Spectroscopy
Andrei Yu. Panarin,a Inna A. Khodasevich,a Olga L. Gladkova,b Sergei N. Terekhova,*
a
b
B.I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, Nezalezhnasti Ave., 68, 220072, Minsk, Belarus
Belarusian State University of Informatics and Radioelectronics, P. Brovka Str. 6, 220013 Minsk, Belarus
INTRODUCTION
Heavy metals are ubiquitously present in the environment as a result of natural processes and human activity.
It is known that they have a tendency to accumulate in
living organisms and are considered to be hazardous
substances. Among them, antimony is a toxic element that
exists mainly as Sb(III) and Sb(V) in environmental,
biological, and geochemical samples.14 Antimony derived from increasing anthropogenic emissions is an
environmental pollutant because Sb and its compounds
are industrially important. They are used in manufacturing
paper, plastics, textiles, glass, semiconductor compounds, alloys, rubber, and in the pharmaceutical
industry. The United States Environmental Protection
Agency considers antimony and its compounds to be
Received 1 February 2013; accepted 18 October 2013.
* Author to whom correspondence should be sent. E-mail: terekhov@
imaph.bas-net.by.
DOI: 10.1366/13-07034
0003-7028/14/6803-0297/0
Q 2014 Society for Applied Spectroscopy
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297
EXPERIMENTAL
Reagent and Chemicals. Phenyluorone (9-phenyl2,3,7-trihydroxy-6-uorone), sulphuric acid (H2SO4 98%),
and antimony oxide (Sb2O3) were analytical reagent
grade. Rhodamine 6G (98%), silver nitrate (AgNO3
99.9999%), and hydrochloric and hydrouoric acid
(38%; Sigma-Aldrich) were used without additional
purication. Samples were prepared with distilled water.
Preparation of Sb-Phenyluorone Complex. A standard Sb(III) stock solution of 1000 ng/mL was prepared in
several steps. First, we dissolved 35.914 mg of antimony
oxide (Sb 2O 3 , containing 30 mg of Sb) in 2 mL
hydrochloric acid (1.5 M HCl) water solution. Second,
100 lL of this solution was diluted to 5 mL with 1.5 M HCl.
Finally, 33.3 lL of the resulting solution was diluted with
distilled water to obtain 10 mL of 0.003 M HCl solution of
1 lg/mL Sb mass concentration.
For preparation of a phenyluorone stock solution, 5
mg of PhF powder was added into 56 mL ethyl alcohol
(96%) containing a 100 lL mixture of sulfuric acid with
water (1 : 1). The sample was heated and sonicated for
10 min to PhF full dissolution. Then the obtained
298
SERS spectra shown in the gures represent unsmoothed accumulated data followed by appropriate
background subtraction. The wavenumber peak positions accuracy is 61.0 cm1.
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299
FIG. 3. SEM images of the Ag-coated PSi plates. (a) The plan-view
image representative of the Ag lm. (b) The image of the dendritic
structure of the Ag deposit. (c) The image showing the Ag-nanoparticle
array in the area between dendrites.
Figure 3ac shows SEM images of the surface of AgPSi samples prepared by the immersion plating procedure from the silver nitrate solution at 4 8C. Unlike our
earlier reports44,45 where deposition at room temperature resulted in the formation of small Ag particles, in the
300
FIG. 4. SERS spectra of Sb-PhF (1) and PhF (2), deposited from the corresponding solutions on the Ag-PSi plate. Excitation wavelength was 532.0
nm. [Adapted with permission from Ref. 59. Copyright Springer. 2012.]
PhF
Assignments [58,59]
580
600
607
775
1163
1190
1218
774
1191
1222
1345
1354
1374
1504
1505
1559
1600
1621
1542
1605
1641
a
in-plane bending of bonds or ring; I, II, III: correspondence of
coordinates to a particular ring (see Fig. 1).
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301
302
FIG. 6. Quenching kinetics of the band at 1354 cm1 (a) and SERS
background at 810 cm1, (b) in the air (curves 1), and in a vacuum
(curves 2). Rectangles show optimal time intervals for SERS spectra
registration.
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303
FIG. 11. The log plot of the 1354 and 775 cm1 bands intensity in SERS
spectra of droplet samples versus Sb mass concentration.
concentration of sample solutions and Sb mass, respectively. Error bars represent the standard deviation of the
mean signal intensity of three sampled spots in two
series of samples. It can be seen that in both cases SERS
intensity increases gradually with concentration as well
as with mass. In contrast to photometric data, for which
the optical density plot is linear (as expected) over the
whole range of concentrations (inset in Fig. 9), the
increase of SERS intensity slows when reaching a high
concentration. However, it seems that the concentration
range from 1 to 10 ng/mL (or 50500 pg) can be tted
using a linear function. We performed additional measurements in the range of low concentration. The data
plotted in Fig. 12 reveal that in this region the mass
dependence for the intensity of the band at 1354 cm1 is
linear with slope k = 2.58/pg and a rather high coefcient
of determination R2 = 0.96. We did not t the band at 775
cm1 since it is not the marker of the Sb-PhF complex.
The results obtained show that by using the SERS
method on the Ag-PSi substrates, solutions with a minor
concentration of Sb can be analyzed.
It should be noted that in principle there is a way to
enhance the sensitivity of the SERS method proposed.
For example, one can downshift LOD by increasing the
duration of Ag-PSi soaking in Sb-PhF solution or by
decreasing the volume of droplets. We attempted to
deposit the single 10 lL droplet with c = 1 ng/mL onto
the silvered surface of PSi, and we managed to observe
successfully the Raman bands from Sb-PhF. However, a
strong background of unknown origin interfered with
analyte peaks, making the quantitative analysis difcult.
Nevertheless we were able to get a qualitative answer to
the question of whether or not antimony is present in
solution.
CONCLUSION
FIG. 10. The log plot of peak intensity of the 1354 and 775 cm1 bands
versus detected Sb mass concentration.
304
FIG. 12. The dependence of the 1354 and 775 cm1 bands intensity on
the mass of Sb.
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