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ORIGINAL PAPER
Received: 2 June 2016 / Accepted: 12 October 2016 / Published online: 20 October 2016
# Springer-Verlag Wien 2016
oxidation peak current. This allowed specific detection of FTIR, and UV/Vis spectra of the white powder SrO
L-Cys even in the presence of 500-fold excess of NR had been performed on a Thermo scientific
interferents [16]. Electrochemical sensor based on the NICOLET iS50 FTIR spectrometer (Madison, WI,
Y 2 O 3 -nanoparticles supported on nitrogen-doped re- USA), and 300 UV/Visible spectrophotometer (Thermo
duced graphene oxide onto carbon paste electrode was scientific; (www.thermoscientific.com)) respectively. The
developed for selective L-cysteine, which displayed a XPS experiment was conducted for the determination of
strongly oxidation peak for L-cysteine at pH 7.0. binding energies (eV) between Sr, and O on a K-α1
Further, the sensor exhibited superior electrochemical spectrometer (Thermo scientific, K-α1 1066; www.
performance for electrocatalytic oxidation and detected thermoscientific.com) with an excitation radiation
the target L-cysteine analyte at room conditions [17]. source (A1Kα1, Beam spot size =300.0 μm, pass
Branched chained amino acids such as L-Leucine, iso- e n e r g y = 2 0 0 . 0 e V, p r e s s u r e ~ 1 0 − 8 t o r r ) . T h e
leucine, and valine play a significant regulatory function electrochemical characterizations such as arrangement,
in protein metabolism. L-Leu used as medicine, nutri- elemental analysis, morphology, and particle size of
tion, important dietary nutrient for the standard growth the SrO NR were investigated using FESEM (JEOL,
of fish, and can be produced by fermentation [18]. L- JSM-7600F, Japan; www.jeol.co.jp) equipped XEDS. In
Leu is an essential synthetic building block for novel order to measure the crystalline pattern of SrO NR,
chiral auxiliaries, ligands, and pharmaceutical active in- XRD examination was also carried out under ambient
gredients [19]. L-Leu is the most efficient amino acid conditions. I-V method was performed at a selective
regarding metabolic fuel in skeletal muscle, stimulating point using the fabricated SrO NR by Keithley elec-
amino acid in protein synthesis and inhibition of degra- trometer (6517A, USA; www.tek.com/keithley) to
dation in mammals. It has a vital function in blood detect L-Leu.
glucose homeostasis, body adipose tissue homeostasis,
haemoglobulin production, insulin secretion stimulation,
and nitrogen balance [20]. Biochemical malfunction and Synthesis of SrO nanorods
growth retardation can be happened upon dietary defi-
ciency of L-Leu [21]. Bladder carcinogenesis can also Strontium chloride [SrCl2.6H2O] and sodium hydroxide
be occurred in rats from dietary supplement of L-Leu (NaOH) were used as reacting agents in the preparation
[22]. Loss of skeletal muscle may be attenuated in mice of SrO NR using a simple wet-chemical process [25].
by branched chain amino acid (L-Leu, leucine metabo- The wet-chemical process is a classical solid-state sys-
lite and β-hydroxy-β-methylbutyrate) [23]. Various elec- tem, widely used in the preparation of doped or un-
trochemical techniques have been developed for the de- doped nanomaterials, and the yield will attain smaller
termination and measurement of L-Leu in biological or- grains as well as shorter duration of phase formation.
igins [24] as shown in Table 1. Among these tech- On the basis of this technique, strontium chloride
niques, the electrochemical biosensor is cheap, reliable, (SrCl2.6H2O, 0.1 M, 2.67 g) was dissolved in distilled
sensitive, stable and easy to operate. The aim of this water (100.0 mL) at a conical flask (250.0 mL) under
study was to develop a biosensor based on SrO NR to continuous stirring; pH of the resultant solution was
detect L-Leu using current–voltage (I-V) method. To adjusted to 10.13 by adding up NaOH, and then placed
best of our knowledge this is the first time report of at 90.0 °C for uninterrupted stirring. After 6 h constant
L-Leu detection using I-V technique based on SrO stirring, the stirred solution was washed thoroughly with
nanostructures deposited on GCE. water and acetone consequently, and then kept for dry-
ing (12 h) in open air at room temperature. The resul-
tant white powder (SrO NR) were dried (28 h) in the
Experimental section oven at 60.0 °C, grinding into powder, again dried
(22 h) at 60.0 °C in the oven in order to use for elec-
Materials and methods trochemical examinations including application. The fea-
sible mechanisms of reactions for the development of
The chemical reagents of the analytical grade such as SrO NR are as follows [reaction (i) - (iv)].
