1596 Indones. J. Chem.

, 2023, 23 (6), 1596 - 1608

The Comparative of α- and β-Cyclodextrin as Stabilizing Agents

on AuNPs and Application as Colorimetric Sensors for Fe3+ in Tap Water

Adhi Maulana Yusuf1,2, Satrio Kuntolaksono2, and Agustina Sus Andreani1*

1
Research Centre for Chemistry, National Research and Innovation Agency (BRIN),
Kawasan Puspiptek, Building 452, Serpong, Banten 15314, Indonesia
2
Department of Chemical Engineering, Institut Teknologi Indonesia,
Jl. Raya Puspiptek, Serpong, Banten 15314, Indonesia

* Corresponding author: Abstract: In this study, AuNPs were reduced using ortho-hydroxybenzoic acid (o-HBA)
and various stabilizing agents (α-CDs and β-CDs). The stability, shape, size, and
email: [email protected]
sensitivity of the Fe3+ detection of AuNPs α-CDs and AuNP β-CDs are compared. Both
Received: April 10, 2023 nanomaterials were characterized using ultraviolet-visible (UV-vis) spectroscopy, Fourier
Accepted: July 17, 2023 transform infrared (FTIR) spectroscopy, and transmission electron microscopes (TEM).
DOI: 10.22146/ijc.83796 After the addition of Fe3+, the absorption rate of surface plasma resonance (SPR)
increased to 524 nm, and the color of AuNPs α-CDs and AuNPs β-CDs was changed from
pink to red and purple, respectively. AuNPs α-CDs are more uniform in shape and size
than AuNPs β-CDs with a size of 23.34 nm. Further, AuNPs α-CDs are more stable, and
the absorption rate at 524 nm wavelength decreases by 17.76%. AuNPs α-CDs have a
good linear relationship with a linear regression coefficient of 0.996. The sensitivity of
AuNPs α-CDs was good with LoD and LoQ both with 1.21 and 4.02 ppm, respectively.
These results show that the sensor is superior in determining Fe3+. In addition, AuNPs α-
CDs were used to detect Fe3+ in the tap water in South Tangerang, Banten, Indonesia.

Keywords: AuNPs α-CDs; AuNPs β-CDs; colorimetric detection; Fe3+; tap water

■ INTRODUCTION be controlled at a significant level to avoid disease. This

condition has been driving researchers and academicians
Heavy metals have become the most dangerous
to focus on constructive methods for the qualitative and
chemical for water bodies, soil, and air due to the growth
quantitative detection of Fe3+ ions [8]. On the other
of contemporary industry [1]. Heavy metals are non-
hand, several methods have been developed for the
biodegradable and cannot be digested, therefore, they will
determination of Fe3+, including inductively coupled
be accumulated in living organisms after entering their
plasma mass spectroscopy (ICP-MS) [9], high-
food chain [2] which has become an issue due to their
performance liquid chromatography (HPLC) [10],
significant impact on environmental and health problems
atomic absorption spectroscopy (AAS) [11], fluorescence
[3]. An example of a toxic heavy metal is elemental iron
spectroscopic analysis [12], electrochemical methods
(Fe). Fe element is the most important element and is also
[13], and UV-visible spectrophotometer [14]. However,
important in the natural environment [4]. Ion Fe3+ plays
these methods require advanced equipment, technical
critical roles in many pathological and physiological
expertise, and need time for sample preparation steps.
processes, including cell metabolism, enzyme catalysis,
Therefore, it is thought that these techniques are not
nucleic acid synthesis, and electron transport [5]. Neither
economical and user-friendly. In order to overcome
excess accumulation nor lack of Fe3+ leads to several
these disadvantages, the colorimetric method has been
diseases, such as cancer, Parkinson’s syndrome,
developed for the detection of metal ions in aqueous
Alzheimer’s disease, and anemia [6-7]. Therefore, it must
solutions [15]. Nowadays, metallic nanoparticle sensors

Adhi Maulana Yusuf et al.

