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Sensors and Actuators B: Chemical: Fatemeh Nemati, Rouholah Zare-Dorabei, Morteza Hosseini, Mohammad Reza Ganjali
Sensors and Actuators B: Chemical: Fatemeh Nemati, Rouholah Zare-Dorabei, Morteza Hosseini, Mohammad Reza Ganjali
Sensors and Actuators B: Chemical: Fatemeh Nemati, Rouholah Zare-Dorabei, Morteza Hosseini, Mohammad Reza Ganjali
Research paper
a r t i c l e i n f o a b s t r a c t
Article history: A low-cost, sensitive and convenient fluorescent probe of highly fluorescent Arginine – functionalized
Received 4 June 2017 graphene quantum dots (Arg-GQDs) was designed and synthesized by a facile one–pot hydrothermal
Received in revised form 27 August 2017 treatment of citric acid in the presence of Arginine. The fabricated Arg-GQDs with oxygen-rich functional
Accepted 2 September 2017
groups exhibit a strong blue emission with 28.3% quantum yield (QY). It is found that such Arg-GQDs
Available online 5 September 2017
with high QY can be used as efficient fluorescent probe for thiamine determination. In the detection,
photoluminescence (PL) intensity of the Arg-GQDs was reversibly quenched and recovered by Ag+ and
Keywords:
thiamine, respectively. The effect of different parameters were optimized by central composite design
Graphene quantum dots
Fluorescence probe (CCD) combined with response surface methodology (RSM). Furthermore, results of CCD were evaluated
Central composite design by standard analysis of variance (ANOVA) to assess the accuracy and suitability of the quadratic model.
Thiamine (Vitamin B1) Under optimal conditions, the fluorescence “Off-On” process showed a sensitive response to thiamine
Determination in the concentration range of 0.1–8.0 M with a detection limit of 53 nM. Finally, the Arg-GQDs based
fluorescence method was applied to the analysis of thiamine in pharmaceuticals and foodstuff samples
with satisfying recoveries for the spiked samples.
© 2017 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2017.09.009
0925-4005/© 2017 Elsevier B.V. All rights reserved.
F. Nemati et al. / Sensors and Actuators B 255 (2018) 2078–2085 2079
the intrinsic defects of those QDs limit their widespread applica- carried out by a Perkin-Elmer LS50 luminescence spectrometer.
tion, such as complex synthesis procedures, heavy metals potential Fourier transform infrared (FT-IR) spectrum was recorded on a
toxicity and environmental hazards [24]. Graphene quantum dots Shimadzu-8400S spectrometer in the range of 400–4000 cm−1 at
(GQDs) are generally defined as zero-dimensional carbon-based room temperature using KBr pellets. Energy-dispersive X-ray (EDX)
material that are typically single or few-layer graphenes with lat- spectra were obtained using the Philips XL30 scanning electron
eral dimensions of less than 100 nm [25,26]. Owing to the novel microscope (SEM). The morphologies of Arg-GQDs samples were
properties, such as remarkable conductivity, high edge-to-area characterized by transmission electron microscopy (TEM, Philips,
ratio, stable luminescence, good biocompatibility, and low toxicity, CM30, 300 Kv). The pH was adjusted and measured using pH meter
graphene quantum dots have recently emerged as promising alter- Metrohm. The X-ray diffraction patterns (XRD) were recorded on
natives to traditional quantum dots in some aspects [27]. However, a Philips diffractometer (model X’Pert MPD). Raman spectrum was
the photoluminescence quantum yield of the pristine GQDs is usu- recorded using an Almega Thermo Nicolet Dispersive Raman Spec-
ally low and much lower than semiconductor quantum dots [28]. trometer with a 532 nm laser.
Recently demonstrated that high quantum yields of GQDs quantum
yield can be observed after either functionalization or doping [29]. 2.3. Synthesis of functionalized graphene quantum dots
Among foreign atoms, Nitrogen has been widely used for chem-
ical doping in carbon-based nanomaterials by virtue of it having In a typical synthesis, 0.21 g of citric acid and 0.10 g of Arginine
match able atomic size and five valence electrons for bonding with were mixed with 5 mL water, and stirred to form a clear solu-
carbon atoms [30,31]. The optimization in analytical chemistry is tion. The solution was then transferred into a 20 mL Teflon-lined
generally carried out with a traditional single variable approach stainless autoclave. The sealed autoclave was heated constantly
(SVA) [32]. Its major disadvantage is that it ignores the combination at 160 ◦ C for 4 h. The obtained mixture was filtered with a mem-
influence among the parameters studied. Due to above disadvan- brane (0.22 m) to remove the large dots. Finally, the as prepared
tage, multivariate statistic methods have been applied to optimize Arg-GQDs were stored at 4 ◦ C for further experiments.
