Sensors and Actuators B 228 (2016) 471–479

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Silver based nanomaterial, as a selective colorimetric sensor for visual

detection of post harvest spoilage in onion
Divya Sachdev a,∗ , Vinay Kumar a , Priyanka H. Maheshwari b , Renu Pasricha c , Deepthi c ,
Neeraj Baghel a
a
Department of Agriculture and Environmental Sciences, National Institute of Food Technology Entrepreneurship and Management, Sonepat, India
b
National Physical Laboratory, CSIR, New Delhi 110012, India
c
National Centre for Biological Sciences, Bengaluru, India

a r t i c l e i n f o a b s t r a c t

Article history: Onion being a semi-perishable horticultural bulb crop gets subjected to deterioration during the storage,
Received 11 September 2015 which ultimately leads to huge monetary losses every year. Specific detection tools for onion spoilage
Received in revised form 6 January 2016 will be an asset in relieving losses during post-harvest storage. In this context silver based yellow col-
Accepted 13 January 2016
ored colloidal nanoparticle (AgY-NPs) solution was synthesized and evaluated as a visual sensor for the
Available online 19 January 2016
organo-sulfur compound released during the spoilage of onions. The visual changes during the spoilage
was monitored for ten days wherein the yellow color of the AgY colloidal solution changed to orange,
Keywords:
pink and finally turned transparent. Simultaneous analysis carried out by UV–Vis spectroscopy and col-
Onion
Postharvest spoilage
orimeteric analysis corroborates our investigation of AgY-NPs as a visual sensor displaying selectivity
Silver nano particles and specificity for volatile sulphur compound responsible for spoilage of onions. Furthermore, analysis
UV–Vis spectroscopy of AgY-NPs in presence of healthy onions showed distinct visual results which were complemented by
Colorimetric analysis probable mechanism. Besides this the structural changes in AgY-NPs due to incorporation of sulphur com-
pounds were supported by Powder X-ray diffraction (PXRD), Raman Analysis, Fourier Transform-Infrared
Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM)
which clearly indicated the capacity of these AgY-NPs as a powerful detection tool for onion spoilage.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction that have deteriorating effects in a long run [10,11]. There is an

Onion (Allium cepa L.) is a widely grown crop with world produc-
tion of 75 million metric ton annually (FAO 2012) [1]. Onion being a
good source of minerals, vitamins, polyphenol and phytonutrients
(organosulfur compounds) displays varied health benefits in pre-
venting high blood pressures, diabetes and cancer [2]. Although
onion possess a good nutritive value, but a high-quality check
over its nutritive consistency relies mostly on the adequate stor-
age conditions. Once these crops are harvested they are threatened
by the post harvest diseases mostly caused by bacterial and fun-
gal pathogens that may serve as a vehicle for disease propagation
which in turn reduces their shelf life [3–6]. Microbial infection and
mechanical aberration during transportation also leads to 20–30%
post harvest loss [7–9]. Although many bactericides and fungicides
are employed to mitigate the post harvest infection of onion, how-
ever there is a strong need to alter the prevalent methodologies
∗ Corresponding author.
E-mail address: divya19sachdev@gmail.com (D. Sachdev).
important saying “prevention is better than cure” and therefore it
is important to control the decay and infection at an early stage
of storage for reducing the post harvest losses. Many physiologi-
cal and biological changes accompanied during the initial infection
needs to be sensed; therefore a specific, sensitive sensor is very
much required that can address the above issues. So far, differ-
ent methodologies for analysing the quantitative difference of the
volatiles between healthy and infected onions were analysed by
Gas Chromatography/Mass Spectoscopy [12], and compared to this
an alternative approach such as gas sensor arrays or E-nose technol-
ogy [13–15] have been developed. Although the uniqueness of the
E-nose technology depends on the presence of the type of material
used (metal oxide, conducting polymers) to predict the changes in
the voltage signals via the volatiles released, however the complex
calculations and preparation of customized gas chambers may have
operational problems which may result in erroneous output. Hence,
the need of an hour is to develop a simplified, cost-effective com-
pact way to detect and sense the onset of infection in onions (even
when the deterioration symptoms are not visible). In this regard,
we synthesized yellow colored stabilized silver nanoparticles (AgY-

http://dx.doi.org/10.1016/j.snb.2016.01.049
0925-4005/© 2016 Elsevier B.V. All rights reserved.
472 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479

