Talanta 76 (2008) 96–101

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Application of a metal ion-imprinted polymer based on salen–Cu complex to flow

injection preconcentration and FAAS determination of copper
Stanisław Walas ∗ , Anna Tobiasz, Marta Gawin,
Bartosz Trzewik, Marcin Strojny, Halina Mrowiec
Jagiellonian University, Faculty of Chemistry, ul. Ingardena 3, 30-060 Kraków, Poland

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

Article history: A new Cu(II)-imprinted polymer (Cu-IIP) for preconcentration of copper by liquid–solid extraction via
Received 3 October 2007 flow injection technique has been proposed. Cu-IIP was obtained by copolymerization of salen–Cu(II)
Received in revised form 7 February 2008 complex with styrene and divinylbenzene using suspension polymerization technique. Granules frac-
Accepted 14 February 2008
tion of 60–80 ␮m in diameter was used as a microcolumn packing. Cu(II) sorption was proved to be the
Available online 10 March 2008
most effective from solutions of pH 7, whereas similar elution effectiveness was observed when applying
as eluents hydrochloric or nitric acid in the concentration range of 0.5–10% (v/v). The system exhibited
Keywords:
good long-term stability and acid resistance. Batch sorbent capacity was found to be 0.11 mmol g−1 of a
On-line preconcentration
Salen-based ion-imprinted polymer
dry polymer. Enrichment factor (EF) for 30 s loading time was 16. Preconcentration of Cu(II) and poten-
Copper tially interfering metal ions is strongly pH dependent. Examination of Cu(II) sorption in the presence of
Flow injection-flame atomic absorption Pb(II), Cd(II), Zn(II) and Ag(I) showed significant influence of cadmium and zinc ions only and that was
spectrometry for the interferent concentrations above 0.5 mg L−1 (Cu-IIP mass of ca. 35 mg). The interference effect
was reduced with the sorbent mass increase. Fe(III) and Mn(II) ions, present in treated tap water in rel-
atively high concentrations, did not interfere. Effective pH adjusting of the loaded solution in on-line
mode, when applying diluted Clark–Lubs buffering solution, allowed accurate copper determination in
tap water (compared to graphite furnace atomic absorption spectrometry, GFAAS) using standard addition
or combination calibration method.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Sensitivity of many popular analytical techniques, e.g. flame
atomic absorption spectrometry (FAAS), is generally insufficient for
trace analysis [1], therefore analyte preconcentration is required.
Flow methods are universal tools for sample pretreatment,
including preconcentration of analyte preceding its subsequent
determination [2,3]. They improve selectivity of the analytical
method and provide flexibility of enrichment factors appropriate
for given analytical needs.
Although FAAS is generally a specific determination method,
introducing a preconcentration step may lead to interferences in
this stage due to sorbents insufficient selectivity. For that reason
new packing materials are still being proposed and examined.
Recent achievements in this field have been summarized in a
review by de Pereira and Arruda [4]. Ion-imprinted polymers
(IIPs), based on the idea of molecular imprinting technique, have
attracted much attention as selective sorbents for preconcentra-
∗ Corresponding author. Fax: +48 12 634 05 15.
E-mail address: walas@chemia.uj.edu.pl (S. Walas).
tion of metal ions [5–8]. In ion imprinting it is a metal ion which
serves as a template. The choice of a complexing ligand is of great
importance here, as it directly influences selectivity of the sorbent.
Also the coordination geometry and the coordination number of a
metal ion together with the charge and the size of the ion play an
important role in obtaining selective IIPs [9]. Ion-imprinted poly-
mers have already found various applications, e.g. in separation,
preconcentration and purification processes with regard to metal
ions including transition elements [10], actinides [11], lanthanides
[12] and noble metals in diverse matrices [13].
Shiff bases may be perspective complexing ligands for ion
imprinting purposes due to their complexing abilities towards
heavy metals. They have been applied both as reagents in simple
spectrophotometric determinations [14] and as modifying agents
for various sorbents [15–17]. Among Shiff bases especially salens
have been used for forming organometallic complexes but to the
authors’ knowledge they have not served as complexing ligands
for IIPs yet.
Here we present a salen-based copper-imprinted polymer for
on-line flow injection microcolumn preconcentration of Cu(II). The
system was coupled with flame atomic absorption spectrometer in
order to improve the sensitivity of copper determination.

