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Industrial Crops and Products 48 (2013) 81–88 Contents lists available at SciVerse ScienceDirect Industrial Crops and Products journal h om epage: www.elsevier.com/locate/indcrop Mango peel extract mediated novel route for synthesis of silver nanoparticles and antibacterial application of silver nanoparticles loaded onto non-woven fabrics Ning Yang a,, Wei-Hong Li b a College of Food Science and Engineering, Shanxi Agricultural University, Taigu, Shanxi 030801, China b College of Resources and Environment, Shanxi Agricultural University, Taigu, Shanxi 030801, China a r t i c l e i n f o Article history: Received 26 January 2013 Received in revised form 29 March 2013 Accepted 1 April 2013 Keywords: Silver nanoparticles Mango peel Biosynthesis Non-woven fabrics Antibacterial activity a b s t r a c t Silver nanoparticles were successfully synthesized from aqueous silver nitrate through a simple green route using the extract of Mango peel as a reducing as well as capping agent. The possible biochemical mechanism leading to the formation of silver nanoparticles was studied using FTIR. The various opera- tional parameters were evaluated for biosynthesis process. The results obtained from UV–vis spectrum, X-ray diffraction (XRD), and Transmission electron microscope (TEM) revealed that the biosynthesis of silver nanoparticles are in the size range of 7–27 nm and is crystallized in face centered cubic symme- try. Further, the antibacterial application of these biologically synthesized silver nanoparticles loaded onto non-woven fabrics has also been discussed. The results show that non-woven fabrics loaded with biosynthesis silver nanoparticles displayed excellent antibacterial activity. © 2013 Elsevier B.V. All rights reserved. 1. Introduction Silver nanoparticles are important materials that have been studied extensively. They can be synthesized by several physi- cal, chemical and biological methods (Annadhasan et al., 2012; Abbasi et al., 2012; Vijayaraghavan et al., 2012). Although existing chemical and physical methods have successfully produced well- defined silver nanoparticles, these processes are usually costly and involve the use of toxic chemicals. In addition, synthesis of sil- ver nanoparticles using chemical methods could still lead to the presence of some toxic chemical species being adsorbed onto the surface of nanoparticles which may cause adverse effects in their applications. Because of this, the bio-inspired synthesis of silver nanoparticles has become significant in the recent years. Several biological systems including bacteria, fungi and algae have been used for this purpose (Pugazhenthiran et al., 2008; Fayaz et al., 2009; Xie et al., 2007). And applications in diverse fields such as drug delivery (Keun et al., 2008), biosensors (Amanda et al., 2005), bio-imaging (Mohammed et al., 2009), antimicrobial activ- ity (Mohammed et al., 2010), food preservation (Mohammed et al., 2009) have been reported. However, an extensive literature sur- vey revealed that there are few reports (Rajendran et al., 2012) on the synthesis of silver nanoparticles using agricultural wastes. A Corresponding author. Tel.: +86 354 6268388; fax: +86 354 6288322. E-mail address: [email protected] (N. Yang). classical example of such an abundantly available natural material is the mango peel. Mango is consumed all over the world. The pro- duction of this fruit is very high. After consumption of the pulp, the peel is generally discarded. In the literature there are a few applications of this peel (Kim et al., 2012; Zainuri et al., 2012). This study hypothesized that the polymers composing mango peel such as Polysaccharide, lignin, flavonoid, hemicellulose and pectins (Wilkinson et al., 2011) could be applied in the synthesis of silver nanoparticles. To the best of our knowledge, the use of mango peel has not been investigated so far for their ability in the biosynthe- sis of silver nanoparticles. In this paper, a novel biological route for the synthesis of silver nanoparticles using an extract derived from Mango peel is demonstrated. The silver nanoparticles struc- tures have been characterized by UV–Visible spectroscopy, TEM, XRD. The possible mechanism for the formation and stabilization of silver nanoparticles was investigated using FTIR. The various oper- ational parameters were evaluated for the biosynthesis process and the antibacterial application of these biologically synthesized silver nanoparticles loaded onto non-woven fabrics is also discussed. 2. Materials and methods 2.1. Plants and chemicals The mango (Mangifera indica Linn) was purchased from an agricultural market located in Taigu, China. Silver nitrate was pur- chased from Sigma–Aldrich and used as received. All the other 0926-6690/$ see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.indcrop.2013.04.001
Transcript