 Indones. J. Chem., 2023, 23 (6), 1596 - 1608 1597

have been widely used for colorimetric detection of Fe3+ collective effects of inclusion, size specificity, controlled
ions due to their strong surface plasmon resonance (SPR), release capability, and transport properties, making
stable dispersion, biocompatibility, and controllable them suitable as host molecules [22].
physical/chemical properties [16]. Due to this reason, Both α- and β-CDs can be used as the stabilizing
colorimetric sensors are the best way to detect Fe3+ ions. agent to synthesize AuNPs. For instance, the work of
In recent years, gold nanoparticles (AuNPs) have Gopalan [23] using β-CDs to stabilize metal
attracted a lot of attention as research materials recently nanoparticles (AuNPs and AgNPs), concluding gold and
and have been widely used in a wide range of applications, silver nanoparticles are relatively stable and make it
such as sensing, electronics, surface-enhanced Raman possible to control the size and distribution of the
spectroscopy, drug delivery, bioimaging, catalysis, nanoparticles using β-CDs as a stabilizer. Also, Liu et al.
colorimetric sensors, gene therapy, and so on [17]. The [24] report control of the size and distribution of AuNPs
AuNPs exhibit specific optical characteristics in the 380– were synthesized by the reduction of hydrogen
750 nm wavelength region (visible region). The SPR tetrachloroaurate(III) trihydrate by sodium citrate and
phenomenon is the result of surface plasmon different CDs (α-, β- and γ-) used as the stabilizer,
confinement near a nanoparticle in which the size of the concluding the main reason for why cyclodextrins
nanoparticle is smaller than the wavelength of incident stabilize gold colloids is considered to be hydrophobic-
light; this is known as the optical characteristics of the hydrophobic interactions between CDs and AuNPs. The
metallic nanoparticles. This phenomenon stems from the work of Lakkakula et al. [25] synthesized gold
coherent oscillation of the surface conduction electrons nanoclusters using β-CDs to stabilize for bioimaging
excited by electromagnetic radiation. This phenomenon and selective label-free intracellular sensing of Co2+ ions,
can be found in materials with a negative real and small concluding highly selective, rapid detection method
positive imaginary dielectric constant [18]. The using gold nanoclusters stabilized by CD and highly
mechanism of SPR sensors is based on the sensitivity of biocompatible with did not affect cell growth phases.
the frequency of the oscillating electron to the Furthermore, Co2+ can be detected fast (within 5 min)
environment of the plasmonic nanoparticles [19]. The with high sensitivity and selectivity.
dependency of frequency and intensity of the surface In this study, we described the fabrication of
plasmon resonance adsorption bands on the type, shape, AuNPs using ortho-hydroxybenzoic acid (o-HBA) with
size, and size distribution of the nanoparticles provide a α-CDs and β-CDs, namely AuNPs α-CDs and AuNPs β-
wide variety of sensing applications [20]. Additionally, CDs. The o-HBA contains hydroxyl phenolic and
AuNPs can be used to provide a method for detecting iron carboxylate functional groups that would be suitable to
concentration in tap water samples. act as reducing. Furthermore, we also compare the
Cyclodextrins (CDs) are cyclic oligosaccharides synthesis of AuNPs with a combination of α-CDs and β-
consisting of (α-1,4)-linked D-glucopyranose units. The CDs to act as stabilizers to obtain stability, sensitivity,
most common natural CDs and the only ones used in selectivity, LoD (limit of detection), and LoQ (limit of
pharmaceutical products are α-CDs and β-CDs consisting quantitation). In the last, AuNPs combination with α-
of 6 and 7 D-glucopyranose units. The α-CDs and β-CDs CDs was utilized to determine Fe3+ in tap waters.
are doughnut-shaped molecules with a hydrophilic outer
■ EXPERIMENTAL SECTION
surface and a slightly lipophilic central cavity. The outside
of the CDs toroid is hydrophilic due to the hydroxyl Materials
groups, giving the molecules with good water solubility, The materials used in this study were o-
whereas the inside is relatively hydrophobic because of hydroxybenzoic acid from Central Drug House, New
the glycosidic oxygen bridges [21]. CDs are non-toxic, Delhi, India. α-CDs, β-CDs, sodium hydroxide, HAuCl4,
biodegradable and biocompatible, along with the and ethylenediaminetetraacetic acid (EDTA) were

Adhi Maulana Yusuf et al.

1598 Indones. J. Chem., 2023, 23 (6), 1596 - 1608

purchased from Sigma-Aldrich. The standard solutions Other metal ion interference in the reaction of
like Fe3+, Ni2+, Cd2+, Pb2+, Cu2+, Sn2+, Co2+, and Mg2+ were AuNPs-CDs with Fe3+
obtained from Merck KGaA, Darmstadt, Germany. HCl The interference is evaluated by including
and HNO3 were purchased from Mallinckrodt. All these additional heavy metal ions in the AuNPs α-CDs + Fe3+
chemical agents were used as received. and AuNPs β-CDs + Fe3+. One mL of Fe3+ (10 ppm) and
1 mL of each of the additional (10 ppm) heavy metal
Instrumentation
ions: Mg2+, Ni2+, Cd2+, Pb2+, Cu2+, Sn2+, and Co2+ were
The instrumentations used in this study were added to the mixture with a 2:1:1 volume ratio, which
ultraviolet-visible (UV-vis) spectra using Agilent Cary 60 was then shaken to homogenization and subjected to
UV-vis spectroscopy between 200–800 nm range. The size UV-vis spectrometric analysis.
distribution and morphology of nanoparticles were
Analytical performance
analyzed by transmission electron microscope (TEM)
For the calibration plot, the absorbance values at
Tecnai G2 20S-Twin Function. Fourier transform
524 nm versus the concentration of Fe3+ were applied.
infrared spectroscopy (FTIR) spectra were measured
The LoD and LoQ were determined from three times the
using Shimadzu IR Prestige 21 in the 400–4000 cm−1
standard deviation of the blank signal and ten times the
range. The Fe3+ content of the tap water samples was
standard deviation of the blank signal, respectively [26].
determined using an Agilent 280FS AA.
The LoD and LoQ of the developed colorimetric sensor
Procedure were calculated using Eq. (1) and (2):
Sy
Synthesis of AuNPs-CDs LoD  3  (1)
a
The synthesis of AuNPs α-CDs and AuNPs β-CDs
Sy
was carried out by mixing 100 ppm HAuCl4, 0.01 M o- LoQ  10  (2)
a
HBA at pH 12, and a concentration of 0.02 M CDs (α or where Sy is the standard deviation, and a is the slope of
β) with the volume ratio of 1:1:1 in a water bath at 98 °C the calibration curve, were used to estimate the LoD and
for 20 min. LoQ with variation in concentration of Fe3+ (2, 6, 10, 14,
Stability of AuNPs-CDs 18 ppm). Three times of the detection Fe3+ standard
The stability of AuNPs α-CDs and AuNPs β-CDs solution analysis using AuNPs α-CDs and AuNPs β-
was carried out by storing the synthesized AuNPs for 3 CDs under ideal conditions were tested for repeatability
months in the refrigerator at 4 °C, then examining them and reproducibility. The spiking method was used to
with UV-vis spectrometry to compare with the SPR determine the accuracy parameters. In tap water, the
spectra results of the AuNPs-CDs when they were measurement of the Fe3+ standard solution's recovery
synthesized. value was analyzed.
Colorimetric response of AuNPs-CDs towards metals Reusability of AuNPs-CDs as Fe3+ colorimetric sensor
The synthesized AuNPs α-CDs and AuNPs β-CDs The reusability test was performed by introducing
were evaluated for their colorimetric response to Fe3+, 1 mL of Fe3+ 10 ppm and 1 mL of EDTA 25 ppm to 1 mL
Mg2+, Ni2+, Cd2+, Pb2+, Cu2+, Sn2+, and Co2+. One mL of of AuNPs α-CDs and adding 1 mL of EDTA 40 ppm to
10 ppm heavy metal solution at room temperature was AuNPs β-CDs with a 1:1 volume ratio. The resulting
combined with 1 mL of AuNPs α-CDs and β-CDs mixture was then homogenized by shaking and analyzed
synthesized under optimum conditions (100 ppm using UV-vis spectrometry.
HAuCl4, 0.01 M o-HBA at pH 12, and 0.02 M α or β CDs Application test to tap water
with a 1:1:1 volume ratio). The combination was then Three water samples collected from different tap
shaken to homogenization and analyzed using UV-vis water areas in South Tangerang, Banten, Indonesia, were
spectrometry. filtered with 0.45 μm filter paper and preserved with