0039-9140/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2008.02.008
 S. Walas et al. / Talanta 76 (2008) 96–101
Fig. 1. A scheme of the flow injection preconcentration system FIAS 400: valve
positions for sorption (1) and elution (2) step.
2. Experimental
2.1. Apparatus
PerkinElmer FIAS 400 flow injection system coupled with AAn-
alyst 300 flame atomic absorption spectrometer was applied.
Air/acetylene flame was used and copper was determined at the
wavelength of 324.8 nm. Deuterium background correction was
applied in all measurements. Fig. 1 illustrates the on-line flow injec-
tion preconcentration system coupled with FAAS with the use of
a capillary of 16 cm in length. FIAS 400 preconcentration system
comprises two peristaltic pumps, a two-positional valve and a pre-
concentration column. Two TYGON R3607 red-red pump tubes (I.D.
1.14 mm) were applied for both pumps in most of the experiments.
Only for on-line pH adjusting one yellow-blue tube (I.D. 1.52) and
one red-red tube were used for pump 1.
Elmetron (Zabrze, Poland) CPI-551 pH-meter was used for pH
measurements.
For GFAAS analyses SpectrAA Zeeman 220 (Varian) was applied.
NMR, IR spectra and elemental analysis were performed with
the use of Bruker Avance II 300 MHz spectrometer, Bruker Equinox
55 spectrometer and EuroEA 3000 Elemental Analyzer, respec-
tively.
Scanning electron microscope (SEM), ZEISS Leo 435 VP was
applied to take microphoto of obtained microbeads.
2.2. Reagents and solutions
For organic synthesis of salen–Cu complex: 97% allyl bro-
mide, Aldrich (Milwaukee, USA), ethylenediamine pure for analysis,
Aldrich (Milwaukee, USA), salicylaldehyde pure, Aldrich (Milwau-
kee, USA), copper acetate pure for analysis, Merck (Darmstadt,
Germany) were used. During polymerization process pure styren
and 55% divinylbenzene, Aldrich (Milwaukee, USA) were applied.
All solvents were of pure for analysis grade.
Standard stock solutions (1 g L−1 ) of copper, lead, cadmium,
cobalt, nickel, chromium, manganese, iron, mercury, magnesium,
97
silver and zinc were prepared from Merck (Darmstadt, Germany)
Titrisol solutions. Standard solutions were prepared by dilution of
the stock solutions with deionized water. Eluent solutions (0.5; 1.0;
5.0 and 10.0% (v/v)) were prepared by dilution of concentrated
nitric and hydrochloric acid, pure for analysis, Merck (Darm-
stadt, Germany). Deionized water after reversed osmosis was used
throughout the work, also for preparation of blanks.
Britton–Robinson and Clark–Lubs buffer solutions were pre-
pared according to Ref. [18]. In the former case, the buffers were
prepared by mixing acidic solution (a mixture of 0.04 mol phos-
phoric acid, 0.04 mol boric acid and 0.04 mol acetic acid per litre)
with 0.2 mol L−1 sodium hydroxide solution in appropriate ratios. In
the latter case, 0.1 mol L−1 KH2 PO4 solution and 0.1 mol L−1 NaOH
were the buffer components.
2.3. Preparation of salen–Cu complex