NPs) that behaved as a visual sensor for onion spoilage and to best
of our knowledge this is the first report that visually distinguished
AgNO3 + NaBH4 Ag+ + H2 + B2H6 + NaNO3
-
O
(supported by UV–Vis spectroscopy and colorimeter) healthy and
O
the infected onions.
O
Recent studies have shown large contribution of nanoscience
technology in the field of agriculture and food sciences [16–18]. The OH
current genesis of the detection/sensing lies in the change of optical HO
O
behaviour of novel silver nano-colloid due to the incorporation of O
HO O
-

volatile sulphur. During spoilage, the unstable organosulfur com- O

-

PEG
pounds, present in the onion gets ruptured and further rearranges O H O
- O
OH
to form a stable complex with AgY-NPs which ultimately leads H
O O O O
to color changes. Moreover, the tendency of silver nanoparticles ion-pair interaction ion-pair interaction
+ O HH O-
displaying credibility in terms of protection against microbes [19] Ag O
H O O H
will surely make them a better tool in food safety. And therefore O -
O
H O
O
our study has a commercial scope in detection and distinguish- O
HO O
ing post harvest spoilage of onions from healthy ones without any H
H HO
-
O O OH
interference from moisture, atmospheric oxygen or carbon dioxide. O
O - O
-
TSC
O
-
OH O
O O O
O
2. Experimental OH -
O
HO O
2.1. Synthesis of stable silver nanoparticles (AgY-NPs) OH
O

All the reagents used were of analytical grade. Synthesis of yel-
low colored stable silver nanoparticles were obtained by reduction
of Ag+ ions using NaBH4 as a reducing agent in a combined matrix
of polyethylene glycol (PEG) and trisodium citrate (TSC) [21] act-
ing as a stabilizing and capping agent respectively. All the solutions
employed during the synthesis were freshly prepared. In a typical
synthesis, AgNO3 (10 ml, 30 mM) was mixed to a solution contain-
ing PEG (5 ml, 5 mM) and TSC (5 ml, 30 mM) in a round bottom flask
that was previously stirred for half an hour at room temperature.
To this suspension, freshly prepared cold solution of NaBH4 (5 ml,
26 mM) was added drop wise, the solution initially turned to faint
yellow and gradually the yellow color deepened. The yellow col-
ored colloidal NPs solution of silver nanoparticles was named as
AgY-NPs and was stored in a dark colored closed container for fur-
ther use. AgY-NPs colloidal solution was characterized via PXRD,
UV–Vis spectroscopy and SEM analysis.
2.2. Monitoring the onion spoilage using AgY-NPs as a visual
sensor
In the present study the onion spoilage was monitored by
detecting the release of volatile metabolites evolved during the
spoilage via the stable yellow colored silver colloidal solution. Two
months stored variety of Pusa nasik after curing were purchased
from local storage house. Set of onions at an initial stage of spoilage
were carefully chosen and were placed in a sealed desiccator fitted
with a tube containing AgY-NPs solution, to act as a visual sensor
(as a gas analysing set up) during spoilage. The whole assembly
was placed at a fixed place and ambient conditions were main-
tained for the period of investigation. The changed color of AgY-NPs
during spoilage was examined through UV–Vis spectrophotometer
and colorimetric response. Furthermore the changes in the AgY-
NPs solution were evaluated via PXRD, FT-IR spectroscopy, Raman
and TEM and finally mechanism of color change was also suggested.
2.3. Characterization
Photographs were acquired by Samsung digital camera. UV–vis
spectra were measured using Schimadzu-2600 spectrophotometer.
CHNS analysis for determining sulfur content in healthy onion was
done on EuroVector model no. Euro3000 instruments. Inductively
Coupled Plasma Spectroscopy for finding the amount of volatile
sulfur in nanoparticle solution was done on PerkinElmer model
O
- HO
O
-
O
Scheme 1. Schematic Illustration of stable silver nanoparticle; formed by interac-
tions of PEG and TSC.
Optima 7000DV. The X-ray diffraction examination of the sam-
ples was performed on Rikagu Powder X-ray diffractometer (PXRD)
model: XRG 2KW using Cu K␣ radiation. Raman spectroscopy was
carried out using a Renishaw InVia Reflex Micro Raman Spectrom-
eter equipped with the CCD detector at room temperature and in
air. Argon ion laser (excitation line 514 nm) was used to excite
the samples. One scan per sample was recorded wherein the sam-
ple was exposed to the laser power of 25 mW for 30 s. Infrared
sepectroscopy (ATR-IR) spectra of the samples was recorded on
Bruker–Alpha for evaluating the differences in functional groups
on AgY-NPs solution via infected and the healthy onions. Morphol-
ogy of the sample was analysed by Scanning Electron Microscopy
(SEM), Zeiss. Colorimeter of the samples was conducted on Chro-
mameter CR-400 (Konica Minolta). Particle size was analysed on
Tecnai G2 Spirit Bio-TWIN Transmission Electron Microscope
3. Results and discussions
3.1. Structural analysis of AgY-NPs
Synthesis of silver nanoparticle was done in the presence of two
stabilizing agents polyethylene glycol (PEG) and tri-sodium citrate
[21]; sodium borohydride was used as a reducing agent [21,22]. The
addition of two stabilizers inhibits the aggregation of reduced silver
nanoparticles for many days while keeping them dispersed in the
solution. Moreover the methodology employed induced uniformity
in the shape and size while forming an ultrafine silver nanoparticle.
This may be due to the ion-pair interactions present between the
polyethylene glycol and sodium citrate ion which forms a protec-
tive shell around the silver ions during the reduction and stabilize
them in solution for months as shown in Scheme 1.
UV–Vis spectroscopy is the most prominent technique used for
the structural characterization of Ag-NPs. The absorption spectra
of initially made stable yellow colored AgY-NPs colloidal solution
shows the Surface Plasmon Resonance SPR at 404 nm [21] (Fig. 1(A))
which slightly shifted to 425 nm on diluting with water [23], this
may be due to the presence of the water (Scheme 1) ligands near
 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479 473

