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Polymers 2019, 11, 2000 9 of 21 ICP-OES data on leaching studies (ICP-OES provides elemental specificity and high sensitivity – limits of detection in the μg/L range) was used to determine the extent of Ag-species leaching from the polyviscose substrate into the solution (Figure 2c). Use of rGO as an overlay/protective coating allowed for effective adhesion and durability of AgNP, which minimised the aggregation problem of AgNPs and allows higher overall loadings of silver to be achieved, all with long-term protection capability [59]. In both the solely AgNP and Ag-rGO samples, there was a detectable leaching of silver Polymers 2019, 11, 2000 9 of 21 into the saline solution over the 180 min, even though leachant concentrations are seemingly below the values commonly observed for municipal wastewater treatment plants, and well below levels thought thought to induce cytotoxic effects (e.g., the US Environmental Protection Agency (EPA) sets to induce cytotoxic effects (e.g., the US Environmental Protection Agency (EPA) sets secondary drinking secondary drinking water limits of 1 × 10−6 g.L−1 silver) [104–106]. Results indicated that small traces water limits of 1 × 10−6 g.L−1 silver) [104–106]. Results indicated that small traces of silver leached of silver leached into the solution up to 1.7 × 10−7 g·L−1 silver per sample for Ag-rGO and 2.3 × 10−7 into the solution up to 1.7 × 10−7 g·L−1 silver per sample for Ag-rGO and 2.3 × 10−7 g·L−1 for AgNP, g·L−1 for AgNP, respectively [107,108]. This is in contrast to past reports of leaching between 1.5–5.7 respectively [107,108]. This is in contrast to past reports of leaching between 1.5–5.7 × 10−3 g·L−1 of × 10−3 g·L−1 of silver from various textile samples, by Ureyen et al., under similar testing conditions. silver from various textile samples, by Ureyen et al., under similar testing conditions. As such, these As such, these experimentally produced composites should be safe for use. experimentally produced composites should be safe for use. The experimental UV–Vis data for synthesized plasmonic hybrid nanostructured samples The experimental UV–Vis data for synthesized plasmonic hybrid nanostructured samples demonstrates a well-separated single absorption peak in all cases, which corresponds to the surface demonstrates a well-separated single absorption peak in all cases, which corresponds to the surface plasmon resonance (SPR) of spherical AgNP, as encapsulated within the polyviscose fabric substrate plasmon resonance (SPR) of spherical AgNP, as encapsulated within the polyviscose fabric substrate (Figure 3) [109]. Surface plasmons are the in-phase oscillations of free electrons at the interface of a (Figure 3) [109]. Surface plasmons are the in-phase oscillations of free electrons at the interface of a metal and dielectric, as indicated by a strong absorption at the resonance wavelength in a UV–Visible metal and dielectric, as indicated by a strong absorption at the resonance wavelength in a UV–Visible absorption spectrum [110–117]. The SPR band position depends on parameters such as size, shape, absorption spectrum [110–117]. The SPR band position depends on parameters such as size, shape, and and polydispersity of nanostructures, even though it is the ability of rGO to otherwise enhance and polydispersity of nanostructures, even though it is the ability of rGO to otherwise enhance and control control the loading and embedding of AgNPs, due to improved specific surface areas thought to be the loading and embedding of AgNPs, due to improved specific surface areas thought to be the reason the reason for the divergence in the signal between the Ag and Ag-rGO samples [56]. Resonance for the divergence in the signal between the Ag and Ag-rGO samples [56]. Resonance wavelengths wavelengths strongly depend upon the refractive index of the dielectric medium. It increases if an strongly depend upon the refractive index of the dielectric medium. It increases if an additional thin additional thin layer of high dielectric constant material is over-coated, and decreases for a lower layer of high dielectric constant material is over-coated, and decreases for a lower dielectric constant dielectric constant material [74]. Thus, for Ag-rGO, the synergistic plasmonic effects between AgNP material [74]. Thus, for Ag-rGO, the synergistic plasmonic effects between AgNP and the rGO network, and the rGO network, and the differing dielectric constants between the two components, affects the anchdatrhaectderiffoefritnhge dSPieRlescitgrnicalco[5n2s]t.aTnytspbiceatlwlye,esnoltehlye tawsoilvceormproesnenctes,isaffseacidtsttohesucfhfearafrcotemr ocfhethmeicSaPlR siignnstaalb[i5l2it]y. tThyaptilcealdlys,tsooolxeildyaatisoinlvaenrdpresuelntsceinisansaSiPdRtoresdu-ffsheirftfraonmddcahmempeicnainlgin.sTthaubsil,istiylvtehrasttlaebaidlistyto oxtoidoaxtiodnataionndirnecsruelatseisnwanithSPrRGrOedu-seh,ifwt ahnicdhdisaminpeanccinorgd.aTnhcuesw, siitlhveprastarbeiplitoyrttsowoxhiedraet,ioinginencreerasl,es wpitrhotreGctOiveusceo,awtinhgischaisveinhaelcpceodrdraetnacredwsiiltvherpcaosrtrroespionr,tsaswwhelrlea,sinaltgeernthereaol,pptircoatlepcrtoivperctoieastionfgssilhvaerve he[5lp3]e.d retard silver corrosion, as well as alter the optical properties of silver [53]. Figure 3. UV–Vis absorption spectra for blank substrates, AgNP-impregnated, rGO-impregnated, and Figure 3. UV–Vis absorption spectra for blank substrates, AgNP-impregnated, rGO-impregnated, and Ag-rGO-impregnated polyviscose non-woven fabrics, at surface treatment NaBH4(aq) reducing agent Ag-rGO-impregnated polyviscose non-woven fabrics, at surface treatment NaBH4(aq) reducing agent concentrations of 200 mmol, both (a) before, and (b) after, laundering durability testing, indicating the concentrations of 200 mmol, both (a) before, and (b) after, laundering durability testing, indicating surface plasmon resonance (SPR) band where plasmonic AgNP are present. the surface plasmon resonance (SPR) band where plasmonic AgNP are present. Related to the ICP-OES data, the enhanced loading and adhesion of the Ag-rGO composites was investigated via the SPR band profiles after 12 equivalent standard washing cycles (due to sample physical damage, while further wash cycles were not conducted). Figure 3 shows that both AgNP and Ag-rGO samples still displayed strong SPR bands even though, seemingly, the use of rGO was absent. More silver leached from the substrate than when rGO was used concurrently. This, indicates that AgNP are still present in substrates after serial washing, which indicates wash-fastness to laundering of samples.PDF Image | Antimicrobial from Silver-Graphene Coated Medical Textiles
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