The chelating ligand—salen was obtained in a three-step organic
synthesis. Salicylaldehyde (0.33 mol) was dissolved in acetone
(0.5 mL), then allyl bromide (0.35 mol) and potassium carbonate
(55.7 g) were added to the solution. The mixture was heated under
reflux for 3 h, then the solvent was removed using rotary evaporator
and finally the residue was distilled under reduced pressure. The
intermediate product (refractive index (RI) 1.557) was subsequently
subjected to Claisen rearrangement by heating. Thus, obtained
product (0.06 mol) (RI = 1.564) and ethylendiamine (0.03 mol) were
dissolved in ethanol (110 mL) and heated under reflux for 2 min. Yel-
low crystals of salen were obtained and filtered. 1 H NMR (CDCl3 ):
ı = 13.52 (s, 1H, OH), 8.36 (s, 1H, CH N), 7.19 (dd, J = 7.5, 1.8 Hz, 1H,
H-3), 7.12 (dd, J = 7.5, 1.8 Hz, 1H, H-5), 6.82 (t, J = 7.5 Hz, 1H, H-4),
6.03 (ddt, J = 23.2, 10.5, 6.6 Hz, 1H, CH ), 5.10 (ddd, J = 8.6, 3.6,
1.5 Hz, 1H, CH2 ), 5.06 (t, J = 1.5 Hz, 1H, CH2 ), 3.93 (s, 2H, N CH2 ),
3.74 (s, 3H, OCH3 ), 3.44 (d, J = 6.6 Hz, 2H, CH2 ). 13 C NMR (CDCl3 ):
ı = 166.7 (C N), 158.9 (C-1), 136.6, 132.6, 129.7, 127.8, 118.3, 118.1,
115.6, 59.6 (CH2 N), 33.6 (CH2 ). FT-IR (KBr, cm−1 ): 3500 ( (OH);
broad), 1631 ( (C N)), 1448 ( (C C)), 912 ( ( C H); vinyl), 744
( (C H); aromatic). Calculated for C22 H24 N2 O2 (%): C, 75.84; H,
6.95; N, 8.04. Analytically found: C, 75.70; H, 6.98; N, 8.14.
Complexation reaction was performed as follow: salen (2 mmol)
was dissolved in ethanol (15 mL) and added to solution of copper
acetate (2.4 mmol) in water (5 mL) upon stirring. Dark violet crys-
tals of salen–Cu complex were obtained and filtered. FT-IR (KBr,
cm−1 ): 1624 ( (C N)), 1546 ( (C C); vinyl), 916 ( (C H); aro-
matic), 462 ( (N Cu)). Calculated for C22 H22 N2 O2 Cu (%): C, 64.14;
H, 5.38; N, 6.82. Analytically found: C, 64.65; H, 5.52; N, 6.89.
2.4. Preparation of copper(II)-imprinted polymer microbeads
IIP microbeads were prepared by suspension polymerization
technique. The procedure was as follow: (i) dispersion medium was
prepared by dissolving sodium chloride (0.3 g) and gelatine (2.1 g)
in water (100 mL); (ii) salen–Cu complex (0.11 g) was dissolved in
chloroform (11 mL) and subsequently mixed with styrene (7.5 mL)
and divinylbenzene (1.5 mL); then benzoylperoxide (BPO) (0.5 g)
was added as an initiator; (iii) both solutions were transferred to
thermostatted reactor and mechanically stirred. The reactor tem-
perature was kept constant at 90 ◦ C for 4 h. The scheme of the Cu-IIP
preparation process is presented in Fig. 2.
Thus, obtained spherically shaped microbeads were separated
from the polymerization medium, thoroughly washed with water
and dried in a vacuum oven for 24 h. Control (non-imprinted)
polymer was prepared in a similar way but salen ligand (0.10 g)
was used instead of salen–Cu complex. Both imprinted and non-
imprinted polymers were subsequently sieved and the fraction of
98 S. Walas et al. / Talanta 76 (2008) 96–101

