Improving the Antimicrobial and Mechanical Properties of Epoxy Resins via Nanomodification: An Overview
Abstract
:1. Introduction
2. Enhancement of Antimicrobial Properties via Nanomodification of Epoxies
2.1. Antimicrobial Agents and the Effects of Immobilization on Their Activities
- Observation of a zone of inhibition: the procedure involves placing a portion of the epoxy resin loading of the antimicrobial agent in contact with a growth media loaded with bacteria. As the antimicrobial agent elutes from the resin into the media, a region with an inhibited growth of bacteria is observed. The data must be compared with the same experiment carried out with the same epoxy resin, which does not contain the antimicrobial agent [9,19]. The method is not able to distinguish between bacteriostatic (delay of the bacterial growth) and bactericidal (inhibition of bacterial growth) effects, both depending on several factors; usually, the antimicrobial effectiveness involves both activities.
- Immersive method: the procedure involves the immersion of the bioactive sample into the media containing bacteria, under stirring, and the measure of the colony-forming units (CFUs) derived from the inoculum solution. The same experiment is carried out with a control (comparing the measured CFU), even if its surface could be significantly different from that of the sample, which could be positively charged if an ammonium moiety is the antimicrobial agent, thus strongly influencing the cell-surface adhesion. The method was developed as a standard procedure by ASTM (ASTM E2149).
- Direct inoculation: the Japanese Industry Standard (JIS Z-2801) involves placing a droplet of inoculum directly on the surface of the sample and, after a suitable inoculation time, the release of cells, under defined conditions, and enumeration as CFU.
- Surface growth method: it involves the application of a thin film of pathogens on the surface of the sample, following its growth, compared to that of the control, for a long time, typically days, thus evaluating the surface ability to form a biofilm.
2.2. Nanoscale Antimicrobial Agents
2.2.1. Metal-Based and Inorganic Nano-Modifiers
- (i).
- Nanocomposites, prepared by dispersion of nanoparticles into the epoxy mixture, where the interactions are essentially of physical/electrostatic nature [22]; and
- (ii).
- Nanohybrid materials, where the inorganic phase is formed in situ, achieving covalent chemical bonds between the epoxy matrix and the inorganic part [23] through sol–gel processes or reaction of functionalized nanoparticles with the epoxy mixture.
2.2.2. Metal Complexes Modifiers
2.2.3. Nanoclay Modifiers
2.2.4. Organic Nanomodifications
- Blending with intrinsically biocidal polymers such as chitosan [70,71] or copolymerization, with organic moieties able to modify the surface polarity, such as PANI [72] or non-isocyanate polyurethane [73], or epoxy polymers made from phenolic branched fatty acids [74,75], or using antibacterial polyether biguanide as a curing agent [76].
- Incorporating into the epoxy resin of quaternary ammonium moieties, which could be formed by (a) direct reaction of NH groups along the epoxy-resin chain with alkyl bromides [77,78,79], or preparing hybrid siloxane epoxy coatings by reaction of diamine-bearing epoxy moieties with siloxane-bearing amine groups [80]; (b) dispersing quaternary ammonium polyethylenimine nanoparticles previously prepared [81]; (c) preparing polysiloxane quaternary ammonium salts, containing epoxy groups to react with amines [82] and (d) preparing poly(quaternary ammonium salt-epoxy) grafted on Ce or ZnO nanoparticles [83,84].
- Incorporating biocidal compounds, such as triclosan [85].
