Microchim Acta (2010) 170:313319
DOI 10.1007/s00604-010-0322-4
ORIGINAL PAPER
New poly(aryleneethynylene)s as optical active platforms
in biosensing. Selective fluorescent detection of Hg(II)
obtained by the use of aminoacidic groups anchored
on conjugated backbones
Dario Compagnone & Antonella Ricci &
Michele Del Carlo & Marco Chiarini & Alessia Pepe &
Claudio Lo Sterzo
Received: 23 December 2009 / Accepted: 20 February 2010 / Published online: 21 March 2010
# Springer-Verlag 2010
Abstract Newly synthesized poly(aryleneethynylene)s
carrying substituents such as leucine, glycine and methio-
nine have been prepared and tested for their ability to bind
Hg(II) ions. Binding resulted in strong quenching of the
fluorescence emission of all the compounds tested. A
comparative study of the quenching efficiency by Hg(II)
was then carried out in a flow injection system. Quenching
efficiency was amplified in the polymeric material because
of the so-called wire effect that is observed with organic
conducting polymers. Under the experimental conditions
used, detection limits are in the 50100 ppb range. The
selectivity for Hg(II) is remarkable in that a series of other
divalent cations did not give any measurable effect, a slight
response being observed for methylmercury only. The
materials hold promise for selective determination of Hg
(II) ion.
Keywords Conducting polymers . Hg(II) . Poly
(aryleneethynylene)s . Optical detection . Fluorescence .
Sensors . Aminoacidic based sensors
D. Compagnone (*) : A. Ricci : M. Del Carlo : M. Chiarini :
A. Pepe : C. Lo Sterzo
Dipartimento di Scienze degli Alimenti,
Universit degli Studi di Teramo,
Via Carlo R. Lerici 1,
64023 Mosciano SantAngelo, Teramo, Italy
e-mail: dcompagnone@unite.it
M. Del Carlo : C. Lo Sterzo
Istituto CNR di Metodologie Chimiche (IMC-CNR),
Sezione Meccanismi di Reazione, Dipartimento di Chimica,
Universit La Sapienza,
Piazzale Aldo Moro 5,
00185 Roma, Italy
Introduction
Conjugated organic materials have received much attention
in recent years for the fabrication of efficient chemo- and
bio-sensors [19]. Conjugated oligomeric and polymeric
systems are organic materials characterized by an extended
electronic delocalization spanning along the entire molec-
ular backbone, that provides charge mobility, and induces
remarkable properties such as electrical conductivity, low
ionization potential and low energy optical transitions [10].
In these systems, interaction with analyte species may cause
severe perturbation of electronic delocalization, and thus
the occurring of changes of related opto-electronic proper-
ties. Therefore, conjugated organic materials can efficiently
convert the interaction with target analytes into an
observable signal, that can either be optical (absorption,
fluorescence), electrical (redox, resistive), or both.
By exploitation of our extended one-pot (EOP) synthetic
procedure [11, 12], we have recently provided a convenient
access to highly ethynylated materials such as poly
(aryleneethynylene)s (PAEs), one of the most interesting
classes of materials to be used for sensing purposes whose
widespread use is impaired by synthetic difficulties [3, 7, 8,
13, 14].
We recently described detection of metal ions using as
sensing elements co-polymers, obtained by a synthetic
modular approach, made of alternating arylene and
phenanthroline (1) or bithiophene (2) moieties spaced by
ethynylene units [15] (Fig. 1). In that study, a clear
quenching of the fluorescence emission for the whole range
of metal ions with a completely unselective response was
observed for the phenanthroline containing polymer, while
the bithiophene containing material although with only a
314 D. Compagnone et al.