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Industrial Crops and Products 48 (2013) 81– 88

Contents lists available at SciVerse ScienceDirect

Industrial Crops and Products

journa l h om epage: www.elsev ier .com/ locate / indcrop

ango peel extract mediated novel route for synthesis of silveranoparticles and antibacterial application of silver nanoparticles

oaded onto non-woven fabrics

ing Yanga,∗, Wei-Hong Lib

College of Food Science and Engineering, Shanxi Agricultural University, Taigu, Shanxi 030801, ChinaCollege of Resources and Environment, Shanxi Agricultural University, Taigu, Shanxi 030801, China

a r t i c l e i n f o

rticle history:eceived 26 January 2013eceived in revised form 29 March 2013ccepted 1 April 2013

a b s t r a c t

Silver nanoparticles were successfully synthesized from aqueous silver nitrate through a simple greenroute using the extract of Mango peel as a reducing as well as capping agent. The possible biochemicalmechanism leading to the formation of silver nanoparticles was studied using FTIR. The various opera-tional parameters were evaluated for biosynthesis process. The results obtained from UV–vis spectrum,

eywords:ilver nanoparticlesango peel

iosynthesison-woven fabrics

X-ray diffraction (XRD), and Transmission electron microscope (TEM) revealed that the biosynthesis ofsilver nanoparticles are in the size range of 7–27 nm and is crystallized in face centered cubic symme-try. Further, the antibacterial application of these biologically synthesized silver nanoparticles loadedonto non-woven fabrics has also been discussed. The results show that non-woven fabrics loaded withbiosynthesis silver nanoparticles displayed excellent antibacterial activity.

ntibacterial activity

. Introduction

Silver nanoparticles are important materials that have beentudied extensively. They can be synthesized by several physi-al, chemical and biological methods (Annadhasan et al., 2012;bbasi et al., 2012; Vijayaraghavan et al., 2012). Although existinghemical and physical methods have successfully produced well-efined silver nanoparticles, these processes are usually costly and

nvolve the use of toxic chemicals. In addition, synthesis of sil-er nanoparticles using chemical methods could still lead to theresence of some toxic chemical species being adsorbed onto theurface of nanoparticles which may cause adverse effects in theirpplications. Because of this, the bio-inspired synthesis of silveranoparticles has become significant in the recent years. Severaliological systems including bacteria, fungi and algae have beensed for this purpose (Pugazhenthiran et al., 2008; Fayaz et al.,009; Xie et al., 2007). And applications in diverse fields suchs drug delivery (Keun et al., 2008), biosensors (Amanda et al.,005), bio-imaging (Mohammed et al., 2009), antimicrobial activ-

ty (Mohammed et al., 2010), food preservation (Mohammed et al.,

009) have been reported. However, an extensive literature sur-ey revealed that there are few reports (Rajendran et al., 2012) onhe synthesis of silver nanoparticles using agricultural wastes. A

∗ Corresponding author. Tel.: +86 354 6268388; fax: +86 354 6288322.E-mail address: [email protected] (N. Yang).

926-6690/$ – see front matter © 2013 Elsevier B.V. All rights reserved.ttp://dx.doi.org/10.1016/j.indcrop.2013.04.001

© 2013 Elsevier B.V. All rights reserved.

classical example of such an abundantly available natural materialis the mango peel. Mango is consumed all over the world. The pro-duction of this fruit is very high. After consumption of the pulp,the peel is generally discarded. In the literature there are a fewapplications of this peel (Kim et al., 2012; Zainuri et al., 2012).This study hypothesized that the polymers composing mango peelsuch as Polysaccharide, lignin, flavonoid, hemicellulose and pectins(Wilkinson et al., 2011) could be applied in the synthesis of silvernanoparticles. To the best of our knowledge, the use of mango peelhas not been investigated so far for their ability in the biosynthe-sis of silver nanoparticles. In this paper, a novel biological routefor the synthesis of silver nanoparticles using an extract derivedfrom Mango peel is demonstrated. The silver nanoparticles struc-tures have been characterized by UV–Visible spectroscopy, TEM,XRD. The possible mechanism for the formation and stabilization ofsilver nanoparticles was investigated using FTIR. The various oper-ational parameters were evaluated for the biosynthesis process andthe antibacterial application of these biologically synthesized silvernanoparticles loaded onto non-woven fabrics is also discussed.