Fig. 2. Scheme of the proposed Cu(II)-imprinted polymer preparation.

diameter range of 60–80 ␮m (Fig. 3) was used as a microcolumn
filling.
2.5. Extraction procedure
Cylindrical column (0.5 cm in length and 3 mm in diameter)
packed with ca. 35 mg of the prepared polymer was used for most of
the experiments—such a small portion of the sorbent was applied
intentionally to show the polymer properties in detail. A column of
3.0 cm in length (3 mm in diameter; 150 mg sorbent) was applied
for special purposes. In order to prevent leakage of the sorbent
SPE polyethylene frits were used. FI-FAAS set was controlled by a
computer program including: pre-filling, filling, loading and elution
step (Table 1).
Each preconcentration cycle was proceeded by a short loading
and elution step performed to fill the tubes. Loading time was 30 s
for most of the experiments. Elution, including 10 s reading time,
lasted for another 30 s. During the sample loading step, 10 s before
the valve was moved to the elution position, the signal readings
were stabilized with the eluent solution and finally set zero. To
assure effective and stable nebulization, the flow rate in the elution
step was set at 8 mL min−1 . Absorbance peak was registered and
its height was the analytical signal. For every standard and sample
solution four series of measurements were carried out in a random
order. Each measurement was followed by a blank check.

Table 1
FI program for preconcentration of copper; +: on; −off.

Step Time (s) Pump 1 Pump 2 Loading Elution Reading

Pre-fill 1 + + + – –
1 10 + – + – –
2 20 – + – + –
3 20 + – + – –
4 10 + + + – –
5 30 – + – + +
Fig. 3. Scanning electron microscope photo of the Cu(II)-imprinted polymer 6 1 – – – + –
microbeads.
 S. Walas et al. / Talanta 76 (2008) 96–101 99

determined as follow. 35 mg of the sorbent was packed into a micro-

Fig. 4. Signal dependence on copper concentration with and without preconcentra-
tion step; — FAAS; · · · FI-FAAS; sorption time 30 s; - ·- ·- · 60 s; sorbent mass 35 mg;
pH 7.
3. Results and discussion
3.1. Copper extraction from Cu-imprinted polymer
Copper ions acting as a template in the imprinting process were
removed from the polymer to free the active sites in the polymeric
net. Extraction was carried out directly in the flow system and vari-
ous eluents including EDTA, nitric or hydrochloric acid solutions of
different concentrations were used. 5% HNO3 (v/v) appeared to be
the most effective of the above-mentioned solutions, hence it was
used as eluent for template extraction. Elution efficiency of copper
sorbed on the polymer in the preconcentration process was also
evaluated and 1% HNO3 was chosen for this purpose.
3.2. Optimum pH range for preconcentration of copper
Complex formation between salen immobilized in the poly-
meric net and copper ions present in a sample was expected to
be pH dependent. For this reason pH influence of the loading
solution on the preconcentration of copper was tested. Copper
standard solutions (0.3 mg Cu L−1 ) within a wide range of pH
(2.87–11.98) were prepared and analyzed according to the above-
mentioned procedure. For buffering purposes Britton–Robinson
(phosphate–borate) buffers were used. In low pH range copper
preconcentration was hindered due to strong protonation of the
active sites in the sorbent. The medium pH increase facilitated com-
plex formation and the maximum was reached at pH 7. For higher
pH values the signal decrease was observed. Therefore, for further
preconcentration experiments pH of copper solutions was set at 7.
column and used for copper preconcentration. Loading time was
set at 30 s. The absorbance was rising with growing concentration
of copper, although the increase was non-linear. No plateau was
reached in the tested range of concentration. To find the percent-
age of copper ions retained on the sorbent standard solutions of
0.1–0.4 mg Cu L−1 were loaded onto the sorbent and the effluent
was collected for subsequent copper determination by graphite fur-
nace atomic absorption spectrometry (GFAAS). The obtained results
indicated that only about 70% of copper ions was retained on the
sorbent. This result is an effect of a compromise between the sam-
ple loading rate (higher than the optimal one) and determination
sensitivity resulting from total quantity of coper ions loaded on the
sorbent in 30-s sorption time.
Batch sorption capacity was examined as follow: 35 mg of the
polymer was added to 20 mL of a standard solution (3, 5, 10, 20,
50 mg L−1 ) and the mixture was magnetically stirred for 60 min.
After that time an aliquot was analyzed with the use of FAAS.
Mass of the retained copper was calculated as a difference of ini-
tial Cu(II) mass in the solution and the one left after reaching the
equilibrium. Batch sorption capacity was found to be 0.11 mmol g−1
(7.22 mg g−1 ).
3.5. Sorbent stability
Sorbent stability in the working conditions was evaluated for
one hundred repetitive preconcentration cycles (0.3 mg Cu L−1 , pH
7) and 30-s loading time. The obtained absorbance values did not
form any trend which proved good sorbent stability in the working
conditions.
3.6. Interference studies
Selectivity of the polymer was investigated in a three-stage pro-
cedure. In the preliminary stage a possibility of different metal ions
sorption was evaluated for two concentration levels of a particular
ion (0.2 and 1.0 mg L−1 ) both with and without preconcentration
step. As different elements determination sensitivity vary when
applying AAS as a detector, enrichment factors (EFs) for potential
interfering ions were calculated and compared instead of compar-
ing absorbance values obtained in a single measurement. Among
Cu(II), Cd(II), Co(II), Cr(III), Mn(II), Hg(II), Ag(I), Mg(II), Zn(II), Fe(III),
Ni(II), Pb(II) significant enrichment was found for Cu(II), Pb(II),
Cd(II), Ag(I) and Zn(II).
In the second stage influence of the loading solution pH on pre-
concentration of a given ion was evaluated. The results presented in
Fig. 5 indicate that in the pH range optimal for copper sorption the