Adhi Maulana Yusuf et al.

 Indones. J. Chem., 2023, 23 (6), 1596 - 1608 1599

HNO3 to pH < 2. Samples were analyzed by AAS to more stable than AuNPs β-CDs (Fig. 2).
compare the results. The application test was performed After testing using TEM, the average results of
by 1 mL samples added with 1 mL of AuNPs α-CDs nanoparticle size for AuNPs α-CDs and AuNPs β-CDs
analyzed by UV-vis spectrometry. were 23.34 and 40.74 nm, respectively. The shape of the
AuNPs α-CDs is spherical, and the shape of the AuNPs
■ RESULTS AND DISCUSSION
β-CDs is various (triangle, hexagon, and square). Thus,
Synthesis of AuNPs-CDs AuNPs α-CDs nanoparticles are more uniform in shape
o-HBA was chosen as the reducing agent of AuNPs than AuNPs β-CDs (Fig. 3).
due to its ability to convert Au3+ to Au0 with an Colorimetric Response of AuNPs-CDs toward
optimization peak which is found in o-HBA at pH 12 [27]. Metals
α- and β-CDs were selected as a stabilizer because CDs are
The comparison of AuNPs using different
hollow compounds that have steric hindrance, so they can
stabilizers of α-CDs and β-CDs with the presence of heavy
stabilize the nanoparticles. After the production of
AuNPs α-CDs and β-CDs, the maximum wavelength for 1.0
the SPR is detected at 524 nm which is included in the 0.9 AuNPs -CDs
AuNPs -CDs
specific optical SPR of AuNPs in the wavelength region of 0.8
350–750 nm (visible region) [18] with an absorbance of 0.7
0.49 for AuNPs α-CDs and 0.51 for AuNPs β-CDs with
Absorbance

0.6 -CDs -CDs

the color of the resulting solution is bright pink (Fig. 1). 0.5
The size of AuNPs α-CDs and β-CDs was relatively small
0.4
because the SPR peak was sharp [28]. The size of AuNPs
0.3
α-CDs and β-CDs was confirmed by the TEM.
0.2
The stability of AuNPs after 3 months of incubation
0.1
of AuNPs α-CDs and AuNPs β-CDs in the refrigerator at
0.0
4 °C did not change the color solution. There is a decrease 300 400 500 600 700 800
in absorbance at the same wavelength at 524 nm from Wavelength (nm)

0.49 to 0.40 (17.76%) for AuNPs α-CDs and from 0.51 to Fig 1. The UV-vis spectra of AuNPs α-CDs and AuNPs
0.39 (22.95%) for AuNPs β-CDs. Thus, AuNPs α-CDs are β-CDs with their color solution as inset

1.0 1.0
(a) (b) AuNPs -CDs after synthesis
AuNPs -CDs after synthesis
0.9 0.9 AuNPs -CDs after 3 months
AuNPs -CDs after 3 months

0.8 0.8

0.7 0.7
Absorbance

After After 3
0.6
Absorbance

0.6 synthesis months

0.5 After After 3 0.5

synthesis months

0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1
0.0 0.0
300 400 500 600 700 800 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)
Fig 2. SPR spectra of the stability of AuNPs after 3 months incubation (a) AuNPs α-CDs and (b) AuNPs β-CDs with
their color solution as inset

Adhi Maulana Yusuf et al.

1600 Indones. J. Chem., 2023, 23 (6), 1596 - 1608

Fig 3. TEM images of (a) AuNPs α-CDs and (b) AuNPs β-CDs

metal ions. Several heavy metal ions such as Fe3+, Mg2+, into AuNPs (less than 1 min, rapid detection).
Ni2+, Cd2+, Pb2+, Cu2+, Sn2+, and Co2+ with a concentration Moreover, the change in color is visible to the naked eye
of 10 ppm were added with AuNPs-CDs in a 1:1 ratio (Fig. 4). On the other hand, the selectivity of AuNPs α-
volume. The SPR of AuNPs α-CDs and AuNPs β-CDs CDs and AuNPs β-CDs with the addition of several
before being added with metal ions are 524 nm. The only heavy metal ions. Some heavy metal ions did not change
metal ions that changed the color and absorbance of the absorbance of AuNPs α-CDs and AuNPs β-CDs at
AuNPs-CDs at 524 nm were Fe3+ [29-30]. The color of 524 nm. However, only Fe3+ increases the absorbance of
AuNPs α-CDs and AuNPs β-CDs were changed from the AuNPs α-CDs and AuNPs β-CDs at 524 nm from
bright pink to red and purple, respectively. The response 0.18 to 0.37 and 0.23 to 0.39, respectively. This indicates
time of color change by the addition of Fe3+ is about 2 s that AuNPs α-CDs and AuNPs β-CDs are selective for
because there was a rapid color change when Fe3+ drops detecting ion Fe3+ (Fig. 5).