Fig. 1. (A) UV–vis spectrum of AgY-NPs (originally formed and diluted for further use). (B) SEM image showing uniformly distributed AgY-NPs.

Fig. 2. (A) Spectral changes of AgY-NPs collected in presence of different concentration of sulphite solution after a period of 30 min incubation. (B) Variation in absorbance
depression with respect to concentration at ( = 425 nm).

metal centre which may change the refractive index of the sur-
rounding medium [24]. As a result it leads to formation of spherical
silver nanoparticle with an average size of 3–4 nm that was further
confirmed by TEM images (Fig. 8(A)). However, the diluted silver
nanoparticles stored in dark, retained the stability for months (no
variations in the color and UV–Vis spectra was found, supplemen-
tary material Figs. S1, S2) because of which they could be employed
as visual sensor for onion spoilage activity. The PXRD pattern shown
in the later part of the manuscript (Fig. 6) clearly indicates the
formation of silver nanoparticles.
The uniformity in the particle size distribution of the AgY-NPs
over a large surface was also observed by SEM. SEM image (Fig. 1(B))
shows a high-density of silver nanoparticles, with structural unifor-
mity. The surface morphology showing cluster formations of NPs
gives a clear indication of stabilization of AgNPs by the capping
agents.
3.2. Optimization of silver (AgY-NPs) nanoparticles for onion
spoilage
To corroborate our endeavour of employing AgY-NPs for the
detection of onion spoilage, primarily, analogous behaviour of spec-
troscopic changes was studied wherein colloidal AgY-NPs solution
was incubated with a sulphur moiety (as also anticipated from
onion spoilage). In this respect different concentrations of sodium
sulphite solutions from 0.1, 0.3, 0.5, 1, 5, 10, 20, 50 ␮M were incu-
bated with the colloidal AgY-NPs solution for 30 min followed by
the spectral analysis of the above solutions for estimating UV-
absorbance changes (Fig. 2 (A)). The amount of elemental sulphur
within the healthy onion whence detected via CHNS a destruc-
tive method was found to be (i.e. 2.5–3 mg/g). It is well known
that the amount of volatile sulphur compounds goes on increas-
ing on spoilage [12,25] and when detected via destructive or non
destructive method was approximately 110 ppm [26] and 196 ppm
[27] respectively. Particularly, addition of sulfite to colloidal AgY-
NPs solution alters the absorbance value, this distinctive sensitivity
of SPR towards sulphur addition might have occurred due to the
change in nanostructural morphology of the AgY-NPs colloidal
solution [28,29]. For a corresponding absorption change in Surface
Plasmon Absorption Resonance (SPR) maxima, Yang et al. [30] have
also shown similar relationship between absorbance value and sul-
fite concentrations varying from 0.1 ␮M to 5 ␮M (Fig. 2(B)); this
retrieves our presumption of change in UV absorption, on interac-
tion of AgY-NPs with volatile organo-sulphur compounds released
during onion spoilage. The Moreover, sodium sulphite was chosen
for interaction studies with AgY-NPs colloidal solution since sul-
phite in the medium also acts as a scavenger for the oxygen which
further confirms that the change in absorbance is only due to the
presence of the sulphur (in sulphite form) which transforms Ag ions
474 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479