Fig. 1 Structure of OC8H17 OC8H17

polyaryleneethynylenes
S
functionalized with
phenanthroline (1) and N N n S n
bithiophene (2) H17C8O H17C8O
1 2

weak decrease of the fluorescence intensity, showed a Mercury is a heavy metal that is widespread in the
selective response for Hg(II) ions. lithosphere and water and is an environmental pollutant of
Here we report about sensing properties of new family of major concern due to its persistency, bioaccumulation and
PAEs derivatives carrying aminoacidic side arms as active toxicity. Adverse long-term health effects are significant
sites for the capture of metal ions [16], directly connected even upon exposure to trace concentrations of this element
to the conjugated molecular backbone. Aminoacids and [22, 23].
peptides are known to possess coordinating ability vs. metal Classic analytical approaches to mercury sensing are
ions. However, despite these premises, in 2001 Gooding atomic absorption spectrometry, inductively coupled plasma
and Hibbert [17], reviewing the use of aminoacids and mass spectrometry, anodic stripping voltammetry, and X-ray
peptides as recognition elements in sensing devices, found fluorescence spectrometry, all of which require expensive
very few examples. More recently, several reports in the hardware, sophisticated sample treatment, and/or well-trained
literature demonstrate the growing interest in this research operators. On the contrary, the development of sensitive and
field, focusing on the exploitation of the high selectivity of selective optical tests for mercury is an intensely pursued goal
peptides for the binding and detection of specific metal as demonstrated by recent literature [2429].
ions, using both fluorescence measurements [18] and Good sensitivity and remarkable selectivity for Hg(II) was
chemically modified electrodes [1921]. observed using the tested compounds in solution. A flow
In this work we have exploited the coordinating ability injection procedure has been used to compare the analytical
for Hg(II) of highly ethynylated polymers and model behaviour of the sensing materials; amplification of fluores-
compounds carrying L-leucine (4,6,8), L-glycine (3,7) and cence quenching was demonstrated for the polymers 7 and
L-methionine (5) covalently bound to the conjugated 8 (the socalled wire effect [30, 31]). Both the model and
backbone of PAEs platforms (Fig. 2). polymeric compounds appear promising materials to be used