0.5 AuNPs α-CDs 0.5 (b)

(a) AuNPs β-C
Fe3+ Fe3+
Mg2+ Mg2+
0.4 Ni2+ 0.4 Ni2+
Cd2+ Cd2+
Pb2+ Pb2+
Cu2+
Absorbance

Cu2+
Absorbance

0.3 0.3
Sn2+ Sn2+
Co2+ Co2+

0.2 0.2

0.1 0.1

0.0 0.0
300 400 500 600 700 800 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)

Control Fe3+ Mg2+ Ni2+ Cd2+ Pb2+ Cu2+ Sn2+ Co2+ Control Fe3+ Mg2+ Ni2+ Cd2+ Pb2+ Cu2+ Sn2+ Co2+
Fig 4. The UV–vis spectra of AuNPs using different stabilizer agents, (a) α-CDs and (b) β-CDs in the presence of
various metal ions (10 ppm)

Adhi Maulana Yusuf et al.

 Indones. J. Chem., 2023, 23 (6), 1596 - 1608 1601

Fig 5. The selectivity of AuNPs in the presence of different stabilizers, (a) α-CDs and (b) β-CDs and metal ions
concentration of 10 ppm from the absorbance data at 524 nm

Other Metal Ions Interference in the Reaction of Analytical Performance

AuNPs-CDs with Fe3+
The dynamic linear range of the calibration curve
The other metal ions were added, and their effects is one crucial factor to consider when assessing the
on the selectivity of AuNPs α-CDs or AuNPs β-CDs effectiveness of AuNPs α-CDs and AuNPs β-CDs as
towards Fe3+ were investigated using a UV-vis colorimetric sensors of Fe3+. Changes in the absorbance
spectrophotometer three times. It was shown that the (ΔAbs) of AuNPs α-CDs and AuNPs β-CDs at 524 nm
absorbance of AuNPs α-CDs or AuNPs β-CDs with Fe3+ towards the changes in Fe3+ concentration were
was not significantly affected by the addition of the other monitored with UV-vis spectrometry. As the Fe3+
metal ions (Fig. 6). Thus, under the optimum conditions concentration increased, the color changed AuNPs α-
of Fe3+ sensing using AuNPs α-CDs or AuNPs β-CDs, the CDs and AuNPs β-CDs to red and purple, respectively,
addition of other metal ions does not cause interference and the absorbance at 524 nm increased. The Δ
which proves good selectivity of AuNPs α-CDs or AuNPs absorbance of AuNPs α-CDs and AuNPs β-CDs versus
β-CDs for colorimetric sensors of Fe3+. concentration of Fe3+ was plotted as a linear calibration

Fig 6. The interference of AuNPs in the presence of different stabilizers, (a) α-CDs and (b) β-CDs and metal ions
concentration of 10 ppm from the absorbance data at 524 nm

Adhi Maulana Yusuf et al.

1602 Indones. J. Chem., 2023, 23 (6), 1596 - 1608

plot in the range of 2–18 ppm. The rise in absorbance Table 1 shows the list time of analysis and the LoD
following the addition of Fe3+ is compared to the original for some colorimetric Fe3+ sensors developed based on
absorbance before the addition of Fe3+ to determine Δ SPR sensitivity as others [31-32]; it was more sensitive
absorbance. than other works [33-34]. The sensor developed here
The calibration curve at 524 nm as a function of Fe3+ had the advantage of a short analysis time (less than
concentration is given in (Fig. 7). When the relationship 1 min). It proved that this research developed a Fe3+
between the absorbance of AuNPs and the concentration colorimetric sensor that provided better sensitivity and
of Fe3+ is linear, this plot can be used to determine the level rapid detection.
of Fe in the sample. The value of R2 obtained was 0.996 for
Precision and Recovery
AuNPs α-CDs and 0.902 for AuNPs β-CDs with LoD
1.21 ppm, LoQ 4.02 ppm for AuNPs α-CDs and LoD The repeatability and reproducibility for
6.21 ppm, LoQ 20.72 ppm for AuNPs β-CDs, respectively. colorimetric of AuNPs α-CDs and AuNPs β-CDs are
In the same concentration range, AuNPs α-CDs are more given in Table 2. The repeatability of the sensor reflected
sensitive than AuNPs β-CDs evidenced by the LoD value the quality of sensor response and was investigated by
of AuNPs α-CDs smaller than AuNPs β-CDs. Based on measuring its absorbance at 524 nm in optimum
the same correlation coefficient (R2) value obtained, it can conditions for 3.0 determination (n = 3) on the same day
be categorized into a good linear regression equation resulting in an acceptable relative standard deviation
(R2 ≥ 0.99) for AuNPs α-CDs, so it is used for the (RSD) lower than that determined by AOAC (7.3%) and
detection of Fe3+ in tap water. Horwitz (11.3%) [35] confirms good repeatability. The

18 ppm
0.5 (c) 14 ppm
10 ppm
0.4 6 ppm
2 ppm
Absorbance

0.3

0.2

0.1

0.0
300 400 500 600 700 800
Wavelength (nm)
18 ppm
0.5 (d) 14 ppm
10 ppm
6 ppm
0.4
2 ppm
Absorbance

0.3

0.2

0.1

0.0
300 400 500 600 700 800
Wavelength (nm)

Fig 7. The linear relationship between the concentration of Fe3+ and Δ Absorbance of (a) AuNPs α-CDs and (b) AuNPs
β-CDs at 524 nm. UV-vis Spectra of (c) AuNPs α-CDs and (d) AuNPs β-CDs with various concentrations of Fe3+ from
2 to 18 ppm

Adhi Maulana Yusuf et al.

