Ait Benhamou ,Anass, El Bachiri ,Ali, Salhi ,Samira, Brahmi ,Rachid, Moubarik ,Amine, and Tahani, A., 2024. Synergistic enhancement of chlorophenols removal using eco-friendly alginate@montmorillonite hybrid bio-capsules: insights from encapsulation and kinetic release studies. J. Microencapsul. 41, 601–619. doi:https://doi.org/10.1080/02652048.2024.2395968.10.1080/02652048.2024.2395968 ↗
20. A study of poly (butylene adipate-co-terephthalate)/orange essential oil films for application in active antimicrobial packaging10.1016/j.lwt.2020.109148 ↗
21. Formation and characterization of calcium alginate hydrogel beads filled with cumin seeds essential oil10.1016/j.foodchem.2020.128143 ↗
22. A novel method for the preparation of inorganic and organo-modified montmorillonite essential oil hybrids10.1016/j.clay.2017.06.018 ↗
23. Enzymes immobilized on montmorillonite K 10: effect of adsorption and grafting on the surface properties and the enzyme activity10.1016/j.clay.2006.04.007 ↗
24. Oregano and Thyme Essential oils Encapsulated in Chitosan Nanoparticles as Effective Antimicrobial Agents against Foodborne Pathogens10.3390/molecules26134055 ↗
25. Adsorption of Lippia multiflora essential oil on two surfactant-modified clays: qualitative approach10.1180/clm.2020.26 ↗
26. Incorporation of essential oil in alginate microparticles by multiple emulsion/ionic gelation process10.1016/j.ijbiomac.2013.09.054 ↗
27. Chemical composition and antibacterial activity of essential oil of Senecio graciliflorus10.22270/jddt.v9i1-s.2265 ↗
28. Novel Carvacrol@activated Carbon Nanohybrid for innovative Poly(lactide Acid)/Triethyl Citrate based Sustainable active packaging Films10.3390/polym17050605 ↗
29. Calcium Chloride/Chitosan-Crosslinked Alginate Microcapsules for Enhanced Parathyroid Cell Transplantation10.1002/slct.202501330 ↗
30. Montmorillonite revolution: a unified exploration of exfoliation techniques and its emerging role as an advanced drug delivery carrier10.1016/j.clay.2025.107845 ↗
31. Laponite vs. montmorillonite as eugenol nanocarriers for low density polyethylene active packaging films10.3390/nano14231938 ↗
32. Investigation into the suitability of layered silicates as adsorption media for essential oils using FTIR and GC–MS10.1016/j.clay.2013.07.009 ↗
33. Adsorption of Cu (II) and Cd (II) from aqueous solutions by chitosan immobilized in alginate beads10.1016/j.jece.2020.103878 ↗
34. Application of Spectroscopic Methods for Structural Analysis of Chitin and Chitosan10.3390/md8051567 ↗
35. Synthesis and characterization of chitosan derivatives with dual-antibacterial functional groups10.1016/j.ijbiomac.2015.01.056 ↗
36. Development of Ca-alginate-chitosan microcapsules for encapsulation and controlled release of imidacloprid to control dengue outbreaks10.1016/j.jiec.2017.07.035 ↗
37. Microencapsulation of marjoram essential oil as a food additive using sodium alginate and whey protein isolate10.1016/j.ijbiomac.2023.123478 ↗
38. Modeling of essential oils adsorption onto clays towards a better understanding of their interactions10.1016/j.molliq.2017.11.012 ↗
39. Ocimum gratissimum essential oil and modified montmorillonite clay, a means of controlling insect pests in stored products10.1016/j.jspr.2012.09.006 ↗
40. Essential oil in bentonite: effect of organofunctionalization on antibacterial activities10.1016/j.clay.2023.107158 ↗
41. A review on the application of clay minerals as heavy metal adsorbents for remediation purposes10.1016/j.eti.2020.100692 ↗
42. Synthesis and characterization of montmorillonite/polyaniline composites and its usage to modify a commercial separator10.1016/j.jelechem.2020.114876 ↗
43. Stabilization of multilayered emulsions by sodium caseinate and κ-carrageenan10.1016/j.foodhyd.2012.08.006 ↗
44. Enhanced entrapment efficiency and modulated drug release of alginate beads loaded with drug–clay intercalated complexes as microreservoirs10.1016/j.carbpol.2010.02.038 ↗
45. Chitosan as Antimicrobial Agent: applications and Mode of Action10.1021/bm034130m ↗
46. Smectite Clay Nanoparticles as a Sustained Release System for Cinnamom Essential Oil Targeting Candida albicans10.1007/s42250-024-01027-9 ↗
47. Santos, D.C., Santos, R.R., Ventura, L.A.F., Melo, N.R., Costa, B. de S., Rojas, E.E.G., Salgado, N.L., 2016. Antimicrobial activity Studies and Characterization of Cellulose Acetate Films containing Essential oils. Italian Journal of Food Science 28, 248–257. doi:10.14674/1120-1770/ijfs.v28.
48. Chemical Migration from Beverage packaging Materials—a Review10.3390/beverages6020037 ↗
49. Ca/Na Montmorillonite: Structure, forces and Swelling Properties10.1021/la9036293 ↗
50. Controlled release of the fungicide thiram from starch–alginate–clay based formulation10.1016/j.clay.2009.03.001 ↗
51. Histidine modified montmorillonite: Laccase immobilization and application to flow injection analysis of phenols10.1016/j.clay.2013.10.014 ↗
52. Microencapsulation and antimicrobial activity of carvacrol in a pectin-alginate matrix10.1016/j.foodhyd.2019.01.006 ↗
53. Preparation and characterization of pectin-alginate-based microbeads reinforced by nano montmorillonite filler for probiotics encapsulation: improving viability and colonic colonization10.1016/j.ijbiomac.2024.130543 ↗
54. Microencapsulation of probiotics in chitosan-coated alginate/gellan gum: Optimization for viability and stability enhancement10.1016/j.foodhyd.2024.109788 ↗
55. Dual pH responsive via double - layered microencapsulation for controlled release of active ingredients in simulated gastrointestinal tract: a model case of chitosan-alginate microcapsules containing basil oil (Ocimum basilicum Linn.)10.1016/j.polymdegradstab.2021.109660 ↗
56. LLDPE based food packaging incorporated with nanoclays grafted with bioactive compounds to extend shelf life of some meat products10.1016/j.lwt.2015.06.030 ↗
57. Shrinkage and deformation during convective drying of calcium alginate10.1016/j.lwt.2018.06.056 ↗
58. Montmorillonite and alginate co-stabilized biocompatible Pickering emulsions with multiple-stimulus tunable rheology10.1016/j.jcis.2019.11.081 ↗
59. Facile fabrication of chitosan colloidal films with pH-tunable surface hydrophobicity and mechanical properties10.1016/j.foodhyd.2022.108429 ↗
60. Mixing Oil-based Microencapsulation of Garlic Essential Oil: Impact of Incorporating three Commercial Vegetable oils on the Stability of Emulsions10.3390/foods10071637 ↗