Fig. 3. Photographs showing visual color changes observed in AgY-NPs solution with respect to the days kept inside the spoiled onions (A) the spoiled onions set up with
AgY-NPs colloidal solution (B) Original AgY-NPs (C) the darkened color of AgY-NPs. Visual color of AgY-NPs solution changed to (D) orange color (E) pink colored (F) faint
pink color (G) totally fainted transparent. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

to stabilized Ag2 S NPs and not due to the presence of atmospheric

oxygen.

3.3. AgY-NPs as an onion deterioration indicator

In order to evaluate the distinct property of colloidal AgY-NPs

as a visual sensor for spoilage of onions; a small set of spoiled
onions in a vacuum sealed desiccator were arranged with a gas out-
let pipe that encompasses AgY-NPs in a tube. The released volatile
(presumed to be organo-sulphur compounds released during onion
spoilage) [14,20,31] infuses inside the AgY-NPs colloidal solution,
leading to a change in yellow color. For the initial two days, no
visual changes in the color of AgY-NPs was observed but gradually
as the days surpassed the yellow color started changing towards
orange, pink, and finally to transparent as we proceeded for 10th
day (Fig. 3). These consecutive changes in the color of AgY-NPs
colloidal solutions is possibly due to the interactions between nano- Fig. 4. UV–Vis spectral changes of AgY-NPs observed in presence of the organosulfur
silver and volatile organosulfur compounds that react to form a compounds evolved from spoiled onions (1st day to 10th day). (For interpretation
of the references to colour in this figure legend, the reader is referred to the web
stable silver sulphur complexes due to the higher stabilization con-
version of this article.)
stant between silver and sulphur elements [32,33]. The profound
color difference of reacted AgY-NPs colloidal solution (10th day)
with respect to the 1st day of the spoiled onions was also supported 3–4 nm as also indicated from TEM images (Fig. 8(a)). As the con-
by the UV–Vis spectroscopy and colorimetric analysis. centration of volatile sulphur gases increase with time (spoilage
UV–vis spectroscopy of AgY-NPs colloidal solution was per- days) the absorption spectrum showed a red shift in Surface Plas-
formed periodically for monitoring the changes in the spoiled mon band from 425 nm to 547 nm as shown in (Fig. 4) Further to
onions. After the introduction of volatile organo-sulfur compounds ascertain the above hypothesis, AgY-NPs were also placed inside
in AgY-NPs colloidal solution via onion spoilage (Fig. 4); a distinct a set of healthy onions for similar time frame and tested for any
variations in the absorbance value (at wavelength 425 nm) were visual changes in AgY-NPs colloidal solution via periodical UV–Vis
observed. The absorption spectra appeared due to localized Surface spectrometry and colorimetric analysis.
Plasmon resonance LSPR [34]. particularly because of the collective For the healthy onions, the absorption spectra of AgY-NPs col-
excitation of the conduction band electrons of silver nanoparti- loidal solution due to LSPR, was found to blue shift with respect
cles consisting of spherical shaped AgY-NPs with an average size of to the spectra observed originally at wavelength 430 nm (pre-
 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479 475