 Indones. J. Chem., 2023, 23 (6), 1596 - 1608 1603

Table 1. Comparison of AuNPs α-CDs based UV-vis spectrometric method with the reported methods for detection
of Fe3+
Capping Reagents Samples Time of analysis LoD Ref.
pyrophosphate Lake water samples 30 min 312 ng/mL [31]
oxamic acid, Water, urine, and 15 min 330 ng/mL [32]
p-aminobenzoic acid plasma samples
acidic thiourea mixture - 15 min 50 ppm [33]
ascorbic acid, some proteins - 2 min 8.1 ppm [34]
and flavonoids from Hibiscus
cannabinus
o-hydroxybenzoic acid and α- Tap water < 1 min 1.2 ppm This work
cyclodextrin

Table 2. Repeatability and reproducibility of (a) AuNPs range of 86.4 to 109.9% when compared with acceptable
α-CDs and (b) AuNPs β-CDs at 524 nm recovery percentages according to the concentration
(a) Repeatability Reproducibility level of analyte in 10 ppm (80–110%) [35]. The results
Concentration RSD (%) RSD (%) obtained are within that range so that the recovery
Fe³⁺ (ppm) AOAC Horwitz AOAC Horwitz results are acceptable and clearly confirm the
2 0.02 1.80 6.63 1.80 applicability of the developed colorimetric sensor for the
6 0.32 1.53 4.30 1.53 accurate determination of Fe3+ ions in tap water.
10 0.18 1.41 1.29 1.41
14 0.45 1.34 2.40 1.34 Reusability
18 0.06 1.29 3.32 1.29 The reusability of AuNPs α-CDs and β-CDs was
(b) Repeatability Reproducibility carried out by adding EDTA which is commonly used as
Concentration RSD (%) RSD (%)
a binding agent or ligand for several metal ions or
Fe³⁺ (ppm) AOAC Horwitz AOAC Horwitz
elements, especially Fe³⁺. The use of EDTA is expected
2 0.03 1.80 4.12 1.80
to bind Fe3+ ions so that AuNPs-CDs can be used again.
6 0.10 1.53 4.15 1.53
10 0.06 1.41 0.86 1.41 In order to recover the initial absorbance from AuNPs
14 0.02 1.34 1.46 1.34 α-CDs and β-CDs, the concentration EDTA for AuNPs
18 0.05 1.29 0.93 1.29 α-CDs and β-CDs is 25 and 40 ppm, respectively. Further,
the color change AuNPs α-CDs and AuNPs β-CDs after
reproducibility was examined at an absorbance of 524 nm the addition of Fe3+ is red and purple, respectively.
in optimal conditions on different days so that the
obtained RSD was lower than that determined by the Table 3. Recovery of AuNPs α-CDs for the analysis of
AOAC (7.3%) and Horwitz (11.3%) [35] confirming good Fe3+ in the samples
reproducibility. Detected Recovery
Samples Spiked (ppm)
AuNPs α-CDs are used in recovery because of their by AAS (ppm) (%)
average size, shape uniformity, stability and sensitivity 6.68 0.51 86.4
Sample I
better than AuNPs β-CDs. Recovery tests with real 8.05 0.51 92.4
samples were carried out using tap water taken at 3 5.75 ND 97.8
Sample II
6.30 ND 93.7
different places in South Tangerang, Banten, Indonesia.
9.66 0.59 109.9
Tap water samples were spiked with standard ion Fe3+ Sample III
10.52 0.59 105.1
solutions (10 ppm) and then analyzed. The results ND: Not Detected is the content of Fe3+ is below the limit of detection
summarized in (Table 3) demonstrated the recovery (LoD) of AAS

Adhi Maulana Yusuf et al.

1604 Indones. J. Chem., 2023, 23 (6), 1596 - 1608

The color change after the addition of EDTA in AuNPs α- values of 0.04; 0.52; and 0.04, respectively (the t-test
CDs + Fe3+ and AuNPs β-CDs + Fe3+ was from red and value is 4.30 at a 95% confidence level); it is possible that
purple to bright purple, respectively. The change in color the two methods did not reveal significantly different
and widening of the absorbance peaks indicate (Fig. 8) results. The outcomes of this application, therefore,
that the shape and size of the AuNPs α-CDs and β-CDs demonstrated the applicability of the AuNPs α-CDs
cannot return to their original shape and size. Thus, AuNPs sensor method to the samples.
α-CDs and β-CDs can be reused only twice (Fig. 9).
Characterization of AuNPs-CDs
Application Test to Tap Water
TEM analysis
The average size, shape uniformity, stability and AuNPs α-CDs are used for test applications to tap
sensitivity of AuNPs α-CDs are better than AuNPs β-CDs, water, so for characterization using TEM, only AuNPs
so AuNPs α-CDs are chosen for application test to tap
water. The analytical results of Fe3+ using the AuNPs α- Table 4. Results of Fe3+ detection in samples of tap water
CDs which were obtained by the proposed method, were Samples Developed method (ppm) AAS (ppm)
not significantly different from those obtained by AAS, as Sample I 0.55 0.51
shown in Table 4. That’s because the correlations between Sample II 0.52 ND
Sample III 0.55 0.59
the as-developed method and the AAS obtained t-test

(a) AuNPs -CDs (b) AuNPs -CDs

0.5 AuNPs -CDs + Fe3+ 10 ppm 0.5 AuNPs -CDs + Fe3+ 10 ppm
AuNPs -CDs + Fe3+ 10 ppm + EDTA 25 ppm AuNPs -CDs + Fe3+ 10 ppm + EDTA 40 ppm
0.45
0.45