experimental parameters. Among the most relevant multivari-
ate techniques, response surface methodology (RSM) has shown
considerable application in analytical optimization [33]. Response 2.4. General procedure
surface methodology, a collection of mathematical and statistical
techniques, is a very useful tool for determining the effect of opera- For thiamine detection, 25 L of 40 mg mL−1 Arg-GQDs, 1 mL pH
tional variables for process development and optimization [34,35]. 6 phosphate buffer and 40 L (0.01 M) of Ag+ solution were added
The most frequent and efficient methods used in response surface in a quartz cuvette and the mixture was stirred thoroughly. Then,
methodology is central composite design (CCD) [36]. The aim of the mixture was finally diluted to 2 mL with ultrapure water. Next,
this work was to develop a simple, fast and non-toxic method, of different amounts of thiamine added to the above mixed solution.
maximum possible sensitivity, to detection of thiamine in phar- Finally, the fluorescence intensity of the mixture was recorded at
maceuticals and foodstuff samples. For this, we have synthesized excitation wavelength of 350 nm, and the band-slits of both exci-
water-soluble Arg-GQDs by using citric acid and Arginine (Arg) as tation and emission were set as 10.0 and 15.0 nm, respectively.
carbon and nitrogen sources respectively. Based on the excellent
photoluminescent of the Arg–GQDs, a simple, potent, fast, non- 2.5. Quantum yield measurements
toxic fluorescent probe was designed. In this paper, the influence
of time, temperature and pH on fluorescence sensing was investi- The quantum yield of the as-synthesized GQDs were determined
gated using response surface methodology (RSM) based on central by using quinine sulfate as the fluorescence standard and was cal-
composite design (CCD). The range of linearity, the stability, the culated according to the following Eq. (1):
response to interferents and the detection limit (LOD) of the sensor
have been evaluated. The optical sensor based on the Arg-GQDs has Iu Ast n2u
Yu = Yst (1)
been successfully applied in sensitive detection of thiamine in real Ist Au n2st
spiked samples.
Where Y is the quantum yield, I is the measured integrated emission
intensity, n is the refractive index, and A is the extinction. The sub-
2. Experimental section script “st” refers to the standard and “u” for sample with unknown
QY.
2.1. Chemicals and materials
2.6. Analysis of thiamine in real samples
Citric acid (+99%), Arginine were purchased from Sigma–Aldrich
Co. Thiamine hydrochloride (98%) was purchased from Alfa Fluorescent detection of thiamine in food samples was per-
Aesar. All the other chemicals used were of analytical reagents formed through the following steps: 1.0 g of samples that was
grade. Stock standard solution of thiamine hydrochloride purchased from a local supermarket was grounded and mixed with
(1.0 × 10−3 mol L−1 ) was prepared in water and stable for at 0.1 mol L−1 HCl solution. After integrating for 15 min, the mixture
least 1 month when kept refrigerated. Working solutions of lower was centrifuged for 15 min at 5000 rpm, and the supernatant was
concentrations were prepared daily from the above stock solution filtered through a 0.45 mm cellulose acetate filter and diluted up to
as required. All chemicals used were of analytical grade or of the 10 mL with ultra-pure water. The pharmaceutical sample (vitamin
highest purity available. All solutions were prepared with doubly B1 tablet from Jalinous Pharmaceutical Co., Iran) was obtained from
deionized water (DDW). the local drug store. For analysis, a piece of vitamin B1 tablet was
powdered in a mortar and dissolved in ultrapure water. The mixture
2.2. Apparatus was sonicated for 10 min for fully dissolution. The insoluble com-
ponents were removed by filtration. After that, the solution was
UV–vis measurements were carried out on a PG Instruments transferred into 25 mL volumetric flask and stored in dark at 4 ◦ C.
T80+ UV/Vis spectrophotometer and the spectra were collected Standard addition method was used for determination of thiamine
from 200 nm to 700 nm. All fluorescence measurements were in the real samples.
2080 F. Nemati et al. / Sensors and Actuators B 255 (2018) 2078–2085
Fig. 1. (a) TEM image of the Arg-GQDs (inset: size distribution of Arg-GQDs) (b) EDX spectrum of the Arg-GQDs (c) Raman spectra of as-prepared Arg-GQDs (d) XRD patterns
of the Arg-GQDs.