ethanol, nafion (5 % ethanolic solution), sodium hy-
droxide, L-Aspertic acid, Creatine, Glycine, L-Cystine, NaOH(s) → Na+(aq) + OH−(aq) (i)
L-Glutamic acid, L-Glutathione, L-Tyrocine, L-Leucine, SrCl2 → Sr2 +(aq) + 2Cl−(aq) (ii)
Thionine acetate, and Uric acid were used without fur- Na+(aq) + 2OH−(aq) + Sr2 +(aq) + Cl−(aq) → Sr(OH)2 (aq) ↓ + NaCl(aq) (iii)
ther purification that had been purchased from the 2Sr(OH)2 (aq) → 2SrO(s) ↓ + 2H2O(aq) (iv)
Sigma-Aldrich company (www.sigmaaldrich.com).
Microchim Acta (2016) 183:3265–3273 3267
According to the reaction (iii), unstable strontium hy- porosity, and permeability, which directly dependent on the
droxide had been formed at a particular pH during structural morphology prepared by reactant precursors
SrCl 2 .6H 2 O hydrolyzed by reducing agent, NaOH. (Strontium chloride) for making SrO NR in basic medium at
Where, NaOH operated a buffer to control the pH of low-temperature. The SrO NRs were synthesized by a wet-
the solution and contributed of OH− ions in slowly dur- chemical method using NaOH reducing agents at ambient
ing the entire synthetic route. The precipitation of conditions. This technique has several advantages including
Sr(OH)2 nuclei began to start when the concentrations facile preparation, accurate control of the reactant tempera-
of the Sr2+ and OH− ions had been reached above the ture, easy to handle, one-step reaction, and high-porosity as
critical value. As there, high concentration of Sr2+ ions well as porous natures. Optical, morphological, electrical, and
in the reaction system beside OH− ions, the nucleation chemical properties of SrO nanorod materials are of huge
of SrO crystals become easier due to the lower activa- significance from the scientific aspect, compared to other
tion energy barrier of heterogeneous nucleation. undoped materials. Non-stoichiometry, mostly oxygen vacan-
Based on the principle of Ostwald-ripening method, cies, makes it conducting nature in the nanomaterials. The
SrO nucleus growth takes place initially by self and formation energy of oxygen vacancies and metal interstitials
mutual-aggregation, then nano-crystal re-aggregated and in semiconductor is very low and thus these defects form
aggregated SrO nanocrystals were formed. Nanocrystals eagerly, resulting in the experimentally elevated conductivity
crystallized and re-aggregated with each other counter of SrO NR compared to other undoped materials such as CuO,
parts through Vander-Waals forces and SrO spherical NiO, ZnO, etc. SrO NR materials have also attracted consid-
morphology had been reformed (Scheme 1). The cal- erable interest owing to their potential applications in fabricat-
cined doped NR was characterized in detailed in terms ing opto-electronics, electro-analytical, selective detection of
of their elemental, morphological, optical, structural bioassays, biological devices, hybrid-composites, electron-
properties and applied for L-Leu detection. field emission sources for emission exhibits, biochemical de-
tections, and surface-enhanced Raman properties etc.