0.4 0.4

0.4 0.35

0.3
0.4 0.35

0.3
Absorbance

0.25
Absorbance

0.25
0.2
0.2
Absorbance
Absorbance

0.15

0.3 0.3
0.1 0.15
0.05
0.1
0
AuNPs α-CDs AuNPs α-CDs + Fe AuNPs α-CDs + Fe + EDTA 0.05

0
AuNPs β-CDs AuNPs β-CDs + Fe AuNPs β-CDs + Fe + EDTA

0.2 0.2

0.1 0.1

A B C A B C
0.0 0.0
300 400 500 600 700 800 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)
Fig 8. Reversibility of Fe3+ in the presence of various EDTA by using different stabilize agents, (a) α-CDs and (b) β-
CDs. The color of AuNPs α-CDs and β-CDs (A) with change color after the addition of Fe3+ (B) and after the addition
of EDTA (C). Bar diagram exhibiting magnitude of absorbance for reversibility as inset

Fig 9. Reversible cycles of AuNPs α-CDs (a) and AuNPs β-CDs (b) addition with Fe3+ system with EDTA

Adhi Maulana Yusuf et al.

 Indones. J. Chem., 2023, 23 (6), 1596 - 1608 1605

stretching ortho for AuNPs α-CDs and AuNPs α-CDs +

Fe3+ (Fig. 11(a)) at 1732 cm−1, for AuNPs β-CDs at
1732 cm−1 and AuNPs β-CDs + Fe3+ at 1730 cm−1,
proved that o-HBA acts as a reducing agent and
cyclodextrin acts as a stabilizer [37]. Stretching vibration
of C=O carbonyl for AuNPs α-CDs and AuNPs β-CDs
emerge at 1642 and 1643 cm−1 due to the presence of an
electrostatic bond C=O with Au metal (Table 5). After
the addition of Fe3+ (AuNPs α-CDs + Fe3+ and AuNPs β-
CDs + Fe3+), the wavenumber at the C=O stretching
vibration carbonyl was shifted to 1647 and 1695 cm−1.
Fig 10. TEM images of the AuNPs α-CDs + Fe3+ The shift of wavenumber was caused by the C=O
carbonyl groups that were believed to bind with Fe3+
α-CDs + Fe3+ are used. The average results of nanoparticle [37]. Other than that, O–H bending carbonyl and C=C
size for AuNPs α-CDs + Fe3+ were 24.02 to 72.23 nm. The stretching aromatic of AuNPs α-CDs and AuNPs β-CDs
TEM images (Fig. 10) show that the presence of Fe3+ reduces appeared at 1602 and 1452 cm−1. After the addition of
the distance between the AuNPs α-CDs, but the AuNPs Fe3+ (AuNPs α-CDs + Fe3+), the wavenumber at the O–
α-CDs retain their original shape, and aggregation occurs. H bending carbonyl and C=C stretching aromatic were
FTIR analysis shifted to 1608 and 1455 cm−1, respectively. The shift of
The IR spectra of AuNPs α-CDs and AuNPs α-CDs wavenumber was caused by the O–H bending carbonyl
+ Fe3+ (Fig. 11(a)) and AuNPs β-CDs and AuNPs β-CDs and C=C stretching aromatic to form bridges between
+ Fe3+ (Fig. 11(b)) state an absorption peak which AuNPs, causing a decrease in the distance among
corresponded a C–H stretching + C–H (CH2) stretching AuNPs α-CDs and AuNPs β-CDs. Therefore, the
and C–H stretching at 2920 and 2860 cm−1 probably schematic between AuNPs α-CDs, AuNPs β-CDs, and
owned by cyclodextrin (α-CDs and β-CDs) [36]. Fe3+ based on FTIR results may be interpreted as shown
Absorption peak which corresponded to a ketone C=O in Scheme 1.

AuNPs-CDs AuNPs-CDs
AuNPs-CDs+Fe AuNPs-CDs+Fe

(a) (b)
1643
1642

1732 1732
Transmittance (a.u.)

1602
Transmittance (a.u.)

1602

1452
1452
2860
2860
1647
1608

1732
2920
2920

1695
1602

1730
1455

2860 1451
2860
2920
2920

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig 11. FTIR spectra of (a) AuNPs α-CDs and AuNPs α-CDs + Fe3+ and (b) AuNPs β-CDs and AuNPs β-CDs + Fe3+

Adhi Maulana Yusuf et al.

1606 Indones. J. Chem., 2023, 23 (6), 1596 - 1608

Table 5. Wavenumbers (cm−1) of AuNPs CDs and AuNPs CDs-Fe3+ complexes

AuNPs α-CDs AuNPs α-CDs + Fe³⁺ AuNPs β-CDs AuNPs β-CDs + Fe³⁺
2920 2920 2920 2920 C–H stretching + C–H (CH2) stretching
2860 2860 2860 2860 C–H stretching
1732 1732 1732 1730 Ketone C=O stretching ortho
1642 1647 1643 1695 C=O stretching vibration carbonyl
1602 1608 1602 1602 O–H bending carbonyl
1452 1455 1452 1451 C=C stretching aromatic

