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https://doi.org/10.1007/s10876-019-01721-6(0123456789().,-volV)(0123456789().
,- volV)
ORIGINAL PAPER
Abstract
A novel and facile synthetic route were evaluated towards the formation of silver nanoparticles (AgNPs) by exploiting
molasses as a biomaterial for the first time. The sugar molasses is a viscous material produced from sugarcane refining and
the bio-components responsible for the formation of crystalline AgNPs validated by FTIR, UV–Vis spec., EDX, and XRD.
The almost oval-shaped AgNPs with an average of 16 nm size were analyzed through DLS and TEM, respectively. Based
on the significant characterization results, the AgNPs was employed for simple colorimetric detection of mercury (Hg2?) at
low concentration. Here, we also described its catalytic efficacy for the reduction of 4-NP. The AgNPs found to have
excellent efficacy in the detection of Hg2? at 0.02 lM concentration. It also proved to have a prominent role in the
reduction of 4-NP with 80% conversion efficiency even after 6 cycles. Combining highly selective and sensitive sensors as
well as efficient and convenience catalysts have been proposed as detection and catalyzing nanomaterial for the envi-
ronmental pollutants in water. The approach in this work is cost-effective and provides potential opportunities in envi-
ronmental fields for a sustainable future.
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1138 G. Manjari et al.
bio-components like glucose, fructose as fermentable car- commonly gaining importance. The rapid catalytic hydro-
bohydrates, phenolic compounds, minerals, vitamins, and genation of 4-NP using green synthesized metal nanopar-
non-sugar organic compounds, an eco-friendly and eco- ticles has been extensively studied for a long time [29, 30].
nomically attractive source for energy [7]. Molasses is one Although, the synthesis of metal nanoparticles from sec-
of the cheap sources of carbon stock in the fermentation ondary waste to valuable material for sustainable devel-
process of bio-fuel and ethanol production and also a chief opment is widely investigating recently. Herein, we report
supplement for livestock feed [8]. It is used in the pro- for the first time for the sustainable synthesis of Ag
duction of baker’s yeast, various bio-surfactants, lactic nanoparticles from readily available molasses as a sec-
acid, e-poly-L-lysine, isomaltulose, and other organic ondary waste product of sugarcane, and their characteri-
chemicals and also used as a sweetener and colorant in the zation studied. The synthesized Ag NPs were utilized in the
food industry [9–11]. Also, the molasses has a high range selective detection of Hg2?, and the catalytic hydrogena-
of polyphenol content resulted in the potent antioxidant tion of 4-NP to 4-AP was successfully demonstrated.
capacity [12, 13]. Several authors reported the potential
antioxidant activity of molasses as an alternative to com-
mercial ones [14–16]. Experimental Details
The heavy metals like Mg2?, Cd2?, Ba2?, Hg2?, Pb2?,
and Sn2?, etc., are toxic and carcinogenic in the ecological Chemical and Materials
systems because of the formation of complexes by inter-
action with ligands of biological matter. For this reason, the All chemicals used in the experiment were of analytical
facile detection of heavy metals like Mg2?, Cd2?, Ba2?, grade, and the solutions were prepared using double-dis-
Hg2?, Pb2?, and Sn2?, etc., at deficient concentration has tilled water. Silver nitrate (AgNO3 99.8%), 4-nitrophenol
become a vital need in environmental and food safety (4-NP), and Sodium borohydride (NaBH4) were purchased
remedial processes concern [17]. Mercury contamination from Himedia Laboratories Ltd. India. Different cations
has severe detrimental effects on human beings compared like HgCl2, CoCl2, SnCl2, Na2HAsO4 FeCl2, Pb(NO3)2,
to other heavy metals. Several authors have reported dif- CaCl2, CdCl2, CuCl2, and MnSO4 were purchased from
ferent sensing approaches for heavy metals detection in Sigma-Aldrich chemical companies and used as received
various bodies using alloys, synthetic and biological without further purification. The molasses was collected
receptors, electrochemical, and light emission fluorescence, from the sugar refinery industry, Puducherry, India.
etc. [18–21]. All these methods are possessing high sen-
sitivity with some limitations like time consuming proce- Sustainable Synthesis of Ag Nanoparticles
dure, unsustainable and costly [22]. Recently, green
synthesized metal nanoparticles gaining more attention for Sustainable Ag nanoparticles were prepared by adding
the colorimetric sensing of heavy metals in water due to its 10 ml of 1% aqueous molasses solution in 100 ml of 1 mM
size, shape, optical properties, eco-friendly, cost-effective Ag precursors solution at room temperature. The color
and easy procedure with excellent sensitivity [23, 24]. change of the solution was observed after 12 h, and the
Therefore, metal nanoparticles for colorimetric detection of reaction went to completion after 36 h, which indicates the
heavy metals are of great interest due to its surface plasmon formation of Ag NPs.