Fabrication of glassy carbon electrode with SrO NR Undoped strontium oxide NR offers improved performance
due to the large-active surface area which increased of con-
NaH2PO4 (0.2 M), Na2HPO4 (0.2 M), and distilled water ductivity and current responses of SrO NR/Nafion/GCE as-
(200.0 mL) had been used for the preparation of phosphate sembly during electrochemical investigation.
buffer (PB, 200 mL, 0.1 M, pH = 7). Ethanol and conducting
binder, nafion were used to fabricate GCE with SrO NR. After Optical and structural characteristics
that, the fabricated electrode was kept at room temperature
(6 h) for uniform film formation with completed drying. The The optical characteristic is one of the significant properties
fabricated GCE and platinum (Pt) were used as a working and for the evaluation of catalytic activity of the white powder SrO
counter electrode respectively in order to find out the current– NR. Based on the principle of the UV/Vis. spectroscopy, the
voltage signals. outer electrons of the atom may be shifted to the upper energy
level, and the spectrum including band-gap energy of the met-
al oxide can be acquired due to the adsorption of radiant en-
Results and discussion ergy. The UV/Vis spectrum of the SrO NR had been recorded
in the visible range (400 ~ 800 nm), and a broad absorption
Choice of materials band at around 296.8 nm was observed (Fig. 1a). According to
the maximum level band absorption, the band-gap energy of
SrO nanorods have employed a great deal of consideration the SrO NR was calculated based on the Tauc’s rule (direct
due to their chemical, structural, physical, and optical proper- band-gap rule, v) [26]. (αhv)2 vs hv had been plotted and then
ties in terms of large-active surface area, high-stability, high extrapolated to the x-axis, and from the extrapolated curve, the
Scheme 1 Schematic representation of growth mechanism of SrO nanorods using by facile wet-chemical method.
3268 Microchim Acta (2016) 183:3265–3273
band-gap energy for SrO NR was found ~2.4 eV (Fig. 1b). 32.0 (110), 42 (111), 46.0 (200), 57.5.0 (210), 58.5
Where, α = Absorption coefficient, h = Plank’s constant, v = (211), 64.0 (220), 72 (221) and 78.0 (310) degrees
Frequency, r = 0.5 (Direct transition), A = Constant related to (Fig. 1d). All the denoted peaks in the spectrum were
the effective mass of the electrons, and Ebg = Band gap energy. assigned according to the JCPDS file (No: 6–520, 001–
1113, 37.5–0263, and 01–073–0661). The potential peak
(αhv)1/r = A (hv − Ebg) (v) indicated the crystalline pattern and purity of the NR.
According to the XRD analysis it may be recommended
FTIR examination was conducted (Region: 4000– that a good quantity of crystalline SrO was present in the
400 cm−1) under normal condition in perspective of atomic synthesized NR [28, 29]. Based on the Scherrer formula
and molecular vibrations to recognize the functional character (vi), the crystalline size of the SrO NR was calculated,
of the SrO NR. The IR spectrum shows peaks at 3287, 2107, and average diameter was found as 42.0 ± 5.0 nm (n =
1583, 1368, 1115, 867, and 619 cm−1 that assigned the pres- 15). Where, λ = wavelength of x-ray radiation, β = the
ence of O-H (stretching), −C≡C− (stretching), −C=C− full-width at half maximum (FWHM) of the peaks at the
(stretching), C–H (rocking), Sr–O–Sr (stretching), C–H, and diffracting angleθ.
Sr=O (stretching) in the NRs respectively (Fig. 1c). The prag-
matic peaks at 1115, and 619 cm−1 has been denoted for the D = 0.9λ/(β cos θ) (vi)
arrangement of metal-oxide (Sr=O) bond which recognized
the configuration of the SrO NR [27].
XRD analysis was conducted (2θ range =10–80°) to Morphological and elemental Examination
identify the crystalline pattern of the synthesized SrO NR
because the crystalline nature is the indication of metal- FESEM is a well-known process to study the morphology of SrO
oxygen framework. The prospective peaks intensity with NR. The morphology and elemental character of the synthesized
indication for 2θ values were observed at 25.0 (100), white SrO NR were examined using FESEM equipped XEDS
Fig. 1 Optical and structural estimation of SrO NR. (a) UV/Vis spectrum (Sample is dispersed in water under ultra-sonication for 1 h), (b) Band-gap
energy plot, (c) FTIR spectrum, and (d) XRD pattern
Microchim Acta (2016) 183:3265–3273 3269
respectively. The classical shapes of the white SrO NR had been elements that present within a material can be examined using
recorded at low to high magnified range (Fig. 2a and b). Based this technique. Based on the XPS analysis, strontium and ox-
on the XEDS analysis, strontium (Sr), and oxygen (O) were ygen were present in the synthesized SrO NR (Fig. 3a). The
presented in the white grown SrO NR. The NRs contains O spin orbit of Sr3d3/2, Sr3d5/2, and O1s spectra is conferred the
(27.35) and Sr (72.65) wt% respectively [27]. major peak at 134.7, 138.5 and 531.8 eV respectively, which
recognized that (Sr2+) and oxygen (O2−) are existed in the SrO
Estimation of binding energy NR (Fig. 3b and c) [30, 31]. Therefore, it is concluded that the
wet-chemically prepared SrO NR materials have single-phase
X-ray photoelectron spectroscopy (XPS) is a quantitative material. Also, this conclusion is reliable with the XRD data
spectroscopic technique that can be used to determine the noticeably.
