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Nanomaterials 2019, 9, x FOR PEER REVIEW 9 of 20 Hydrodynamic size estimation of hypothetical spheres by DLS using number distribution with respect to size shows the existence of nanoparticles from 4 to 60 nm. DLS data also indicates the presence of a higher number of particles within 10 nm range and a lesser number of larger particles Nanomaterials 2019, 9, 1042 9 of 20 (Figure 5), which resembles the TEM distribution quite closely. The polydispersity index value (PDI) of suspension was found to be 0.547, which is well below the acceptable range of 0.7. PDI values are Nanomaterials 2019, 9, x FOR PEER REVIEW 10 of 20 dimensionless, ranging from 0 to 1; values lower than 0.05 indicate a monodispersed sample, whereas dimensionless, ranging from 0 to 1; values lower than 0.05 indicate a monodispersed sample, values high−1er than 0.7 indicate a broad particle size distribution. 8w7h9.e3r8eascmval,ueasnhdighthereth-aCnH02.7binedndiciantge avbirboradtiopnartpicelaeksizbeedcaismtreibuvteioryn. strong; however, bands corresponding to amide II, C-O, and primary alcohol groups at 1542.77, 1388.50, and 1211.08 cm−1, respectively, dis l groups of the pigment change ment at a pH of 12alsoevidencenaddition,the UV-Visspectruionalgroupsat high pH values at pH 13 could reduce the prec increase in the bioavailabilityoHandcouldbe appeared. Therefore, it can be argued that the properties of functiona d depending on the pH value. The visual change in colour of the pig s the change in optical and absorption properties (Figure 6b, inset). I m clearly shows shifts in peaks, thereby indicating changes in its funct . Verma and Mehata (2016) showed that the Azadiractha indica extract ursor to AgNPs [32]. They concluded that this might be due to an f functional groups in the reaction mixture caused by the change in p effective synthesis. In this study, the changes in FTIR spectra and ncreased bioavailability, leading to increased reduction ability of fun e difference in the reduction activity cannot be solely explained by H was revealed as an accelerator in the AgNP generation process. hat NaOH not only plays an important role in the formation of inter also increases the reduction and nucleation rates by oxidizing the the reason for might indicate i Nevertheless, th Previously, NaO (2011) showed t reduction, but UV-Vis spectra ctional groups. these changes. Nishimura et al. mediates in Ag+ reducing agent itself, while using sodium acrylate as a reducing as well as capping agent [33]. Similarly, these Figure 5. DLS size distribution of AgNPs with number. factors might account for the better generation of AgNPs by the pigment in alkaline conditions. Further study is essential to realize the mechanisms involved in this process. 3.3.2. FTIR Analysis 3.3.2. FTIR Analysis The presence of -OH groups along with phenolic/alcoholic groups, and C–O groups with amide FTIR examination was carried out to determine the functional groups present in the pigment, FTIR examination was carried out to determine the functional groups present in the pigment, groups have been known to induce reduction and stabilization/capping, respectively [34,35]. which may have played a vital part in the reduction and capping of AgNPs. Because AgNPs were which may have played a vital part in the reduction and capping of AgNPs. Because AgNPs were Phenolic groups take part in redox reactions, which leads to the generation of quinones and generated in alkaline conditions, FTIR analysis was performed for the pigment without a pH change, generated in alkaline conditions, FTIR analysis was performed for the pigment without a pH change, donating electrons. These electrons in turn reduce the metal ions to nanoparticles [36]. These groups as well as for the pigment at pH 12 to comprehend the change caused by the increased pH (Figure 6a). as well as for the pigment at pH 12 to comprehend the change caused by the increased pH (Figure might also be involved in this reduction process too. Since the synthesis of AgNPs is mediated by Table 2 provides information regarding the peaks found in FTIR analysis and their functional groups. 6a). Table 2 provides information regarding the peaks found in FTIR analysis and their functional bioactive groups, they can possibly be utilized in biomedical applications. groups. 100 (a)3(b) Pigment—pH 12 90 80 Table 2. Peaks obtained by1F5T4I2R.7a7nalysis and corresponding functional groups. 1388.50 Peak (cm−1) 1774.19 Peak (cm−1) Functional Group broad -OH bending =CH2 asymmetric stretching -C=O group 3386.39 Broad H-bonded -OH stretching 3432.67 1658.48 =CH2 asymmetric stretching 2931.27 3432.67 amide I/-NH bending 1774.19 Pigment pH-12 60 2931.27 50 1643.05 40 1542.77 30 1457.92 20 1388.50 10 amide II 1658.48 Pigment 1211.08 phenol/C-O- stretching 1450.21 879.38 primary alcohol/C-O- stretching C-O stretch/primary alcohol stretching -CH vibrations 1056.80 0 0 4000 3200 2400 1600 800 Wavelength (cm-1) 200 Wavelength (nm) 3386.34 Pigment Functional Group 70 2 1 Pigment amide group 1643.05 -CH bending 1450.21 phenol/-OH bending 1072.23 Pigment pH- 12 The vibration bands of -OH, amide group, -CH bending, and C-O/primary alcohol groups shifted in the FTIR spectrum of the pigment at pH 12, whereas the =CH2 asymmetric stretching band Figure 6. (a) FTIR spectrum of pigment without pH change and pigment at pH 12. (b) UV-Vis spectrum Figure 6. (a) FTIR spectrum of pigment without pH change and pigment at pH 12. (b) UV-Vis waspforresbeonthtipnigtmhenstpceocntrdaitoiofnbs.otIhnstehteinsa(mb)pClehsa.nAgetianlkpailgimnenptHco,lnoeuwr:b0.a5ngd/sLappigpmeaernetdwaith1o7u7t4p.1H9and spectrum for both pigment conditions. Inset in (b) Change in pigment colour: 0.5 g/L pigment change (left), at pH 12 (right). without pH change (left), at pH 12 (right). 3.3.3. EPMA The EPMA data qualitatively indicates the existence of elemental silver in the sample (Figure 7). The EPMA maps clearly show the presence of silver in the targeted part of the sample along with strong methylene -CH bending 400 600 800 Transmittance (%) AbsorbancePDF Image | Biosynthesis of Silver Nanoparticles Talaromyces purpurogenus
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