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Polymers 2019, 11, 2000 12 of 21 improved activity versus the uncoated substrate (P < 0.05, Table 1) [19]. Absent the use of a protective coating (e.g., silica), such post-laundering performance compares favourably with past reports [96,136]. The antibacterial activities of solely rGO-incorporated samples were limited (82.5%), although some improvement was observed as compared to the untreated surface. The reason for enhanced activity remains under question but is in line with past reports of mild antimicrobial effects, with both a compromise of cellular membrane integrity (via prolonged, direct physical contact with the rGO sheets) and oxidative stress mechanisms (as mediated by the production of reactive oxygen species) thought to be potentially responsible [127,137,138]. The enhanced E. coli inhibition activity of Ag-rGO hybrids exhibit promise for biomedical applications, as compared to individual rGO and AgNP agents [139]. Bactericidal efficacy is dependent on absorption variations of the formed plasmonic composite systems as well as the size, shape, and type of bacteria [140–142]. Past reports indicate that the rGO presence in plasmonic systems can improve charge carrier generation, enhance electron transfer efficiency, and suppress electron-hole pair charge recombination, which reduces the back-transfer of electrons [142–145]. Such properties are fundamental to the generation of free radicals that effect an antibacterial function. Thus, rGO presence, both in conjunction with AgNP, as well as on its own (to a lesser degree), inhibits growth of gram negative bacteria and also allows avoidance of oxidation by air, which enhances the stability in line with previous reports [146,147]. Alternatively, the higher loading of AgNP, and/or the presence of smaller, less agglomerated AgNP, as obtained here, enhances the known antimicrobial properties of silver, inactivating bacteria via the interaction with bacterial protein and enzymatic thiol groups [148,149]. Furthermore, the longer-term isolation of AgNPs as a result of higher loadings to laundering and abrasion ensures a degree of retained antibacterial activity [80]. This is reflected in the continued bactericidal efficacy (90.1 %) for the Ag-rGO sample as compared to an untreated ‘control’ blank substrate sample. However, post-wash, the solely rGO-incorporated sample displays severe degradation in capability, perhaps due to the amelioration of the sharp edges (as observable in the SEM images), which dent the physical mechanisms of microbial retardation, while the copious amount of extra carbonaceous feedstock material present, may serve to accelerate microbial growth. Table 1. A comparison of the relative significance (i.e., +: significant; −: not significant) in bacterial reduction performance between the different composite systems, according to the Mann-Whitney U test, at P < 0.05, both before and after laundering durability testing (i.e., post-wash (PW)). P < 0.05 Control Control / Blank Substrate + rGO + rGO:PW − Ag + Ag:PW + Ag-rGO + Ag-rGO: PW + Blank Substrate + / + − + − + + rGO rGO: Ag Ag: Ag-rGO PW PW +−+++ +−+−+ / + − + + + / + + + − + / + − + + + / + + + − + / Ag-rGO: PW + + + + + − + +++−+/PDF Image | Antimicrobial from Silver-Graphene Coated Medical Textiles
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