OCH3 OCH3 S
O
C O C O C
OCH3
O O O
N N N
C C C
H H H

H H H
C C C
N N N
CH3O O O O
C 3, DGM 4, DLM 5, DMM
C O C O
O
CH3O S CH3O

OCH3 OCH3 O OCH3

O C O C C O C
OCH3
O O O O
N N N N
C C C C
H H H H

n n
H H H H
C C C C
N N N N
O O CH3O O O
C
C O C O 7, DGP C O 8, DLP
O
CH3O CH3O 6, TLM CH3O

Fig. 2 Structure of the compounds tested in this work: model (6, TLM); polymers containing diL-glycine (7, DGP) and diL-leucine
compounds carrying diL-glycine units (3, DGM), diL-leucine units (8, DLP) functionalized aromatic units
(4, DLM), diL-methionine units (5, DMM) and tetraL-leucine units
New poly(aryleneethynylene)s as optical active platforms in biosensing
as sensitive elements for the development of optical selective
sensors for Hg(II).
Experimental
Reagents
All the reagents and solvents used were of analytical or
HPLC grade and were from Sigma chemicals, Italy (www.
sigmaaldrich.com).
Synthesis of chelating compounds
The synthesis of L-leucine containing models DLM and
TLM and polymer DLP, and their full characterization has
been reported in detail elsewhere [16]. By following the
procedures therein described, N,N-[2,5-dibromoterephtha-
loyl](S,S)di-glycine methyl ester (9) and N,N-[2,5-dibro-
moterephthaloyl](S,S)di-methionine methyl ester (10) were
prepared to attach the respective aminoacidic functionalities
on conjugated backbones of PAEs platforms. DGM and
DMM were obtained by coupling of tributyl(phenyl-
ethynyl)tin with the dibromides 9 and 10 respectively,
while the reaction of the difunctionalized 9 and bis
(tributylstannyl)acetilene afforded the polymeric material
DGP. All the aminoacidic moieties have been introduced
onto the PAEs skeleton as methyl ester derivatives, in order
to safely perform subsequent transformations. All the
experiments reported in the paper were run using com-
pounds represented in Fig. 2, where the aminoacidic side
arms are methoxylated.
Flow injection analysis
The flow injection analysis measurement was carried out
using a HPLC system consisting in a peristaltic pump (Perkin
Elmer series 200), a fluorimetric detector (Perkin Elmer LC
240) and an autosampler (Perkin Elmer series 200).
Di-aminoacidic model compounds (DLM, DGM,
DMM) were tested at a concentration of 3,6 M, TLM at
38 M, DGP at 25 M and DLP at 88 M. The injection
volume was 1 L for all compounds, except for DGP
(5 L). The mobile phase was methanol for TLM e DLP
and acetonitrile for DGM, DLM, DMM and DGP, flow
rate 0,5 mlmin1. Stock solutions of 100 ppm of Hg(II) in
water were prepared from Hg(NO3)2. An appropriate
diluted amount was later added to the testing solutions
using an incubation time of 1 min at room temperature.
100 ppm stock solutions of methylmercury were prepared
dissolving CH3HgCl in acetonitrile.
The effect of the tested compounds is determined by
calculating the difference between the area obtained in
315
presence and absence of mercury, using the following
formula:
I% Area compound
 Area compound with Hg=area compound  100
Measurement on film
DLM films were obtained onto polistirene ELISA Micro-
wells by casting 100 L of 2.74103 M solution of the
compound in acetonitrile. The solvent was let to evaporate
overnight at room temperature. Hg(NO3)2 0.04 M solutions
in CH3CN:H2O 1:9, CH3CN:H2O 3:7, CH3CN:H2O 1:1
were used to run incubation of Hg(II) onto DLM films.
Incubation time was 2 min. The ELISA Microwells was
irradiated by UV lamp having a max at 365 nm (4 W)
positioned in the top side of a black box. The images were
recorded by a Logitech QuickCam.
Results and discussion
All the compounds reported in Fig. 2 have been synthesized
and tested to assess their ability to bind and detect metal
ions. Three different aminoacidic side arms were selected to
compare their ability to bind the metal species: glycine was
selected as the simplest aminoacidic structure found in
proteins, leucine to increase the complexity and methionine
in order to evaluate the effect of sulfur on metal ion
binding. Model compounds carrying 2 aminoacidic arms
bound to a conjugated platform consisting in three benzene
rings connected by two acetylenic units, were prepared
(DGM, N,N-[2,5-bis(phenylethynyl)terephthaloyl](S,S)di-
glycine methyl ester; DLM, N,N-[2,5-bis(phenylethynyl)
terephthaloyl](S,S)di-leucine methyl ester; DMM, N,N-
[2,5-bis(phenylethynyl)terephthaloyl](S,S)di-methionine
methyl ester). Another leucine model compound, with a
different conjugated platform constituted of two benzene
rings connected by one acetylenic unit, carrying 4 amino-
acidic arms was also synthesized (TLM, N,N,N,N-
[(2,2-ethyne-2,1-diyl)diterephthaloyl](S,S,S,S)tetra-leucine
methyl ester). Finally, glycine and leucine containing
polymeric materials were prepared (DGP, poly[N,N-(2-
ethynylterephthaloyl)(S,S)di-glycine methyl ester] and
DLP, poly[N,N-(2-ethynylterephthaloyl)(S,S)di-leucine
methyl ester]) (see Fig. 2).
UV-Vis absorption and emission spectra characteristics
in acetonitrile of the newly synthesized compounds are
reported in Table 1. Adsorption maxima were 310 nm for
TLM, 320350 nm for DGM, DLM and DMM, and 360
380 nm for the polymers DGP and DLP; for the polymeric
material, we observed a red shift effect both in absorption
316 D. Compagnone et al.