3.3. Enrichment factor

Enrichment factor was calculated as a ratio of the calibration

curve slope obtained when applying the preconcentration step
(FI-FAAS) and the slope obtained without it (FAAS). For standards
buffered to pH 7 and 30-s loading time EF accounted for 16.
Although the enrichment factor was higher when 60-s loading time
was applied (EF 23), to assure satisfactory sample throughput for
further studies 30-s loading time was accepted. The mentioned
calibration functions are presented in Fig. 4.

3.4. Sorption capacity

To estimate sorption capacity of the tested polymer experiments

were performed both in a flow injection and a batch mode. In
the former case the dependence of the analytical signal on a wide Fig. 5. Influence of pH on preconcentration of Cu(II), Cd(II), Zn(II), Ag(I); Cu-IIP mass:
concentration range of the loaded solution (0.1–10 mg Cu L−1 ) was 35 mg, concentration of the standard solutions: 0.3 mg L−1 .
100 S. Walas et al. / Talanta 76 (2008) 96–101

Table 2
Influence of Zn(II), Cd(II), Ag(I) and Pb(II) on copper(II) preconcentration

Concentration of interferent (mg L−1 ) Recovery (%)

0.2 mg L−1 a 0.4 mg L−1 a

Control polymer Cu-IIP Control polymer Cu-IIP

Zn((ll)
0.1 95.6 ± 0.3b 94.7 ± 0.3 88.5 ± 0.6 100.3 ± 0.9
0.2 94.0 ± 0.2 104,8 ± 0.2 86.3 ± 0.7 96.5 ± 0.5
0.5 87.4 ± 0 1 99.5 ± 0.1 85.4 ± 0.3 94.2 ± 0.2
1.0 76.2 ± 0.3 91.3 ± 0.4 84.4 ± 0.1 77.1 ± 0 1

Cd(ll)
0.1 98.7 ± 0.5 100.0 ± 0.9 100.8 ± 0.4 96.9 ± 0.1
0.2 100.5 ± 0.5 94.9 ± 0.3 90 5 ± 02 95.2 ± 0.8
0.5 90.4 ± 0.1 94.9 ± 0.3 87.9 ± 0.1 96.3 ± 0.2
1.0 86.1 ± 0.5 74.2 ± 0.3 88.9 ± 0.4 93.4 ± 0.1

Ag(l)
0.1 100.3 ± 0.1 95.3 ± 0.3 103.8 ± 0.1 101.9 ± 0.2
0.2 100.6 ± 0.2 101.9 ± 0.5 99.1 ± 0.2 95.7 ± 0.4
0.5 91.3 ± 0.2 103.1 ± 0.3 994 ± 0.3 97.0 ± 0.3
1.0 87.7 ± 0.3 102.7 ± 0.2 99.8 ± 0.6 100.5 ± 0.7
2.0 84.7 ± 0 5 100.4 ± 0.2 92.1 ± 0.2 96.8 ± 0.2
5.0 85.9 ± 0.3 96.5 ± 0.7 79.8 ± 0.2 96.5 ± 0.2