Table 1 Table 2
Experimental factors and levels in CCD. The design matrix for four variables with enhancement ratio (F- F0 )/F0 as response
(R).
Levels
Runs Block x1 x2 x3 (F − F0 )/F0
Independent variable -␣ -1(low) 0 (center) +1(High) +␣
1 1 6 15 35 2.73
(x1) pH 4 5 6 7 8 2 1 7 10 30 2.68
(x2 ) time(min) 5 10 15 20 25 3 1 5 10 30 2.54
◦
(x3) temperature ( C) 25 30 35 40 45 4 1 5 20 40 2.26
5 1 5 20 30 2.10
6 1 7 20 30 2.48
7 1 7 20 40 2.43
2.7. Optimization of factors affecting the fluorescence sensing of 8 1 7 10 40 2.28
thiamine using RSM approach 9 1 5 10 40 2.09
10 1 6 15 35 2.60
11 2 6 15 35 2.55
Central composite design was applied to investigate the effects 12 2 6 15 35 2.49
of the three operational factors on the response function. The 13 2 8 15 35 2.02
studied parameters were selected based on the preliminary experi- 14 2 6 15 45 2.39
ments and prior knowledge from literature. The high and low levels 15 2 6 15 35 2.53
16 2 4 15 35 1.37
defined for three independent variables are shown in Table 1. After
17 2 6 15 35 2.70
running the 20 trials, a second order polynomial model for predict- 18 2 6 25 35 2.51
ing the optimal point was explained by the following Eq. (2): 19 2 6 5 35 2.37
20 2 6 15 25 2.75
k
k
k
k
Y = ˇ0 + ˇi xi + ˇij xi xj + ˇii xi2 (2)
i=1 i=1 j=i+1 i=1
Fig. 4. A plot of the internally studentized residuals vs. the predicted response.
Table 4
Comparison of the present approach with other reported methods for the detection of thiamine.
Acknowledgements
References
[11] T. Pérez-Ruiz, C. Martıı́nez-Lozano, V. Tomás, J. Martıı́n, Flow-injection [35] M.S. Tehrani, R. Zare-Dorabei, Competitive removal of hazardous dyes from
spectrofluorimetric determination of dissolved inorganic and organic aqueous solution by MIL-68 (Al): Derivative spectrophotometric method and
phosphorus in waters using on-line photo-oxidation, Anal. Chim. Acta 442 response surface methodology approach, Spectrochim. Acta Part A Mol.
(2001) 147–153. Biomol. Spectrosc. 160 (2016) 8–18.
[12] A.B. Tabrizi, A cloud point extraction-spectrofluorimetric method for [36] A. Keramat, R. Zare-Dorabei, Ultrasound-assisted dispersive magnetic solid
determination of thiamine in urine, Bull. Korean Chem. Soc. 27 (2006) phase extraction for preconcentration and determination of trace amount of
1604–1608. Hg (II) ions from food samples and aqueous solution by magnetic graphene
[13] T. Pérez-Ruiz, C. Martínez-Lozano, M.D. García-Martínez, Simultaneous oxide: central composite design optimization, Ultrason. Sonochem. 38 (2017)
determination of thiamine and its phosphate esters by a liquid 421–429.
chromatographic method based on post-column photolysis and [37] T.-T. Xu, J.-X. Yang, J.-M. Song, J.-S. Chen, H.-L. Niu, C.-J. Mao, S.-Y. Zhang, Y.-H.
chemiluminescence detection, J. Pharm. Biomed. Anal. 50 (2009) 315–319. Shen, Synthesis of high fluorescence graphene quantum dots and their
[14] R.E. Echols, J. Harris, R.H. Miller, Modified procedure for determining vitamin selective detection for Fe3+ in aqueous solution, Sens. Actuators B 243 (2017)
B1 by gas chromatography, J. Chromatogr. A 193 (1980) 470–475. 863–872.
[15] R.E. Echols, R.H. Miller, W. Winzer, D.J. Carmen, Y.R. Ireland, Gas [38] C. Zhang, Y. Cui, L. Song, X. Liu, Z. Hu, Microwave assisted one-pot synthesis of
chromatographic determination of thiamine in meats, vegetables and cereals graphene quantum dots as highly sensitive fluorescent probes for detection of
with a nitrogen-phosphorus detector, J. Chromatogr. A 262 (1983) 257–263. iron ions and pH value, Talanta 150 (2016) 54–60.