2. Materials and methods

2.1. Plants and chemicals

The mango (Mangifera indica Linn) was purchased from anagricultural market located in Taigu, China. Silver nitrate was pur-chased from Sigma–Aldrich and used as received. All the other

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hemicals were used as received. The experiments were done inriplicates. Double distilled water was used for the experiments.

.2. Preparation of the mango peel extract

Mango peel was washed thoroughly with double distilled water.uch peels (100 g) were added to 250 mL distilled water andrushed by a juicer. The extract was filtered through a cheese clothnd stored at −4 ◦C for further experiments.

.3. Synthesis of silver nanoparticles

For all experiments, the source of silver was silver nitrateAgNO3) in distilled water. Typical reaction mixtures contained

mL of the extract in 27 mL of AgNO3 solution (1 mM). Other reac-ion conditions included incubation at 80 ◦C in a water bath for5 min unless otherwise stated. All experiments were carried out

n triplicates and representative data is presented here. The effect ofH on nanoparticle synthesis was determined by adjusting the pHf the reaction mixtures to 2.0, 3.0, 5.0, 7.0, 9.0, and 11.0. The effectf the silver salt was determined by varying the concentration ofgNO3 (0.5, 1.0, 2.0 and 4.0 mM). The extract content was varied

0.1, 0.4, 0.7, 1.0 and 3.0 mL). To study the effect of temperaturend incubation time on nanoparticle synthesis, reaction mixturesere incubated at 25, 40, 60, 80 and 100 ◦C for 15, 30, 45, 60, 75 and

0 min, respectively. The stability of nanoparticles was examined

y exposing them to ambient condition for several months. It wasbserved that the nanoparticles solution was extremely stable forore than 3 months with no signs of aggregation even at the end

f this period.

ig. 1. (a) UV–vis spectra of the silver nanoparticles synthesized at different pH values

anoparticles prepared at pH 3.0 and 11.0.

and Products 48 (2013) 81– 88

2.4. Silver nanoparticles loaded onto non-woven fabrics

Non-woven fabric cut into little squares were immersed in apreformed synthesized silver nanoparticles solution (temperature:80 ◦C, silver nitrate concentration: 0.5 mM, pH 11, 0.1 mL of theextract and incubation time: 90 min). For the successive treatmentof non-woven fabric with colloidal silver, the solution was agitatedcontinuously for 30 min. The non-woven fabric was then dried at120 ◦C for 5 min under vacuum condition. The dried samples werewashed with distilled water to removal the unreduced Ag+ ions.The washed samples were again dried at 120 ◦C for 5 min undervacuum conditions. The antibacterial efficacy was evaluated for: (1)samples treated with mango peel extract (0.1 mL in 27 mL distilledwater) (control) and (2) samples treated with silver nanoparticlessolution.

2.5. Characterization of silver nanoparticles and nano-silvernon-woven fabrics

The optical absorption spectra of the synthesized nanoparticleswere observed by UV-2450 Shimadzu UV spectrometer. The mor-phology and size of freshly synthesized silver nanoparticles wereevaluated using a transmission electron microscope model (JeolJEM100SX). FTIR analysis was carried out after the removal of thefree biomolecules that were not absorbed by the nanoparticles afterrepeated centrifugation and redispersion in water. Thereafter, thepurified and dried silver nanoparticles was subjected to FTIR anal-ysis (Shimadzu FTIR spectrophotometer 8400). X-ray diffractionpattern of dried silver nanoparticle powder was obtained using

XPERT-PRO diffractometer using Cu K� radiation (� = 0.1542 nm).The morphology of nano-sized silver particles incorporated intonon-woven fabrics was studied with SEM (Hitachi S-4500 SEMmachine) after gold coating.

[A: 2.0, B: 3.0, C: 5.0, D: 7.0, E: 9.0, and F: 11.0] and (b) TEM images of the silver

N. Yang, W.-H. Li / Industrial Crops and Products 48 (2013) 81– 88 83

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ig. 2. (a) UV–vis spectra of the silver nanoparticles synthesized at different mangohe silver nanoparticles prepared at mango peel extract content of 0.1 mL and 3.0 m

.6. Antibacterial activity

Three different groups of bacteria Escherichia coli (gram negativeacteria), Staphylococcus aureus (gram positive bacteria), and Bacil-

us subtilis (spore forming) were investigated in this study. Nutrientgar was used as media to grow bacteria. The bacterial strains weretored in a refrigerator. The bacterial solutions were prepared in.86% saline. In order to study the antimicrobial activity of theon-woven fabrics, squares of 1 cm of each fabric were preparednd placed in agar plates using an aseptic technique. The platesere then incubated at 37.0 ◦C for 24 h, and the inhibition halo waseasured. The result represented the antibacterial activity and was

xpressed in mm.