resonance absorption and particle distance associated with
dielectric properties of heavy metals by color change [25]. Instruments
Especially, Silver (Ag) nanoparticles possess high molar
extinction coefficients and its fluorescence properties in The optical properties and formation of AgNPs and other
colloidal form for the selective sensing of the Hg2? ions in absorption spectral studies were confirmed by double beam
water bodies [26]. UV–Vis (Thermo Scientific; UV 2600) spectrophotometer
4-Nitrophenol (4-NP) is one of the major toxic com- at regular intervals. The role of bio-compounds present in
pounds in nitro-group and used as a precursor for the the sugar molasses in the formation of AgNPs was con-
4-aminophenol production, which was mainly used as an firmed by Fourier transform infrared (FTIR, Nicolet; model
intermediate compound in many industries [27]. The con- 6700) spectrophotometer of the range of 400–4000 cm-1.
version of 4-NP to 4-AP is not feasible kinetically without The crystalline and morphology of Ag NPs were observed
catalyst because of the high kinetic barrier between 4-NP by X-ray diffraction (XRD, Philips PW 3710/3020) and
and reducing agent by repelling the force of ions (sodium transmission electron microscopy (TEM, JEOL; model
borohydride) [28]. For environmental sustainability, the 2010). The composition, size, and stability analysis was
development of eco-friendly metal nanoparticles as performed by Energy Dispersive X-ray Spectroscopy
nanocatalyst for the conversion of nitro compounds is (EDAX, S3700 N), dynamic light scattering (DLS, Zeta-
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Sustainable Utilization of Molasses Towards Green Synthesis of Silver Nanoparticles for… 1139
sizer Nano, ZS with a 633 nm Helium–Neon laser) and related to the morphology of the nanoparticles [32]. Fig-
Zeta potential analysis (MPT-2 Autotitrator (Malvern, ure 1 shows the formation of AgNPs with an absorbance
UK)). around 450 nm using sugar cane secondary waste as a
reducing agent. The color of the Ag NPs solution was
Colorimetric Sensing of Hg21 Ions unchanged, and the SPR band of AgNPs was stable up to
2 months, which suggests the stability of AgNPs.
The ability of freshly formed bio-synthesized AgNPs col- FTIR analysis was conducted for the functional groups
loidal solution (2.5 ml) was investigated by colorimetric of molasses involved as reducing and capping agents in the
detection of metal ions at the same concentration (1 mM of synthesis of AgNPs (Fig. 2). The pronounced characteristic
0.5 ml) at ambient environmental conditions. The complete bands of sugar cane molasses were observed at around
reaction changes were monitored in the UV–visible 3450 cm-1, 2050 cm-1, 1640 cm-1, and 600 cm-1. A
absorption spectra at room temperature. The reaction was reduction in alcohol/phenols band (–OH stretch,
further monitored by the successful addition of Hg2? ion, 3450 cm-1) of the molasses was observed in the synthe-
and the intensity of SPR (surface resonance plasmon) was sized AgNPs (–OH stretch, 3330 cm-1), indicates the uti-
recorded. lization of phenolic group compounds in the formation of
nanoparticles. Similarly, the reduction in the primary
Real Samples amide band (C=O stretch, 1640 cm-1) to secondary amide
(N–H bend, 1600 cm-1) in AgNPs formation was
For the detection of Hg2? ions in real water samples, the observed. The redshift in the OH vibrations band
river water was collected from the Brahmaputra river, (2050 cm-1) of the molasses to nitrile band (C=N stretch,
drinking and tap water was collected from our laboratory, 2250 cm-1) in AgNPs formation. The other new peaks for
Pondicherry University, India. All the water samples are C-O groups stretching vibration at 1280 cm-1 and C–H
filtered through the microfiltration membrane, and a stan- bending vibration at 794 cm-1 were observed [33–35]. The
dard solution of Hg2? ions in three different concentrations FTIR results confirmed the bio-active compounds of
was spiked in water samples. The colorimetric changes of molasses such as alcohols/phenols, amides, carboxylic, and
the samples in the presence of Ag NPs were analyzed by other compounds are actively involved in the formation of
UV–Vis spectrophotometer. AgNPs.