Pb(ll)
0.1 97.5 ± 0.0 99.5 ± 0.2 97.8 ± 0.8 101.5 ± 0.6
0.2 89.9 ± 0.2 99.6 ± 0.4 99.8 ± 0.3 104.0 ± 0.4
0.5 91 0 ± 0.1 86.0 ± 0.2 91.8 ± 0.6 89.8 ± 0.5
10 87 7 ± 0.2 76 3 ± 0 2 85.7 ± 0.5 87.5 ± 0.3
a
Concentration of Cu(ll).
b
Recovery values higher than 95 % were bolded.

potential interfering ions are also complexed but to a lesser extent.
In spite of lower interferent co-extraction in acidic medium it was
decided to adjust the samples pH to 7 in subsequent experiments
due to significant loss of sensitivity for copper in other pH regions.
In the third stage individual influence of each interfering
metal ion on copper preconcentration at pH 7 was exam-
ined. Solutions containing copper at two concentration levels
(0.2 or 0.4 mg L−1 ) and an interferent at concentration ranging
from 0 to 5.0 mg L−1 were analyzed both for Cu-imprinted and
non-imprinted polymer. For Cu-imprinted polymer presence of
Cd(II), Zn(II) at concentrations higher than 0.5 mg L−1 resulted
in copper signal decrease. Pb(II) at concentration lower than
0.2 mg L−1 did not influence copper sorption. Silver ions did
not affect copper preconcentration. For non-imprinted polymer
interference effect (recovery <95%) occurred for lower interfer-
ent concentration than for Cu-imprinted polymer as presented in
Table 2.
3.7. Preconcentration of copper present in water samples
The imprinted polymer was applied to determination of copper
in tap water samples from water installation containing copper ele-
ments. Two procedures of adjusting a sample pH: (a) manual and
(b) on-line were applied and copper concentration was determined
with the use of the following calibration methods: the set of stan-
dards method (SSM), the standard addition method (SAM) or the
combination calibration method (CCM). The applied combination
calibration method integrates the virtues of the set of standards
method and the standard addition method. In this approach con-
centration of a given analyte in one sample is determined as in
SAM (i.e. in interpolative way), while for the rest of the samples the
analyte concentration is found as in SSM (i.e. in interpolative way).
Regression equations for SSM and SAM with manual pH adjust-
ing (pH 7, sorbent mass 150 mg) were: A = 0.516 cCu and A = 0.578
cCu + 0.043, respectively.
GFAAS analyses were performed in order to compare the results
obtained for copper when applying the proposed method. Relative
error (RE) was calculated according to Eq. (1):
cCu (FI − FAAS) − cCu (ETAAS)
RE = × 100% (1)
cCu (ETAAS)
Relative error of 12.8% and 5.7% was found for SSM and SAM,
while relative standard deviation (R.S.D.) accounted for 2.4% and
3.4%, respectively. The limit of detection (LOD) for the set of stan-
dard calibration method was calculated as a standard deviation (3)
from 10 readings of the blank divided by the slope of the calibration
line and was found to be 9.0 ␮g L−1 .
In the on-line procedure of pH adjustment the flow rate for a
standard or a sample was kept as in the manual one (8 mL min−1 )
while a buffering solution was transported with an additional tube
(4 mL min−1 ) and mixed with a standard/sample before reaching
the column. In order to find the optimal working conditions param-
eters like: the sort of a buffering solution and its concentration,
loading time, length and shape of a mixing coil were optimized. At
first application of sodium hydroxide of different concentrations
was tested for adjusting the standards pH and the highest signal
for copper was achieved when 4 × 10−5 mol L−1 NaOH was applied.
However, for real samples pH adjustment with sodium hydroxide
could be inadequate, hence several other buffering solutions were
examined and Clark–Lubs buffer (pH 7) diluted 8 times was chosen
as optimal.
Influence of the loading time on the sorption process was eval-
uated taking into account EF values. Calibration equation in the
concentration range 0–0.2 mg Cu L−1 was found both for FAAS and