[16] Y. Mrestani, R.H.H. Neubert, Thiamine analysis in biological media by capillary [39] B. Shi, L. Zhang, C. Lan, J. Zhao, Y. Su, S. Zhao, One-pot green synthesis of
zone electrophoresis with a high-sensitivity cell, J. Chromatogr. A 871 (2000) oxygen-rich nitrogen-doped graphene quantum dots and their potential
351–356. application in pH-sensitive photoluminescence and detection of mercury(II)
[17] S. Poongothai, R. Ilavarasan, C.M. Karrunakaran, Simultaneous and accurate ions, Talanta 142 (2015) 131–139.
determination of vitamins B1, B6 B12 and alpha-lipoic acid in multivitamin [40] J. Ju, R. Zhang, S. He, W. Chen, Nitrogen-doped graphene quantum dots-based
capsule by reverse-phase high performance liquid chromatographic method, fluorescent probe for the sensitive turn-on detection of glutathione and its
Int. J. Pharm. Pharm. Sci. 2 (2010) 133–139. cellular imaging, RSC Adv. 4 (2014) 52583–52589.
[18] X. Tang, D.A. Cronin, N.P. Brunton, A simplified approach to the determination [41] J. Ju, W. Chen, Synthesis of highly fluorescent nitrogen-doped graphene
of thiamine and riboflavin in meats using reverse phase HPLC, J. Food Compos. quantum dots for sensitive, label-free detection of Fe (III) in aqueous media,
Anal. 19 (2006) 831–837. Biosens. Bioelectron. 58 (2014) 219–225.
[19] D. Bohrer, P.C. do Nascimento, A.G. Ramirez, J.K.A. Mendonça, L.M. de [42] H. Wang, Y. Liu, S. Wei, Z. Yan, Application of response surface methodology
Carvalho, S.C.G. Pomblum, Determination of thiamine in blood serum and to optimise supercritical carbon dioxide extraction of essential oil from
urine by high-performance liquid chromatography with direct injection and Cyperus rotundus Linn, Food Chem. 132 (2012) 582–587.
post-column derivatization, Microchem. J. 78 (2004) 71–76. [43] K. Dashtian, R. Zare-Dorabei, Synthesis and characterization of functionalized
[20] Z. Zhou, C. Tan, Y. Zheng, Q. Wang, Electrochemical signal response for mesoprous SBA-15 decorated with Fe3O4 nanoparticles for removal of Ce(III)
vitamin B1 using terbium luminescent nanoscale building blocks as optical ions from aqueous solution: ICP?OES detection and central composite design
sensors, Sens. Actuators B 188 (2013) 1176–1182. optimization, J. Colloid Interface Sci. 494 (2017) 114–123.
[21] Y. Ding, S. Wang, J. Li, L. Chen, Nanomaterial-based optical sensors for [44] Kh. Dashtian, R. Zare-Dorabei, An easily organic-inorganic hybrid optical
mercury ions, TrAC Trends Anal. Chem. 82 (2016) 175–190. sensor based on dithizone impregnation on mesoporous SBA-15 for
[22] X. Fu, T. Lou, Z. Chen, M. Lin, W. Feng, L. Chen, Turn-on fluorescence detection simultaneous detection and removal of Pb(II) ions from water samples:
of lead ions based on accelerated leaching of gold nanoparticles on the surface response-surface methodology, Appl. Organomet. Chem. (2017), http://dx.
of graphene, ACS Appl. Mater. Interfaces 4 (2012) 1080–1086. doi.org/10.1002/aoc.3842.
[23] D. Lin, T. Qin, Y. Wang, X. Sun, L. Chen, Graphene oxide wrapped SERS tags: [45] G. Daneshvar Tarigh, F. Shemirani, Simultaneous in situ derivatization and
multifunctional platforms toward optical labeling, photothermal ablation of ultrasound-assisted dispersive magnetic solid phase extraction for thiamine
bacteria, and the monitoring of killing effect, ACS Appl. Mater. Interfaces 6 determination by spectrofluorimetry, Talanta 123 (2014) 71–77.
(2014) 1320–1329. [46] M. Amjadi, R. Shokri, T. Hallaj, A new turn-off fluorescence probe based on
[24] F.-e. Lin, C. Gui, W. Wen, T. Bao, X. Zhang, S. Wang, Dopamine assay based on graphene quantum dots for detection of Au(III) ion, Spectrochim. Acta Part A
an aggregation-induced reversed inner filter effect of gold nanoparticles on 153 (2016) 619–624.
the fluorescence of graphene quantum dots, Talanta 158 (2016) 292–298. [47] C. Li, Y. Yue, Fluorescence spectroscopy of graphene quantum dots:
[25] X.E. Zhao, C.H. Lei, Y.H. Wang, F. Qu, S.Y. Zhu, H. Wang, J.M. You, A temperature effect at different excitation wavelengths, Nanotechnology 25
fluorometric assay for tyrosinase activity and its inhibitor screening based on (2014) 435703.