Table 1 Absorption and emission maxima of the new synthesized 120

polyaryleneethynylenes
100
Abs max (nm) Em max (nm)
80

I%
DLM 320 nm 400 nm 60
TLM 310 nm 370 nm
40 DGM
DLP 370 nm 505 nm
DLM
DGM 320 nm 395 nm 20
DMM
DGP 360 nm 400 nm
0
DMM 320 nm 400 nm
0.00 1.00 2.00 3.00 4.00
Hg (eq)
and emission maxima. This effect, due to a more extended Fig. 4 Fluorescence quenching in FIA of the di-amminoacidic model
electronic conjugation has been already studied and reported compounds
by our and other research groups [11, 12, 32, 33]. All the
compounds exhibited the same trend in the maxima of the different concentration of the metal ion with a Specfit
fluorescence bands. Quantum yields were in the 0.50.6 Program, indicated a 1:2 stoichiometry for the di-aminoacidic
range for the model compounds DGM, DLM and DMM, models (DGM, DLM, DMM)/Hg(II) adduct formation,
0.02 for TLM, and 0.0070.01 for the polymers. while a 2:1 stoichiometry was observed for TLM/Hg(II)
A typical example of the strong decrease of the emission complexation. Calculated dissociation constants were esti-
intensity upon incubation with Hg(II) is given for DMM. In mated in the 10-6107 range for DMM and DGM, and in
Fig. 3a is reported the absorption spectrum of the model the 108109 range for leucine based model compounds
compound in acetonitrile, while Fig. 3b clearly evidences (DLM and TLM).
the quenching effect of increasing amounts of Hg(II) added
in solution. A study of the stoichiometry of the complex for Flow injection analysis of Hg(II)
the molecular models, run by analyzing the data for
The quenching effect was further evaluated in a flow
injection setup. The injected volume (15 L) for each of
a 1

0.8 a
100.0
0.6
80.0
A

0.4
60.0
I%

0.2
40.0
0 TLM
20.0
220 270 320 370 420 470 DLP
wavelength (nm) 0.0
0 0.2 0.4 0.6 0.8 1 1.2
b Hg (eq)
350

300 DMM
b
120.0
DMM + 0.2 eq Hg(II)
250
DMM + 0.6 eq Hg(II) 100.0
I (au)

200 DMM + 1.5 eq Hg(II)

DMM + 2.2 eq Hg(II) 80.0
150
60.0
I%

100
40.0
50 DGM
20.0
0 DGP
370 390 410 430 450 470 490 510 0.0
wavelength (nm) 0 1 2 3
Hg (eq)
Fig. 3 Absorption spectrum of 20 M DMM in CH3CN a; emission
spectra of 5 M DMM in CH3CN in the presence of 02.2 Fig. 5 Fluorescence quenching in FIA: comparison of TLM with
equivalents of Hg(II) b DLP (a) and of DGM with DGP
New poly(aryleneethynylene)s as optical active platforms in biosensing 317