2.2.5. Bio-Based Materials
2.2.6. Graphene Oxide and Carbon Nanotubes Modifiers
2.3. Selected Applications
2.3.1. Antifouling and Anticorrosion Coatings
2.3.2. Dental Sealers and Medicinal Applications
2.3.3. Fibers and Fabrics
2.3.4. Other Examples
3. Enhancement of Mechanical Properties via Nanomodification of Epoxies
3.1. Damage Mechanisms within Polymer Nanocomposites
3.2. Experimental Evidences of Mechanical Properties Enhancement
4. Enhancement of Mechanical and Antimicrobial Properties of Epoxy Composites
4.1. Epoxy Resins with Enhanced Mechanical and Antimicrobial Properties
4.2. Fiber Reinforced Laminates with Enhanced Mechanical and Antimicrobial Properties
5. Concluding Remarks and Future Research Trends
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Standard Method, Title | Test Organisms | Notes | |
---|---|---|---|
Bacteria | Fungi | ||
Agar Diffusion Methods | |||
AATCC Test Method 147-2004 Antibacterial Activity Assessment of Textile Materials: Parallel Streak Method | Staphylococcus aureus, Klebsiella pneumoniae | Measurement of inhibition zone after incubation in agar culture in the presence of the test specimen. Designed for diffusible antimicrobial agents. | |
AATCC Test Method 30-2004 Antifungal Activity, Assessment on textile Materials: Mildew and Rot Resistance of Textile Materials | Aspergillus niger; Penicillium varians; Trichoderma viride | Evaluation using a microscope (50×) of the extent of fungal growth on the test specimens (discs). | |
BS EN 1104-2018 Paper and board intended to come into contact with foodstuffs-Determination of the transfer of antimicrobial constituents | Bacillus subtilis | Aspergillus niger | Evaluation of the diameter of inhibition zone around each specimen disc. |
BS EN ISO 20645/AATCC 90 Textile fabrics, determination of antibacterial activity—Agar diffusion test plate | Staphylococcus aureus, Escherichia coli Klebsiella pneumoniae | Measurement of the inhibition zone after incubation in agar culture in the presence of the test specimen (< or >1 mm). | |
BS ISO 16869 Plastics assessment of the effectiveness of fungistatic compounds in plastic formulations | Aspergillus niger Chaetomium globosum Penicillium funiculosum Trichoderma longibrachiatum | Observation of fungal growth after pouring the inoculated molten nutrient–salt agar onto the surface of the base agar and test specimen to form a thin second layer. | |
ASTM E2722-14 Standard test method for using seeded-agar for the screening assessment of antimicrobial activity in fabric and air filter media | Staphylococcus aureus Serratia marcescens | Aspergillus brasiliensis | Designed to qualitatively evaluate the presence of antibacterial and antifungal activity in (or on) fabrics, or air filter media, simulating actual use conditions. |
E2922-15 Standard guide for the use of standard test methods and practices for evaluating antibacterial activity on textiles | Staphylococcus aureus, Escherichia coli Klebsiella pneumoniae | Candida albicans | An index of procedures. |
Suspension Methods | |||
E2149-20 Standard methods for determining the antimicrobial activity of antimicrobial agents under dynamic contact conditions (fabric, paper, powder and granular material, surfaces) | Escherichia coli | Enumeration of CFU after contact between pieces of specimen with known bacterial concentration on the wrist-action shaker. Designed for non-diffusible antimicrobial agents. | |
AATCC test method 100-2004 antibacterial finishes on textile materials: assessment of | Staphylococcus aureus, Klebsiella pneumoniae | Designed to measure the antimicrobial activity of textiles after direct inoculation of the textile surface. | |
JIS L 1902 Testing antibacterial activity and efficacy on textile products | Staphylococcus aureus, Klebsiella pneumoniae | Final microbial concentrations are determined after test fabrics are allowed to incubate undisturbed in sealed containers at body-temperature for 18 h. | |
ISO 20473-2013 Textile determination of antibacterial activity of textile products | Staphylococcus aureus, Klebsiella pneumoniae | Three inoculation methods are proposed: (a) Absorption method (an evaluation method in which the test bacterial suspension is inoculated directly onto specimens); (b) Transfer method (test bacteria are placed on an agar plate and transferred onto specimens); (c) Printing method (test bacteria are placed on a filter and printed onto specimens). | |
Quantitative Methods Based on Direct Contact of Microorganisms with Surfaces | |||