Fig. 5. UV–Vis spectral changes of AgY-NPs observed in presence of healthy onions (1st day to 8th day). Photographs showing AgY-NPs (A) AgY-NPs in presence of healthy
onions (B and C) showing almost nil color variations of AgY-NPs solution. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

H3C
O H3C
O

S OH
+
S OH
O NH2
-
O NH2
isoalliin

fresh during spoilage

H 3C
S
H3C OH + pyruvate + NH3
H3C

S Ag--complex + CH2 CH2

O S S
O - H3C
H3C O O
H 2N O
OH propane thial S-oxide 3-ethyl oxathirane S

Ag--complex Ag--complex
-S
C
CH2 O
A (Ag--complex)--S
H3C CH +
B

Scheme 2. Plausible Mechanism of AgY-NPs solution undergoing visual change in presence of organosulfur compound (isoallin).

pared via diluting original AgY-NPs solution) (Fig. 5(B)) in the
wavelength ranging from 387 nm to 352 nm [35]. These discrep-
ancies in the wavelength shift for spoiled (red shift, Fig. 4) and
healthy onions (blue shift, Fig. 5(A)) from the original AgY-NPs
can be explained due to the structural changes occurring in the
isoalliin (+)-S-(1-propenyl)-l-cysteine sulfoxide which splits dur-
ing spoilage [14,31,36]. A brief plausible mechanism shown in
Scheme 2 explains the visual changes occurring, since during
spoilage isoallin hydrolyses and ultimately splits, while releasing
sulphur moiety which combines with silver (in the form of B or C
in Scheme 2). An increased polarization over silver nanoparticles is
possible that will contribute to the delocalization of electron den-
sity. And as a consequence, lowering of the energy levels for both
unexcited and excited states causes a red shift.
However in healthy conditions of onions degradation of isoallin
is almost negligible [37,38], wherein the sulphur site is not freely
available (as seen from Scheme 2(A)) for any interactions between
sulphur and silver. Therefore the UV–Vis absorbance trend totally
differs in case of healthy onions while inheriting the blue shift.
There may be possibility of increase in electronic effects on sil-
ver during formation of these complexes which might result in
lowering of the unexcited energy levels and results in a blue shift.
The visual changes on AgY-NPs colloidal solution was also
administered by colorimeter. The color indicative response of the
NPs solution was evaluated by Chromameter CR-400 wherein the
color variations were associated by parameter (L*, a*, b* and E*).
L* is for lightness with values ranging from 100 (white) to 0 (black),
while parameters like a* and b* respectively indicates (+a) red
476 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479

Fig. 6. PXRD pattern of yellow colored AgY-NPs (original) and faint AgY-NPs Fig. 7. Raman spectra of yellow colored AgY-NPs (original) and faint AgY-NPs
(exposed to spoiled onions). (For interpretation of the references to colour in this (exposed to spoiled onions). (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.) figure legend, the reader is referred to the web version of this article.)