chemical character of the elements present in the SrO NR.
The kinetic energy plus electrons number of a sample can be Detection of L-Leucine with SrO NR
anticipated during XPS examination by irradiating of an X-ray
beam with a nanorod. Generally, the elemental-composition, Expansion of the fabricated electrode with NR is the prelim-
chemical-state, empirical-formula, and electronic-state of the inary stage of appliance as a sensor. The major function of SrO
NR assembled as a sensor onto the GCE has been char- The apparent I-V curve is presented in Scheme 2c. The
acterized for the detection, and measurement of target resultant practical electrical response of L-Leu that was
analyte, L-Leu in PB system. The SrO NR/Nafion/ investigated by a simple and reliable I-V technique
GCE sensors have several advantages such as chemical- using SrO NR/Nafion/GCE is presented in Scheme 2d.
ly inert, easy to fabricate & assemble, non-toxic, safe, Based on the theory of I-V system, the current re-
and stable in air. The SrO NR sensor was fabricated sponses of SrO NR/Nafion/GCE noticeably altered dur-
with conducting binder on the GCE surface ing the adsorption of L-Leu as an analyte by electro-
(Scheme 2a). The easy and probable reaction mecha- chemical oxidation. Due to SrO NR/Nafion/GCE on
nism was generalized in Scheme 2b in presence of L- thin-film as a role of current-potential, the current re-
Leu on SrO NR/Nafion/GCE sensor surfaces. L-Leu had sponse with useful potential was markedly recognized
been converted into acid under redox reaction at PB having the holding time of electrometer was 1.0 s.
system in presence of SrO NR, where electrons were The fundamental purpose of SrO NR assembled onto
released upon oxidation which enhanced the current re- an electrode as a sensor has been used to recognize the
sponses against potential during the current–voltage mark agents that are not significantly valuable in health
measurement at room conditions (Scheme 2b) [24, 32]. care system. The pH of the different PB (pH = 5.7, 6.5,
7, 7.5, and 8) were optimized to identify which system NR fabricated electrode. Therefore it was noticeably re-
was more suitable to detect the amino acid, L-Leu, and ported that the sensor was more selective towards L-Leu
pH = 7.5 was found more responsive. The current re- compared with other chemicals (Fig. 4b). The current
sponses (potential range = 0.1 ~ 1.0 V) of the bare GCE signals of analyte were also recorded without and with
and coated with SrO NR onto the working electrode target analyte. An elevation of current responses had
were presented in Fig. 4a. The differences of the current been occurred for the modified SrO NR electrode with
responses between bare and coated GCE occurred due to L-Leu which has maintained a large surface area with
current signals have been enhanced by coated in com- better exposure in absorption and adsorption potentiality
pared with bare GCE. The biological chemicals such as onto the porous SrO surfaces of the rods. However, it
L-Asp acid, Crt, Gly, L-Cys, L-Glu acid, L-GSH, L-Tyr, was also compared individually the current responses of
L-Leu, Thionine acetate, and Uric acid were examined in selective 1.0 μM L-Leucine with and without 1.0 μM
order to measure the maximum current responses to SrO other analytes such as creatine, glycine, L-aspertic acid,
Table 1 Detection of L-Leu using various materials modified electrodes measured by electrochemical approaches
20. Gulao ES, Souza CJF, Andrade CT, G-Rojas EE (2016) Complex
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