Scheme 1. Scheme illustration of AuNPs AuNPs α-CDs and AuNPs β-CDs

■ CONCLUSION Research and Innovation Agency (BRIN) through E-

Layanan Sains, Badan Riset dan Inovasi Nasional.
This study's results indicated that AuNPs α-CDs
were more stable than AuNPs β-CDs, with an absorbance ■ AUTHOR CONTRIBUTIONS
drop of 17.76% at a 524 nm wavelength. With the average
Adhi Maulana Yusuf: data curation, investigation,
size of 23.34 nm, AuNPs α-CDs have a more consistent
formal analysis, writing-original draft; Satrio
nanoparticle size and shape. The linear calibration curve
Kuntolaksono: investigation, methodology, validation,
at 524 nm's R2 value of 0.996 with a LoD of 1.21 ppm and
supervision, and writing-review; Agustina Sus
a LoQ of 4.02 ppm confirms the AuNPs α-CDs are more
Andreani: conceptualization, formal analysis, funding
sensitive than AuNPs β-CDs. From this comparison,
acquisition, investigation, methodology, supervision,
AuNPs α-CDs can be utilized to detect Fe3+ in tap water
validation, writing-review & editing.
because it exhibits good precision, accuracy, and recovery.
■ REFERENCES
■ ACKNOWLEDGMENTS
[1] Liang, W., Wang, G., Peng, C., Tan, J., Wan, J., Sun,
This research would like to acknowledge funding
P., Li, Q., Ji, X., Zhang, Q., Wu, Y., and Zhang, W.,
from the RIIM Gelombang 3 (2023) 12/II.7/HK/2023 and
2022, Recent advances of carbon-based nano zero
the facilities, scientific and technical supports from
valent iron for heavy metals remediation in soil and
Advanced Characterization Laboratories Serpong, National

Adhi Maulana Yusuf et al.

 Indones. J. Chem., 2023, 23 (6), 1596 - 1608 1607

water: A critical review, J. Hazard Mater., 426, [11] Soares, B.M., Santos, R.F., Bolzan, R.C., Muller, E.I.,
127993. Primel, E.G., and Duarte, F.A., 2016, Simultaneous
[2] Amirjani, A., Kamani, P., Hosseini, H.R.M., and determination of iron and nickel in fluoropolymers
Sadrnezhaad, S.K., 2022, SPR-based assay kit for by solid sampling high-resolution continuum
rapid determination of Pb2+, Anal. Chim. Acta, 1220, source graphite furnace atomic absorption
340030. spectrometry, Talanta, 160, 454–460.
[3] Li, H.Y., Zhao, S.N., Zang, S.Q., and Li, J., 2020, [12] Lv, X., Man, H., Dong, L., Huang, J., and Wang, X.,
Functional metal-organic frameworks as effective 2020, Preparation of highly crystalline nitrogen-
sensors of gases and volatile compounds, Chem. Soc. doped carbon dots and their application in
Rev., 49 (17), 6364–6401. sequential fluorescent detection of Fe3+ and ascorbic
[4] Zuo, Z., Song, X., Guo, D., Guo, Z., and Niu, Q., 2019, acid, Food Chem., 326, 126935.
A dual responsive colorimetric/fluorescent turn-on [13] Pang, L.Y., Wang, P., Gao, J.J., Wen, Y., and Liu, H.,
sensor for highly selective, sensitive and fast 2019, An active metal-organic anion framework
detection of Fe3+ ions and its applications, J. with highly exposed SO42− on {001} facets for the
Photochem. Photobiol., A, 382, 111876. enhanced electrochemical detection of trace Fe3+, J.
[5] Tammina, S.K., Yang, D., Li, X., Koppala, S., and Electroanal. Chem., 836, 85–93.
Yang, Y., 2019, High photoluminescent nitrogen and [14] Karami, C., Alizadeh, A., Taher, M.A., Hamidi, Z.,
zinc doped carbon dots for sensing Fe3+ ions and and Bahrami, B., 2016, UV-visible spectroscopy
temperature, Spectrochim. Acta, Part A, 222, 117141. detection of iron(III) ion on modified gold
[6] Amirjani, A., and Haghshenas, D.F., 2018, Ag nanoparticles with a hydroxamic acid, J. Appl.
nanostructures as the surface plasmon resonance Spectrosc., 83 (4), 687–693.
(SPR)˗based sensors: A mechanistic study with an [15] Uzunoğlu, D., Ergüt, M., Kodaman, C.G., and Özer,
emphasis on heavy metallic ions detection, Sens. A., 2020, Biosynthesized silver nanoparticles for
Actuators, B, 273, 1768–1779. colorimetric detection of Fe3+ ions, Arabian J. Sci.
[7] Wu, Y., Pang, H., Liu, Y., Wang, X., Yu, S., Fu, D., Eng., s13369-020-04760-8.
Chen, J., and Wang, X., 2019, Environmental [16] Chen, X., Zhao, Q., Zou, W., Qu, Q., and Wang, F.,
remediation of heavy metal ions by novel- 2017, A colorimetric Fe3+ sensor based on an
nanomaterials: A review, Environ. Pollut., 246, 608– anionic poly(3,4-propylenedioxythiophene)
620. derivative, Sens. Actuators, B, 244, 891–896.
[8] Liu, X., Li, N., Xu, M.M., Wang, J., Jiang, C., Song, G., [17] Kumar, A., Zhang, X., and Liang, X.J., 2013, Gold
and Wang, Y., 2018, Specific colorimetric detection nanoparticles: Emerging paradigm for targeted
of Fe3+ ions in aqueous solution by squaraine-based drug delivery system, Biotechnol. Adv., 31 (5), 593–
chemosensor, RSC Adv., 8 (61), 34860–34866. 606.
[9] Wang, R., Jiao, L., Zhou, X., Guo, Z., Bian, H., and [18] Amirjani, A., and Fatmehsari, D.H., 2018,
Dai, H., 2021, Highly fluorescent graphene quantum Colorimetric detection of ammonia using
dots from biorefinery waste for tri-channel sensitive smartphones based on localized surface plasmon
detection of Fe3+ ions, J. Hazard. Mater., 412, 105962. resonance of silver nanoparticles, Talanta, 176,
[10] Xiong, X., Zhang, J., Wang, Z., Liu, C., Xiao, W., Han, 242–246.
J., and Shi, Q., 2020, Simultaneous multiplexed [19] Amirjani, A., Salehi, K., and Sadrnezhaad, S.K.,
detection of protein and metal ions by a colorimetric 2022, Simple SPR-based colorimetric sensor to
microfluidic paper-based analytical device, Biochip differentiate Mg2+ and Ca2+ in aqueous solutions,
J., 14 (4), 429–437. Spectrochim. Acta, Part A, 268, 120692.