. Results and discussion

.1. Effect of initial pH on the biosynthesis of silver nanoparticles

The initial pH value of the aqueous AgNO3 solutions was anmportant parameter in the synthesis of silver nanoparticles using

ango peel extract. It was observed that the color of AgNO3olutions changed from light brown yellow to dark brown whenhe initial pH of solution was increased. The color change would

e an indication of silver bioreduction mediated by mango peelxtract and the subsequent formation of silver nanoparticles after5 min of the reactions. UV–vis absorption spectroscopy is a mainool to analyze the noble metal nanoparticles formation, which

extract content (mL) [A: 0.1, B: 0.4, C: 0.7, D: 1.0 and E: 3.0] and (b) TEM images of

depends on surface plasmon resonance (SPR). The optical absorp-tion spectrum of metal nanoparticles is dominated by the SPR,depending upon the particle size, shape, state of aggregation andthe surrounding dielectric medium (Mulvaney, 1996). The UV–visspectra obtained from solutions at different initial pH after the reac-tion show characteristic absorption bands of silver nanoparticlesat around 412.0–434.0 nm. It is known that an absorption bandappears at about 400–440 nm because of the surface plasmon reso-nance in Ag nanoparticles (Pastoriza-Santos and Liz-Marzaın, 1999,2002). Fig. 1a shows the effect of initial pH on the silver nanopar-ticle formation by UV–vis spectroscopy, in which the experimentswere performed at pH from 2.0, 3.0, 5.0, 7.0, 9.0 and 11.0. The colorand the intensity of the peaks were pH dependent. At pH 2.0 (curveA), a light brown yellow color was observed but no characteristicpeak was observed. At higher pH (pH from 3.0 to 11.0), a varyingdark brown color and intense peaks were observed (curves B–F).The silver nanoparticles synthesized at pH of 3.0, 5.0, 7.0, 9.0 and11.0 presented absorption peaks at 434.0, 426.5, 422.5, 418.5 and412.0, respectively. The absorption peaks shifted to shorter wave-length and became narrower with the elevated pH value, possiblydue to the decreased size and/or anisotropy degree of the silverparticles (Evanoff and Chumanov, 2004; Mie, 1908; Noguez, 2007).TEM measurements were carried out to observe the size and mor-

phology of the silver nanoparticles prepared under pH 3.0 and11.0. As shown in Fig. 1b, all the particles prepared were quasis-spherical in shape. The shape of the product prepared under lowerpH was less regular and more aggregate. The average sizes of the

84 N. Yang, W.-H. Li / Industrial Crops and Products 48 (2013) 81– 88

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ig. 3. (a) UV–vis spectra of the silver nanoparticles synthesized at different silveranoparticles prepared at silver nitrate concentration of 0.5 mM and 4 mM.

articles prepared at pH of 3.0 and 11.0 were 27 nm (±22%) and5 nm (±28%), respectively. The average size decreased with ele-ated pH which was consistent to the blue shift of the absorptioneaks in the UV–vis spectra. This maybe due to the dissociated stateor capping functional groups of the mango peel extract are influ-nced by the pH of the reaction solution. With the elevated pH, theeprotonation of the capping functional groups are strengthened.he deprotonated functional groups might carry more negativeharge. Consequently, the negative charged groups bind to theilver nanoparticles and enhance the stability due to the electro-tatic repulsion. Thus, pH 11.0 is preferred for the formation ofono-dispersed and relatively spherical nanoparticles. No char-

cteristic peak was observed at pH 2, which may be due to thenactivation of reducing functional groups under extremely acidiconditions. Control silver nitrate solutions (without mango peelxtract) neither developed any colors nor did they display the char-cteristic peaks (data not shown). These results indicate that abioticeduction of silver nitrate did not occur under the reaction condi-ions that were used.