JIS Z 2801-2000 Antimicrobial product test for antimicrobial activity and efficacy for plastics | Escherichia coli Staphylococcus aureus, | Enumeration of CFU (after serial dilutions) in the test inoculum applied to the test surface. | |
ISO 22196/JIS Z 2801 Plastic measurement of antibacterial activity on plastic surfaces | Escherichia coli Staphylococcus aureus | Enumeration of CFU (after serial dilutions) in the test inoculum applied to the test surface. | |
ASTM E2180-18 Standard test method for determining the activity of incorporated antimicrobial agent(s) in polymeric or hydrophobic materials | Staphylococcus aureus Klebsiella pneumoniae, Pseudomonas aeruginosa | Designed to measure the antimicrobial activity of highly hydrophobic surfaces. The vehicle for the inoculum is an agar slurry, which reduces the surface tension of the saline inoculum carrier and allows formation of a “pseudo-biofilm”, providing more uniform contact of the inoculum with the test surface. The method can confirm the presence of antimicrobial activity in plastics or hydrophobic surfaces and allows determination of quantitative differences in antimicrobial activity between untreated plastics or polymers and those with bound or incorporated low water-soluble antimicrobial agents. | |
Methods Based on the Biofilm Formation | |||
E3151-18 Standard test method for determining antimicrobial activity and biofilm resistance properties of tube, yarn or fiber specimens | Staphylococcus epidermidis | Determination of planktonic bacteria and adherent bacteria populations that survived exposure to test specimens. Designed for plastic surfaces and other non-porous surfaces including coated substrates |
Material | Size and/or Morphology | Test Microorganism | Application | Reference |
---|---|---|---|---|
Ag NPs | 100 nm | Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Salmonella typhi, Candida albicans, Aspergillus niger | Hygienic pharmaceutical packaging | [35] |
β-Ca3(PO4)2 | 20–550 nm | Escherichia coli, Enterococcus faecalis | Dental sealer | [45] |
Ag/TiO2 | 20–100 nm | Escherichia coli, Staphylococcus aureus | Bactericidal surfaces | [46] |
Ag/APTES | >15 nm | Pseudomonas aeruginosa, Bacillus subtilis, Escherichia coli, Candida albicans | Anticorrosive and antifouling coating | [44] |
Ag/TiO2 | 20–100 nm | Streptococcus mutans | Dental sealer | [47] |
AgO | 100 nm, quadrangle | Escherichia coli, Staphylococcus aureus | Steel protection in the marine environment | [48] |
TiO2 | <100nm | Escherichia coli, Staphylococcus aureus, Cyclotella sp. | Antifouling coating | [49] |
Ag/TiO2 | Flower-like | Self-cleaning, photocatalytic, antimicrobial coatings in public areas | [50] | |
Fe3O4/Fe2O3 | <20 nm | Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa | Coating on carbon steel | [51] |
Ag | <20 nm | Escherichia coli | Nanocomposites with improved mechanical properties | [52] |
ZnO | <20 nm | Enterobacteriaceae | Food packaging | [53] |
CuO/TiO2 | <25 nm | Escherichia coli | Corrosion and antibacterial protection coatings | [54] |
Ag | <20 nm | Listeria monocytogenes | Nanocomposites with improved antimicrobial properties | [55] |
Compound | Description |
---|---|
Lawsone In the leaves of the henna plant (Lawsonia inermis), and in the flower of water hyacinth (Eichhornia crassipes). | |
Capsaicin An active component of chili peppers. | |
Cardenolide Many plants contain cardenolide derivatives and are used by some plant and animal species as defense mechanisms. | |
Cardanol From anacardic acid, it is the main component of cashew nutshell liquid. | |
Artemisinin Extracted from the plant Artemisia annua, sweet wormwood, an herb employed in Chinese traditional medicine. |
Compound | Description |
---|---|
Hinokitiol A natural monoterpenoid present in the wood of trees in the family of Cupressaceae. |
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Bertani, R.; Bartolozzi, A.; Pontefisso, A.; Quaresimin, M.; Zappalorto, M. Improving the Antimicrobial and Mechanical Properties of Epoxy Resins via Nanomodification: An Overview. Molecules 2021, 26, 5426. https://doi.org/10.3390/molecules26175426
Bertani R, Bartolozzi A, Pontefisso A, Quaresimin M, Zappalorto M. Improving the Antimicrobial and Mechanical Properties of Epoxy Resins via Nanomodification: An Overview. Molecules. 2021; 26(17):5426. https://doi.org/10.3390/molecules26175426
Chicago/Turabian StyleBertani, Roberta, Alessandra Bartolozzi, Alessandro Pontefisso, Marino Quaresimin, and Michele Zappalorto. 2021. "Improving the Antimicrobial and Mechanical Properties of Epoxy Resins via Nanomodification: An Overview" Molecules 26, no. 17: 5426. https://doi.org/10.3390/molecules26175426