Adhi Maulana Yusuf et al.

1608 Indones. J. Chem., 2023, 23 (6), 1596 - 1608

[20] Amirjani, A., Bagheri, M., Heydari, M., and Hesaraki, doped graphene quantum dots decorated on
S., 2016, Label-free surface plasmon resonance plasmonic Au nanoparticles, ACS Appl. Mater.
detection of hydrogen peroxide; A bio-inspired Interfaces, 12 (4), 4755–4768.
approach, Sens. Actuators, B, 227, 373–382. [30] Mohaghegh, N., Endo-Kimura, M., Wang, K., Wei,
[21] Jansook, P., Ogawa, N., and Loftsson, T., 2018, Z., Hassani Najafabadi, A., Zehtabi, F.,
Cyclodextrins: Structure, physicochemical Hosseinzadeh Kouchehbaghi, N., Sharma, S.,
properties and pharmaceutical applications, Int. J. Markowska-Szczupak, A., and Kowalska, E., 2023,
Pharm., 535 (1-2), 272–284. Apatite-coated Ag/AgBr/TiO2 nanocomposites:
[22] Roy, N., Bomzan, P., and Nath Roy, M., 2020, Insights into the antimicrobial mechanism in the
Probing host-guest inclusion complexes of ambroxol dark and under visible-light irradiation, Appl. Surf.
hydrochloride with α- & β-cyclodextrins by Sci., 617, 156574.
physicochemical contrivance subsequently [31] Wu, S.P., Chen, Y.P., and Sung, Y.M., 2011,
optimized by molecular modeling simulations, Colorimetric detection of Fe3+ ions using
Chem. Phys. Lett., 748, 137372. pyrophosphate functionalized gold nanoparticles,
[23] Gopalan, P.R., 2010, Cyclodextrin-stabilized metal Analyst, 136 (9), 1887–1891.
nanoparticles: Synthesis and characterization, Int. J. [32] Buduru, P., and Reddy B.C., S.R., 2016, Oxamic acid
Nanosci., 9 (5), 487–494. and p-aminobenzoic acid functionalized gold
[24] Liu, Y., Male, K.B., Bouvrette, P., and Luong, J.H.T., nanoparticles as a probe for colorimetric detection
2003, Control of the size and distribution of gold of Fe3+ ion, Sens. Actuators, B, 237, 935–943.
nanoparticles by unmodified cyclodextrins, Chem. [33] Tripathy, S.K., Woo, J.Y., and Han, C.S., 2013,
Mater., 15 (22), 4172–4180. Colorimetric detection of Fe(III) ions using label-
[25] Lakkakula, J.R., Divakaran, D., Thakur, M., free gold nanoparticles and acidic thiourea mixture,
Kumawat, M.K., and Srivastava, R., 2018, Sens. Actuators, B, 181, 114–118.
Cyclodextrin-stabilized gold nanoclusters for [34] Bindhu, M.R., and Umadevi, M., 2014, Green
bioimaging and selective label-free intracellular synthesized gold nanoparticles as a probe for the
sensing of Co2+ ions, Sens. Actuators, B, 262, 270– detection of Fe3+ ions in water, J. Cluster Sci., 25 (4),
281. 969–978.
[26] Soomro, R.A., Nafady, A., Sirajuddin, S., Memon, N., [35] González, A.G., Herrador, M.Á., and Asuero, A.G.,
Sherazi, T.H., and Kalwar, N.H., 2014, L-cysteine 2010, Intra-laboratory assessment of method
protected copper nanoparticles as colorimetric accuracy (trueness and precision) by using
sensor for mercuric ions, Talanta, 130, 415–422. validation standards, Talanta, 82 (5), 1995–1998.
[27] Andreani, A.S., Kunarti, E.S., and Santosa, S.J., 2019, [36] Hasanah, N., Manurung, R.V., Jenie, S.N.A.,
Synthesis of gold nanoparticles capped-benzoic acid Indriyati, I., Prastya, M.E., and Andreani, A.S.,
derivative compounds (o-, m-, and p- 2023, The effect of size control of gold nanoparticles
hydroxybenzoic acid), Indones. J. Chem., 19 (2), 376– stabilized with α-cyclodextrin and β-cyclodextrin
385. and their antibacterial activities, Mater. Chem.
[28] Ndikau, M., Noah, N.M., Andala, D.M., and Masika, Phys., 302, 127762.
E., 2017, Green synthesis and characterization of [37] Andreani, A.S., Kunarti, E.S., Hashimoto, T.,
silver nanoparticles Using Citrullus lanatus fruit rind Hayashita, T., and Santosa, S.J., 2021, Fast and
extract, Int. J. Anal. Chem., 2017, 8108504. selective colorimetric detection of Fe3+ based on
[29] Das, R., Sugimoto, H., Fujii, M., and Giri, P.K., 2020, gold nanoparticles capped with ortho-
Quantitative understanding of charge-transfer- hydroxybenzoic acid, J. Environ. Chem. Eng., 9 (5),
mediated Fe3+ sensing and fast photoresponse by N- 105962.

Adhi Maulana Yusuf et al.