.2. Effect of the mango peel extract content

For studying the influence of mango peel extract content on syn-hesis of silver nanoparticles, samples were prepared by adding.1 mL, 0.4 mL, 0.7 mL, 1 mL and 3.0 mL of the extract, respectively.ther reaction conditions were: silver nitrate concentration: 1 mM,

ncubation temperature: 80 ◦C, time: 15 min, pH 11.0. The effectf different extract contents can be seen in Fig. 2 a. As the quan-

ity of the mango peel extract was increased from 0.1 to 3.0 mL, itas found that the absorption peaks shifted to longer wavelengths

nd the broadening of the peak increased, which is characteris-ic for an increase in particle size. The particle size distribution

e concentration (mM) [A: 0.5, B: 1, C: 2 and D: 4] and (b) TEM images of the silver

have also been studied by analyzing the TEM of colloids (referredin Fig. 2a A and E). The SPR minimum and maximum wavelengthsare shown in Fig. 2b. The micrographs showed that particles weremostly spherical and the average size of the spherical particlesincreased from 9 nm (±24%) (0.1 mL of extract) to 15 nm (±28%)(3.0 mL of extract). This was consistent with the shift of SPR peakfrom 400.0 to 412.0 nm. Song and Kim (2009) obtained a similartrend in the size of silver nanoparticles with the increase in Mag-nolia kobus leaf extract. This phenomenon may be due to too manyreducing agents bound to the surface of preformed nuclei, whichintensifies the secondary reduction of silver ions on the surfaceof the nuclei. Consequently, the growing rate of nanoparticles isincreased, leading to larger nanoparticles. On the other hand, toomany reducing agents may enhance the bridging effect among theformed nanoparticles, resulting in the aggregation of nanoparticles.For the generation of small silver nanoparticles, the lowest amount(0.1 mL) of mango peel extract is preferred. These results show thatthe quantity of mango peel extract is also a key factor determiningthe formation and size distribution of nanoparticles.

3.3. Effect of the silver salt concentration

The influence of silver nitrate concentration was investigatedby varying the concentration from 0.5 mM to 4.0 mM. Other reac-tion conditions were: incubation temperature: 80 ◦C, time: 15 min,pH 11.0, and 0.1 mL of the extract. Fig. 3 a shows the effect of sil-ver nitrate concentration on the formation of silver nanoparticles.Peak absorbance increases and shifts to higher wavelengths with

an increase of silver nitrate concentration from 0.5 to 4.0 mM. TEMimages at 0.5 and 4.0 mM silver nitrate concentrations have beenpresented in Fig. 3b. The particle size of silver nanoparticles wasfound to be larger at the higher silver nitrate concentration (7 nm

N. Yang, W.-H. Li / Industrial Crops and Products 48 (2013) 81– 88 85

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±23%) for 0.5 mM and 21 nm (±17%) for 4.0 mM). This may be dueo too many silver ions absorbed on the surface of preformed nuclei,here the secondary reduction process occurred leading to form

arger nanoparticles. To obtain small silver nanoparticles, 0.5 mMilver nitrate concentration is preferred.

.4. Effect of incubation temperature

The effect of temperature on the formation of silver nanoparti-les was also investigated. The SPR spectra and TEM measurementsere taken after heating the sample for 15 min at different

emperatures. Other reaction conditions were: silver nitrate con-entration: 0.5 mM, pH 11.0, and 0.1 mL of the extract. Fig. 4ahows the silver nanoparticles production with different reactionemperatures obtained with mango peel extract. As the reactionemperature increased from 25 ◦C to 100 ◦C, it was found that thePR bands became sharper and shifted to shorter wavelengths sig-ifying a decrease in the particle size. TEM measurements werelso carried out to observe the size and morphology of the sil-er nanoparticles prepared at 25 and 100 ◦C. As shown in Fig. 4b,ll the particles prepared were almost mono-dispersed sphericalanoparticles. The average sizes of the particles prepared at 25 and00 ◦C were 37 nm (±36%) and 8 nm (±16%), respectively. The aver-ge size decreased from 37 nm (25 ◦C) to 8 nm (100 ◦C), which wasonsistent to the blue shift of the absorption peaks in the UV–vispectra. Song and Kim (2009) also mentioned the decrease in par-icle size with increasing temperature for the silver nanoparticles

ynthesized using Diopyros kaki leaf broth. Regarding the reason forhe decrease in particle size with increasing temperature, it can bepeculated as follows. As the reaction temperature increases, theeduction rate increases and thus most silver ions are consumed in

perature (◦C) [A: 25, B: 40, C: 60, D: 80 and E: 100] and (b) TEM images of the silver

the formation of nuclei, blocking the secondary reduction processon the surface of the preformed nuclei. Therefore, small and highlydispersed nanoparticles are formed. There was little variation in thewavelength of SPR band by increasing the reaction temperaturefrom 80 to 100 ◦C. Increasing the temperature beyond 80 ◦C onlyaided minor increase of silver nanoparticles yield. For the purposeof saving energy, the reaction temperature of 80 ◦C is preferred.