FI-FAAS technique (preconcentration time: 30, 60, 120 s; sorbent
mass 150 mg; on-line pH adjustment, pH 7) and thus obtained
slopes were used for calculating the EF values. The dependence was
found linear up to 60-s and changed to non-linear when longer
loading time was applied. The EF values for 30-, 60- and 120-s
sorption time were: 14, 26 and 43, respectively.
 S. Walas et al. / Talanta 76 (2008) 96–101
Table 3
Copper concentration in tap water samples obtained for CCM
Sample FI-FAAS (␮g L−1 ) ETAAS (␮g L−1 ) RE (%) R.S.D. (%)
Extrapolative method
1 19 21 9.4 5.9
Interpolative method
2 27 24 13.2 12.4
3 23 21 9.6 8.3
4 156 146 7.0 1.6
Calibration equation y = 0.5701x + 0.0106; correlation coefficient: R = 0.9975; stan-
dard addition range 0–0.2 mg L−1 .
On-line buffering system was applied to determination of cop-
per in tap water samples by CCM. For the first sample copper
concentration was obtained via extrapolation according to SAM,
whereas for the rest of the samples it was calculated in interpolative
way using the calibration line established for the first sample. Cop-
per concentration found and relative error calculated for exemplary
samples are presented in Table 3.
To evaluate trueness of the proposed method synthetic water
of composition adequate to SPS-SW2 (Reference Material for
Measurement of Elements in Surface Waters, Spectrapure Stan-
dards AS, Oslo Norway) with copper concentration 100 ␮g L−1
was prepared and analyzed. Comparison of copper concentration
found (98 ± 1) and theoretical one proved good trueness of the
method.
4. Conclusions
The salen based Cu-IIP prepared by suspension polymeriza-
tion technique fulfils the most important requirements needed
for FIA preconcentration: spherical shape resulting in low flow
back pressure, good ion-exchange effectiveness, acid resistance
and long-term stability—no significant loss of activity was
observed.
The proposed sorbent does not require the analyte to be con-
verted into a complex prior to retention and the only parameter
strongly influencing sorption and selectivity is pH of the loading
solution, thus sample pretreatment is very easy and incorporates
only pH adjusting which can be done on-line with the same
setup.
The enrichment factor obtained for 30 s loading time is typi-
cal for the applied preconcentration procedure (when the analyte
peak obtained in the elution process appears in about 2 s) and is of
the same order or even better than EFs reported for other sorbents
[19–21], when recalculating data to comparable preconcentration
conditions. Longer loading time resulted in EF increase, albeit no
linear correlation was observed in the tested conditions (sorbent
mass and flow rate).
101
LOD value obtained for the new salen based copper-imprinted
polymer, loading solution volume 4 mL and sample sorption time
30 s is comparable with those found for other sorbents. For some
comparison LOD values: 0.2 ␮g L−1 [19], 8.4 ␮g L−1 [20], 0.4 ␮g L−1
[22], were obtained for loading solution volumes: 11.3, 13 and
14.4 mL, and sample sorption: 90, 120 and 120 s, respectively.
The proposed IIP although appeared not specific for copper
showed good selectivity. The only significant influence on Cu(II)
preconcentration was observed for cadmium and zinc ions at con-
centrations above 0.5 mg L−1 , however the aforesaid metal ions are
not to be found in tap water on this level. Moreover, thanks to the
sorbent selectivity copper is separated from iron or manganese ions
which are present in water due to its treatment. When compared
to non-imprinted polymer, the presented IIP exhibits much higher
selectivity towards all tested ions.
The proposed method may find application in copper determi-
nation in water samples, as was exemplified in analysis of tap water.
The method shows good accuracy especially when the standard
addition method or combination calibration method are used for
potential matrix effects elimination.
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