to (−a) green, (+b) blue to (−b) blue [39,40]. Values in Table (1)
Table 1
give a fair connection between the deviations in the color ranging Color parameter (L* a* b* and  E*) response of AgY-Nps in presence of spoiled
from yellow to orange, pink and finally transparent during spoilage. onions.
From Table 1, L* value increase rapidly from 80 to 84 indicating an
Days L* a* b*  E*
increase in lightness of the medium, further the higher value of
a* from (−) to (+) is significant enough to indicate that the color 1 80.71 ± 0.33 −2.32 ± 0.20 11.69 ± 1.08 14.12 ± 0.87
2 82.64 ± 0.42 −0.76 ± 0.06 9.22 ± 0.43 11.27 ± 0.58
was deviating towards reddish and pinkish tint, (Fig. 3) which is
3 82.70 ± 0.58 0.24 ± 0.07 7.45 ± 0.43 10.52 ± 0.68
in full accordance to the observed pattern of color changes during 4 82.72 ± 0.65 −0.13 ± 0.03 7.76 ± 0.58 10.61 ± 0.80
spoilage. Parameter b* has all positive values on all days however in 5 82.91 ± 0.49 0.17 ± 0.06 5.82 ± 0.22 9.92 ± 0.51
descending way which means that yellow color started disappear- 6 83.28 ± 0.17 −1.35 ± 0.05 7.00 ± 0.14 9.92 ± 0.15
7 83.35 ± 0.29 0.26 ± 0.04 6.42 ± 0.18 9.28 ± 0.53
ing. Variations in the visual pattern of NP solution during spoilage
8 84.07 ± 0.50 0.37 ± 0.11 5.61 ± 0.30 8.76 ± 0.55
occurred due to the morphological changes in the AgY-NPs solution 9 84.25 ± 0.20 0.06 ± 0.02 5.56 ± 0.05 8.55 ± 0.19
(as also shown in Scheme 2). Moreover, an eminent pH change was 10 84.53 ± 0.38 0.17 ± 0.14 5.33 ± 0.36 8.28 ± 0.43
also observed during the spoilage. In the initial phase of spoilage
± SD Mean deviation of a triplicate.
wherein the sulphur content was low, neutral pH was observed, and
as sulphur content increased the pH changed to acidic. A similar col-
orimeteric analysis (Table 1S, Supplementary material) conducted
over the healthy onions periodically showed minor differences as brought changes in the AgY-based visual sensor was very less and
compared to the prominent changes detected from the spoiled went afar from the permissible limits of the equipment. This gives
onions. This interesting behavioural difference of the spoiled onions us an elucidation that AgY-visual sensor is sensitive enough to
on colorimeter and UV–Vis spectroscopy gives a special edge for detect the volatile sulphur compound that is released during the
AgY-NPs to behave efficiently as a visual sensor for spoiled onions. spoilage of onions which can be employed at an early stage for
It is also intresting to note that the monitoring of colour changes in reducing post harvest losses.
AgY-NPs was repeated thrice in case of detioratied onions and twice
for healthy ones with 100% reproducibility. Furthermore, the col-
orimetric response through distinct changes in AgY-NPs colloidal 3.5. Validation of the visual change in AgY-NPs colloidal solution
solution during the spoilage was also investigated by PXRD, FTIR,
Raman, SEM and TEM which supported our prediction. 3.5.1. PXRD
Fig. 6 compares the X-ray spectra of the faint colored AgY-NPs
3.4. Specificity and sensitivity test of AgY-NPs solution colloidal solution (after completion of exposure to spoiled onions,
AgY-S complex) with the original yellow colored AgY-NPs. The
AgY-NPs solution was simultaneously placed in the CO2 cham- broad hump for Ag is probably the result of particles in nano dimen-
ber and O2 chamber to ensure any changes due to the above sion 2–3 nm as is also clear from the TEM micrographs (Fig. 8(a)).
environment or the stipulated time period. The visual and UV Moreover capping of AgNPs with PEG and TSC further suppresses
results indicate that these gases (Supplementary material, Fig S3) the characteristic peaks of Ag. Very small peaks are obtained at
do not interfere in any manner with the AgY-NPs solution; this 2theta values of nearly 38 and 43 corresponding to [1 1 1] and
further confirms the stability of the silver solution. Moreover pres- [2 0 0] planes of Ag NPs [41–43]. However, the spectra of faded
ence of moisture do not interfere the absorbance of the AgY-NPs. AgY-NPs collected at the 10th day of exposure to spoiled onions
We also tried to quantify the sulphur content via Inductively Cou- showed additional diffraction peaks at 2theta 26.09 (1 1 1), 29.8
pled Plasma (ICP) Spectroscopy; during spoilage studies with every (0 1 2), 41.89 (0 3 1) and 45.2 (1 3 0) that can be correlated to the