3.5. Effect of reaction time

The effect of different reaction times was examined in thesynthesis of silver nanoparticles. The other reaction conditionswere: incubation temperature: 80 ◦C, silver nitrate concentration:0.5 mM, pH 11.0, and 0.1 mL of the extract. Fig. 5a shows theUV–vis spectra recorded from the aqueous silver nitrate–mangopeel extract reaction medium as a function of time of reaction.It was observed that the silver surface plasmon resonance bandoccurs at ca. 402.0 nm and steadily increases in intensity as afunction of time without any shift in the peak wavelength. The con-version to silver nanoparticles occurs fairly rapidly. More than 80%conversion is completed within 15 min. No change in absorbancewas noticed after 90 min incubation, confirming the completereduction of silver ions to silver nanoparticles. In earlier studieson the synthesis of silver using plant leaf extracts (Shashi et al.,2010), the time required for completion of the reaction was about300 min and was thus rather slow. This is one big drawback of thebiosynthetic procedures that needs to be focused on if they are to

compete with chemical methods for Ag nanoparticle synthesis. Thesharp fall in reaction time from several hours to one hour and a halfobserved for the mango peel extract is a significant advance towardachieving this goal. The average sizes of the particles prepared at

86 N. Yang, W.-H. Li / Industrial Crops and Products 48 (2013) 81– 88

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5 and 90 min were 10 nm (±13%) and 11 nm (±16%). No signif-cant changes were detected in the particle size distributions byEM (Fig. 5b) during this time interval as well.

.6. Stability of nanoparticles

The stability of the synthesized Ag nanoparticles was studiedy measuring its intensity at 402.0 nm over a period of 3 months inhe following reaction conditions: incubation temperature: 80 ◦C,ilver nitrate concentration: 0.5 mM, pH 11, reaction time: 90 min,nd 0.1 mL of the extract. No significant change in the absorbanceas observed, which proved its stability over a longer period (dataot shown).

.7. X-ray diffraction (XRD) analysis

A XRD profile of biosynthesized silver nanoparticles is shown inig. 6. The diffraction peaks at 2� = 38.26◦, 44.38◦, 64.72◦ and 77.50◦

assigned to the (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes of a facedenter cubic (fcc) lattice of silver] were obtained. The XRD patternsisplayed here are consistent with earlier reports (Satishkumart al., 2009; Bar et al., 2009).

.8. Mechanism of silver nanoparticles formation

In order to determine the functional groups on mango peelnd predict their role in the synthesis of silver nanoparticles,TIR analysis was performed. The control spectra (untreated withilver nitrate) showed a number of peaks thus reflecting a com-

and (b) TEM images of the silver nanoparticles prepared at reaction time of 15 min

plex nature of the mango peel. The band intensities in differentregions of the spectrum for the control and test samples (beforeand after reaction with silver nitrate, respectively) were analyzedand are shown in Fig. 7. There was a shift in the following peaks:3410–3420, 2920–2918, 2367–2266, 1653–1630, 1458–1441, and1051–1032 cm−1. The broad and intense absorption peak at around3410 cm−1 corresponds to the O H stretching vibrations of phe-nols and carboxylic acids. The shift from 3410 to 3420 cm−1 mayindicate the involvement of O H functional group in the synthesisof nanoparticles. The peak 2920 cm−1 (attributed to the symmet-ric and asymmetric C H stretching vibration of aliphatic acids)(Li et al., 2007) shifted to 2918 cm−1, which indicates the possi-ble involvement of this group in silver nanoparticles synthesis. Thepeaks located at around 2367 cm−1 and 1734 cm−1are attributed toC O stretching vibrations in aldehydes and ketones (Farinella et al.,2007). The peak shift from 2367 to 2266 cm−1(becoming weak)and the disappearance of 1734 cm−1 after the reaction with silvernitrate implicate that these groups may be involved in the processof reducing Ag+ ions causing them to get oxidized to carboxylicacids. The peaks at 1653 and 1458 cm−1 are due to asymmetricand symmetric stretching vibrations of C O in carboxylic groups(Farinella et al., 2007). The peak located at 1051 cm−1 may be dueto C OH of carboxylic acids (Guibavd et al., 2003) which shiftsto 1032 cm−1 representing the involvement of these functionalgroups in the nanoparticle synthesis. The FTIR spectra indicate

that the functional groups ( CHO, C O, COOH, and OH) maybe responsible for the reduction and stabilizing of silver nanoparti-cles. Mango peel principally consists of pectin, cellulose, lignin, andflavonoid (Feng et al., 2009; Liang et al., 2009). These components