graphene quantum dots, RSC Adv. 6 (2016) 72670–72675. [48] K. Hemelsoet, D. Lesthaeghe, V. Van Speybroeck, M. Waroquier, Bifunctional
[26] N. Yu, H. Peng, H. Xiong, X. Wu, X. Wang, Y. Li, L. Chen, Graphene quantum acid-base catalyzed reactions in zeolites from the HSAB viewpoint, Chem.
dots combined with copper(II) ions as a fluorescent probe for turn-on Phys. Lett. 419 (2006) 10–15.
detection of sulfide ions, Microchim. Acta 182 (2015) 2139–2146. [49] R. Tabaraki, A. Nateghi, Nitrogen- doped graphene quantum dots: turn-off
[27] M. Arvand, S. Hemmati, Magnetic nanoparticles embedded with graphene fluorescent probe for detection of Ag+ ions, J. Fluoresc. 26 (2016) 297–305.
quantum dots and multiwalled carbon nanotubes as a sensing platform for [50] H. Li, D. Chen, H. Wang, J. Li, W. Wang, Sub-picomole level
electrochemical detection of progesterone, Sens. Actuators B 238 (2017) photoelectrochemical sensing of l-cysteine based on plasmonic silver
346–356. nanoparticles modified hierarchically structured zinc oxide, J. Electroanal.
[28] T. Yang, F. Cai, X. Zhang, Y. Huang, Nitrogen and sulfur codoped graphene Chem. 759 (Part 1) (2015) 21–26.
quantum dots as a new fluorescent probe for Au3+ ions in aqueous media,
RSC Adv. 5 (2015) 107340–107347.
[29] S. Kundu, R.M. Yadav, T.N. Narayanan, M.V. Shelke, R. Vajtai, P.M. Ajayan, V.K. Biographies
Pillai, Synthesis of N, F and S co-doped graphene quantum dots, Nanoscale 7
(2015) 11515–11519.
[30] X. Du, D. Jiang, Q. Liu, G. Zhu, H. Mao, K. Wang, Fabrication of graphene oxide Fatemeh Nemati is a Ph.D. student in Analytical Chemistry at Iran University of
decorated with nitrogen-doped graphene quantum dots and its enhanced Science and Technology, Tehran, Iran.
electrochemiluminescence for ultrasensitive detection of pentachlorophenol,
Rouholah Zare-Dorabei has a PhD in Analytical Chemistry obtained at University
Analyst 140 (2015) 1253–1259.
of Tehran in 2010. He is currently Assistant Professor in Analytical Chemistry Iran
[31] S. Benítez-Martínez, M. Valcárcel, Graphene quantum dots in analytical
University of Science and Technology, Tehran, Iran. His research work has been
science, TrAC Trends Anal. Chem. 72 (2015) 93–113.
mainly focused on the design of new optical sensors.
[32] H. Ebrahimzadeh, N. Tavassoli, O. Sadeghi, M.M. Amini, Optimization of
solid-phase extraction using artificial neural networks and response surface Morteza Hosseini has a Ph.D. in analytical chemistry obtained at Tarbiat Modares
methodology in combination with experimental design for determination of University in 2005. He is currently an associated professor in nanobiotechnology
gold by atomic absorption spectrometry in industrial wastewater samples, group of Faculty of New Sciences and Technologies of University of Tehran. His
Talanta 97 (2012) 211–217. research work has been mainly focused on the design of new optical nanosensors
[33] M.A. Bezerra, R.E. Santelli, E.P. Oliveira, L.S. Villar, L.A. Escaleira, Response and nanobiosensors.
surface methodology (RSM) as a tool for optimization in analytical chemistry,
Talanta 76 (2008) 965–977. Mohammad Reza Ganjali has a Ph.D. in analytical chemistry obtained at University
[34] R. Zare-Dorabei, S.M. Ferdowsi, A. Barzin, A. Tadjarodi, Highly efficient of Tehran in 1997. He is currently a professor of analytical chemistry at University of
simultaneous ultrasonic-assisted adsorption of Pb (II), Cd (II), Ni (II) and Cu Tehran. His research work has been mainly focused on the design of new chemical
(II) ions from aqueous solutions by graphene oxide modified with 2, sensors.
2 -dipyridylamine: central composite design optimization, Ultrason.
Sonochem. 32 (2016) 265–276.