change in the colour of AgY-NPs solution. The detection via ICP presence of Ag2 S (B) or Ag-Complex bind to the three membered
for the amount of sulphur present in each sample during colour ring (C, Scheme 2) (JCPDS Card File no 00-014-0072) [44–46]. A
changes was done via calibrating standards of silver and sulphur marked difference in the PXRD patterns gives a clear indication of
salts (Fig S6), however the level of sulphur that accumulated and sulphur intrusion inside the silver complex during the spoilage.
 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479
Fig. 8. TEM micrographs of dispersed yellow colored AgY-NPs (original) (A) nanoparticles seen at 50 nm scale and (A1) at 5 nm scale. Micrograph of aggregated faint AgY-NPs
(exposed to spoiled onions) (B) at 50 nm scale (B1) at 5 nm scale. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)
3.5.2. Raman analysis
AgY-NPs were collected after the complete exposure to spoiled
onions and were compared with the original AgY-NPs via Raman
spectroscopy. Raman spectra of original AgY-NPs colloidal solu-
tion (Fig. 7) do not show any excitation with the Ar laser and is
similar to the depicted reference[47]. However well defined peaks
for AgY-NPs exposed to spoilage were obtained at 553.8, 790 and
1094.6 nm. The distinct peaks observed clearly prooves the struc-
tural changes in the colored solution of AgY-NPs corrosponding to
the formation of silver sulfur complex [47]. The vibrational peaks
appearing at 1094, 553 and 790 closely resembles the (S O, asym-
metric stretching), assymmetric bending of ( O S O ) and C S
stretching respectively as also reported in few publications[48];
and majorly points out to the formation of complex (as seen in,
Scheme 2).
3.5.3. FT-IR studies
FT-IR of AgY-NPs (Fig. S4) showing characteristic peaks at
3300 cm−1 and 1690 cm−1 represents O H and C O stretching due
to PEG and TSC that serves as a capping agents of AgNPs that binds
to the metal ion strongly and prevent agglomeration. However in
case of fainted AgY-NPs colloidal solution due to the infusion of
sulphur, the spectral intensity of O H peak diminishes and shifts
to 3100 cm−1 while the intensity of peak at 1690 cm−1 reduced
sharply. Additional bands ranging from 956 to 1061 cm−1 and a
sharp band at 780 cm−1 were obtained corresponding to the S O
stretching and C S stretching frequencies which very well cor-
relates with the values in the literature[49,50]. This infers that
sulphur moiety substitutes inside the silver shell forming a stable
sulphur-silver complex due to the higher stabilization constant for
silver binding with sulphur [33].
3.5.4. TEM and SEM studies
Fig. 8(A) shows the TEM image of yellow colored AgY-NPs
colloidal solution before exposing it to spoiled onions with
nanoparticles size ranging from 3–4 nm [21]. The particles
appeared to be of uniform size and well dispersed. In contrast
to this the exposed AgY-NPs colloidal solution became faint and
477
started aggregating together (as seen from TEM image also, Fig. 8(B)
with increase in the particle size (5–6 nm). Further Fig. 8(A1, B1)
shows AgY-NPs at higher resolution. Additionally SEM-EDAX (Fig.
S5, Supplementary material) of the faint AgY-NPs was done which
displayed clearly the infusion of sulphur inside the AgY-NPs.
4. Conclusions
The work presents a simple, selective AgY-NPs based sensor to
detect and distinguish the spoiled onions from the healthy ones.
The distinct color change in presence of spoiled onions from yellow,
orange to pink and finally to transparent offered a clear indication
of sensitive visual sensor. Furthermore, the color change was cor-
roborated by UV–Vis spectroscopy and colorimetric data followed
by plausible mechanism. AgY-NPs visual sensor displays specificity
for volatile sulphur compound responsible for spoilage of onions.
Moreover the original and fainted solutions were augmented with
PXRD, Raman, FT-IR, SEM and TEM analysis confirming the changes
occurring in AgY-NPs solution.
4.1. Future directions
In cold storage chambers, where onions are stored in two differ-
ent temperature ranges (around 2 ◦ C for long term (till 12 month)
and at 25–32 ◦ C for 3–4 month storage, in both the conditions rela-
tive humidity (RH) has to be maintained between 75–80%), during