N. Yang, W.-H. Li / Industrial Crops and Products 48 (2013) 81– 88 87

Scheme 1. Possible pathways of sil

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Fig. 6. XRD pattern of silver nanoparticles.

ontain various functional groups, including aldehydes, ketone,

arboxyl and hydroxyl. The possible reaction between mango peelxtract and silver ions can be written as follows (Scheme 1):

In the solution containing mango peel extract, silver ions areeduced in two possible paths. The first is as follows: 1. In acidic

ig. 7. FTIR spectrum of mango peel extract (A) before and (B) after reaction withilver nitrate.

ver nanoparticles formation.

condition, Ag+ is compounded with the biomolecules (containingcarboxyl and hydroxyl) generating complex ions. Then the alde-hydes and ketones (existing in biomolecules) reduce Ag+ ions toAg nanoparticles and get oxidized to carboxyl. In the process ofthe reaction, the carboxyl and hydroxyl form a protection layer onthe surface of Ag nanoparticles. This protection layer may causesteric hindrance around the particles and thereby stabilize them(Prarthna et al., 2011). The second is as follows: 2. In alkalinecondition, Ag+ ions react with hydroxyl ions, and the productAg2O is generated. In the presence of sodium hydroxide, carboxylsand hydroxyls release H+ ions and the formed carboxylate andhydroxylate ions attach to Ag2O (forming Ag2O complex). Thealdehydes and ketones reduce the Ag2O to Ag nanoparticles andget oxidized to carboxylic ions (alkaline condition) which alsoget attached to the Ag nanoparticles. The negative charged car-boxylate and hydroxylate ions on the surface of Ag nanoparticlesnot only cause steric hindrance but also electrostatic repulsionto stabilize the nanoparticles and inhibit them to grow larger.That is why smaller nanoparticles are formed under alkalinecondition.

3.9. Antibacterial activity of the non-woven fabrics loaded withsilver nanoparticles

The SEM micrograph of non-woven fabrics loaded with silvernanoparticles is shown in Fig. 8. Fig. 8 demonstrates the homo-geneous depositions of silver nanoparticles (black arrow) on thefabrics. The antibacterial activity of silver nanoparticles loaded ontonon-woven fabrics against etalon strains of three different groupsof bacteria E. coli (gram negative bacteria), S. aureus (gram positive)and B. subtilis (spore forming) has been studied. Different mecha-nisms for bacterial action of silver nanoparticles are the following:(i) silver nanoparticles are supposed to attach to the surface of thecell membrane and disturb its function, penetrate bacteria, andrelease Ag; (ii) silver nanoparticles target the bacterial membrane,leading to a dissipation of the proton motive force. The inhibi-tion zones are 13.0, 14.5 and 11.0 mm for E. coli, S. aureus, and

B. subtilis, respectively. This difference may be due to the differ-ent mechanisms and the susceptibility of the organism used in thepresent study. Controls show no zone of inhibition, which indi-cates the antimicrobial activity is due to the bio-inspired silvernanoparticles.

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. Conclusion

It has been shown for the first time that agricultural wasteaterial can be used for the consistent and quick synthesis of

uasis-spherical silver nanoparticles. Variation in reaction condi-ions affected nanoparticle synthesis. The pH, mango peel extractontent, silver salt concentration and incubation temperature aremportant parameters in controlling the size of Ag nanoparticles.he FTIR spectra indicate that the functional groups ( CHO, C O,COOH, and OH) may be responsible for the reduction and stabi-

izing of silver nanoparticles. Non-woven fabrics loaded with theseio-inspired silver nanoparticles displayed excellent antibacterialctivity, indicating that they are a promising candidate for manyedical applications.

cknowledgement

This study is supported by the Youth Science Foundation ofhanxi Province, China (no. 2008021036-4).

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