The Bragg’s reflections (2h) in XRD pattern for sus-
Catalytic Hydrogenation tainable AgNPs were observed at 38.2, 44.98, and 64.34
which corresponds to the lattice plane (111), (200), and
For the catalytic hydrogenation, 1 ml of 10-3 M 4-NP with (220) sets (Fig. 3). The lattice plane sets clearly shown the
1 ml of 10-2 M NaBH4 in the presence of 5 mg of bio- band for a face-centred cubic structure (fcc) of silver with
synthesized AgNPs were performed as a model reaction. At crystalline nature. The average crystal size of sustainable
the end of the catalytic reaction, nanoparticles were AgNPs was calculated from the full width half maximum
recovered for reuse and recycle using simple centrifuga-
tion. The conversion percentage of nitro-compound was
calculated using
Conversion=degradation % ¼ Conversion ð%Þ
¼ A0 At =A0 100 ð1Þ
where A0 and At are absorbance of catalytic hydrogenation
reaction at 0 and t seconds respectively [31].
Characterization
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1140 G. Manjari et al.
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Sustainable Utilization of Molasses Towards Green Synthesis of Silver Nanoparticles for… 1141
Fig. 4 Particle size distribution of Ag NPs (a) and Zeta Potential of Ag Nps (b)
observed because of the direct redox reaction between Possible Mechanism for the Interaction of AgNPs
zero-valent Ag and Hg2? ions, oxidation of Ag nanopar- with the Heavy Metal Ions
ticles to Ag? and reduction of Hg2? ions to Hg atom. A
similar observation has been reported earlier [38, 39]. Based on earlier reports and present study results, a plau-
However, a blue shift in the SPR band intensity with an sible mechanism for the interaction of Ag NPs with Hg2?
increase in the Hg2? ions concentration ranging from ions was proposed and shown in Scheme 1. Based on our
0.01 lM to 1 lM and the linear regression coefficient (R2) results, a blue shift on SPR band absorbance with
value was found to be 0.9809 (Fig. 8b). Figure 8a confirms increasing concentration of Hg2? ions in the presence of
the sustainably synthesized Ag NPs exhibit the minimum the Ag NPs solution by the change in solution color from
detection limit 0.025 lM of Hg2? ions in the aqueous brown to colorless, which could be due to the oxidation of
solution by a slight blue shift on the SPR band. Ag0 to Ag? in the reduction process of Hg2? ions [38]. The
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1142 G. Manjari et al.
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Sustainable Utilization of Molasses Towards Green Synthesis of Silver Nanoparticles for… 1143
Fig. 8 UV-Vis absorbance spectra of AgNPs with different Hg2? concentration (a), linear plot for absorbance difference versus Hg2?
concentration (b) and Particle size distribution of Ag NPs upon addition of 1 lM Hg2? solution (c)
Catalytic Performance
Table 1 A comparison
Probe Limit of detection Linear range References
approaches for the detection of
Hg2? SA - PVA/AgNPs 3 lg L -1
0.9–200 lg L -1
[42]
-1 -1
Green synthesized AgNPs 2200 nmol L 10–100 lmol L [22]
Gln - His/AgNPs 900 nmol L-1 10–500 lmol L-1 [41]
Green synthesized AgNPs Not mentioned 50 nmol L-1–500 lmol L-1 [43]
Green synthesized AuNPs 120 nmol 50 nm–500 lM [40]
Sustainably synthesized AgNPs 0.02 lM 0.01–1 lM Present work
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1144 G. Manjari et al.
Fig. 9 UV-Vis spectra of 4-NP reduction to 4-AP (a) and Resue and recyclability of Ag NPs (b)
catalytic performance of Ag NPs for the conversion of sensing of Hg2? ions with a minimum detection limit of
4-NP in the UV–Vis absorption spectra were displayed in 0.025 lM concentration in real water bodies. The catalytic
Fig. 9a. By adding of Ag NPs catalyst, a strong charac- conversion of 4-NP to 4-AP in the presence of NaBH4 over
teristic peak of 4-nitrophenolate ions at 400 nm was dis- the Ag NPs catalyst was completed almost in 30 s. The
appeared in 30 s and raised a new peak at 300 nm ascribed high-density small-sized AgNPs is responsible for the high
to 4-AP. The size of the nanoparticles plays a significant catalytic activity by offering active sites for sufficient
role in catalytic activity because the surface-to-volume contact and fast electron transfer to 4-NP from reducing
ratio and redox potential are depending on the size of agent. The molasses mediated synthesis of Ag NPs repre-
nanoparticles, that boost the interfacial electron transfer on sent a simple, sustainable and cost-effective method for
the surface of the AgNPs surface to 4-NP from BH4- ions functionally active sensor and catalyst with a wide range of
[44]. The size of the AgNPs is smaller and supports the fast applications.
interfacial electron transfer between 4-NP from BH4- ions.
Moreover, the reuse and recyclability of the AgNPs cata- Acknowledgements The authors thank the Pondicherry University for
its Central instrumentation facility.
lyst for the conversion of 4-NP in the presence of NaBH4
are shown in Fig. 9b. The conversion efficacy was 80%
after six cycles, which indicates highly stable AgNPs for References
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