this period there are chances of initiation of the bacterial and fun-
gal infections. Hence in order to detect the spoilage process and
avoid the spreading of infection, the visual sensor can bring a mark-
able improvement. AgY-NPs based visual sensor can be implanted
near the purging gases coming out of the cold storage chamber and
therefore in future we will be studying its practical implications in
cold storage. This visual sensor can serve its utility to the farmers
because of its economic viability and its effectiveness.
Acknowledgements
DS is grateful to Vice Chancellor, Ajit Kumar, J.G. Varshney
NIFTEM-Kundli for their support, encouragement and permission
478 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479
to publish the results. DS thank Department of Science and Tech-
nology (DST) (Fast Track project SB/FT/CS-011/2013)—NewDelhi,
India for financial support. Authors sincerely thank NPL for charac-
terizing the samples.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2016.01.049.
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Biographies
Dr. Divya Sachdev received her Ph.D in chemistry from
BITS-Pilani and did her masters in organic chemistry from
Delhi University, India. She received young scientist award
and is currently working as a DST-Principal Investigator
at National Institute of Food Technology Entrepreneur-
ship and Management (NIFTEM)—Kundli. She has grabbed
immense experience in the field of nanoscience in last ten
years. Her research interest includes synthesis of magnetic
nanocomposites, bionanomaterials for sensing, heteroge-
neous catalysis and synthesis of novel nanomaterials for
food and agriculture.
Mr VinayKumar received his masters degree in agricul-
ture from Bidhan Chandra Krishi Vishwavidyalya, India.
He worked as a Research fellow at Central Research
Institute for Jute and Allied Fibres (CRIJAF), ICAR, India.
He is currently pursuing Ph.D at National Institute of
Food Technology Entrepreneurship and Management
(NIFTEM)—Kundli. His research interest mainly focuses on
Post harvest management of agricultural and horticultural
crops
 D. Sachdev et al. / Sensors and Actuators B 228 (2016) 471–479
Dr. Priyanka H. Maheshwari is working as a scientist at
CSIR—National Physical Laboratory, New Delhi. She com-
pleted her Ph. D. in 2008 on ‘Development and Studies
of Novel Carbon Materials for Energy Applications’ from
Delhi University. She is the recipient of the CSIR-Young
Scientist Award-2012 in Engineering Sciences. Her basic
research interests include development of Porous con-
ducting carbon paper, catalyst and bipolar plate for fuel
cell applications; development of carbon based anode for
rechargeable Li-ion batteries; and Synthesis/modification
of carbon nanotubes and development of multifunctional
CNT based nano composites.
Dr Renu Pasricha. A PhD in physics from the Pune Univer-
sity and M.tech from IIT Delhi, Dr Renu Pasricha heads the
Electron Microscopy division at National Centre for Biological
Sciences—TIFR, Bangalore. Author of nearly 125 interna-
tional publications in the field of nanoscience, she has the
specialization in the field of Electron Microscopic analysis.
Her current research interests includes Novel methods of
sample preparation for Biological samples, Cryo Electron
Microscopy, 3D tomography, Langmuir Blodgett Films,
Novel approach to nanoparticles system for biomedicine
and Correaltive microscopy.
479
Deepthi has completed her MSc with specialization in
Applied chemistry from Mangalore University. She has
worked as Teaching Assistant in Indian Institute of Sci-
ence, Chemistry department, Undergraduate Program,
Bangalore and is currently working at National Centre for
Biological Sciences as Technical Assistant in EM-Facility.
Her work mainly involves the TEM analysis of chemically
fixed Biological samples
Dr. Neeraj completed his Ph.D. from CCS Haryana
Agricultural University in Horticulture Science with spe-
cialization in postharvest management and worked as
DAAD Research Fellow in Institute fuer Gartenbauwis-
senschaft, Bonn University, Germany. He is working as
Assistant Professor in National Institute of Food Technol-
ogy Entrepreneurship and Management. He is currently
pursuing research in the area of postharvest manage-
ment of fruits and vegetables, supply chain management
of fresh horticultural produce.