Table 2 Quenching effect of methylmercury (I%)
Methylmercury equivalents DLP DLM TLM
0.1 4.9 0.8 8.3
0.5 8.8 13.6 8.5
1.0 9.4 9.7 7.6
1.5 15.1 10.1 8.2
2.0 12.3 12.7 6.7
the compounds was chosen in order to have a fluorescence
signal of comparable magnitude. The incubation time was
1 min at room temperature; in fact, no significant changes
in the signal were registered for longer incubation times (up
to 1 h) for each of the compounds tested. Comparison of
the results obtained for the di-aminoacidic model com-
pounds, reported as I% of the inhibition, is shown in Fig. 4.
A sigmoidal curve was obtained for each of the com-
pounds; the reactivity of DGM and DMM were very
similar, indicating that the presence of the sulfur atom is not
relevant for a quantitative effect on quenching. In fact, the
signal was completely quenched at 2 eq of Hg(II), while
comparable values for 50% of the initial signal (I50) were
obtained, being 1,0 equivalents (eq) for DGM and 1,1 eq in
the case of DMM. The DLM signal was completely
quenched at 3,5 eq, with an I50 1,7 eq. Looking at the
other leucine-substituted model compound TLM (Fig. 5a),
a residual 30% of fluorescence signal was still recorded,
with saturation occurring at 0,8 eq and I50 at 0,5 eq of Hg
(II). The behavior of the inhibition curve obtained using the
leucine containing polymer DLP (Fig. 5a) was different,
since a strong quenching was obtained already at lower
equivalents of Hg(II) (i.e. 20% at 0,05 eq), and saturation
was attained at 0,8 eq with an I50 of 0,4 eq. These data
clearly demonstrated the so called wire effect. The same
sensitivity enhancement was observed for the glycine-
substituted polymer DGP (Fig. 5b) with respect to the
relative model compound DGM; in the case of DGP I50
was registered for 0,15 Hg(II) eq. Relative standard
DMM deviation for all the measurements were in 23% range
with the lowest detection limits (calculated as 3 SD of the
5.0 blank) ranging from 50 to 300 ppb.
2.6
2.2 Selectivity
12.8
15.3 The ability to quench fluorescence emission was also tested
for a number of different metal cations such as Pb2+, Cd2+,
Cu2+, Mg2+, Ni2+, Mn2+, Co2+, Zn2+. No detectable
quenching was observed for each of these metal ions for
concentrations ratios ion:Hg(II) up to 1000:1 with respect
to all the PAEs studied. The effect of the selected metal ions
was tested also in the presence of fixed amount of Hg(II)
(100 ppb), and no significant interference was observed on
the emission quenching. Incubation carried out with a
different mixture of the metal ions or longer incubation
times gave similar results.
In order to rule out the role of the alkyne moieties
toward the binding of Hg(II), a blank test was performed
using diphenylacetylene. No changes in absorption and
emission spectra were recorded after incubation with
different amounts of Hg(II). We can then affirm that the
well known affinity (and in some cases reactivity) of the
Hg(II) for the triple bonds [34, 35] is not sufficient to
explain the observed variation of the fluorescence spectrum
of the synthesized compounds, while an essential role is
played by the pendant aminoacidic units. It should be
noticed that other examples of selectivity toward different
analytes by conjugated materials based sensors have been
reported, and that the mechanism of the phenomenon has
not been yet fully and clearly explained [5, 7].
A further confirmation of this remarkable selectivity was
obtained measuring the quenching effect of methylmercury.
Limited but measurable quenching of the fluorescence was
in fact observed for some of the synthesized compounds
(Table 2), with a maximum decrease of 1215% of the
emission signal for DLP, DLM and DMM and a lower
effect for TLM (6%). In our opinion, the steric hindrance of

Fig. 6 Emission of a DLM

film under UV exposure a; a b
emission quenching after
incubation with Hg(II) H2O:
CH3CN 1:1 solution b
318
the methyl group decreases the quenching effect of Hg(II)
and this is particularly evident for TLM that presents a 2:1
stoichiometry for the formation of the complex.
Quenching on film
In order to prove the possibility of using the synthesized
compounds in solid state for the realization of optical sensor
devices, the ability of Hg(II) to quench the fluorescence was
also tested on DLM films. DLM films were casted onto
polystirene ELISA Microwells (2104 mmol/well) as
described in the experimental section. A picture of one
deposited film containing microwell excited by the UV lamp
is given in Fig. 6a; as expected a strong blue emission was
recorded. Initially, incubation of the film with a 104 M
solution of Hg(II) dissolved in water did not cause any
detectable quenching of the emission. However, the addition
of CH3CN to the Hg(II) solution at different ratios caused a
progressive decrease of the intensity of the emission with
total quenching attained at 1:1 H2O:CH3CN (Fig. 6b). The
necessity of the use of organic solvent should indicate that
the aminoacidic pendant leucine units need a certain degree
of freedom to be able to bind Hg(II) and quench the
luminescence signal. Further experimental work is needed to
optimize films casting and analytical conditions, but this
preliminary experiment demonstrate the feasibility of the use
of these compounds for the realization of membrane based
sensors.
Conclusions
Poly(aryleneethynylene)s containing aminoacids as pendant
units resulted to efficiently bind Hg(II). Intrinsic fluorescence
due to the conjugated backbone was quenched upon binding
and was the basis for the detection of Hg(II). Good analytical
sensitivity and excellent selectivity have been obtained using
the different compounds in solution, with amplification of the
signal for the polymeric materials (wire effect). Both the
model compounds and polymeric materials appear very
promising for the development of optical assays or sensors
for Hg(II).
Acknowledgements This work has been supported by MIUR
through PRIN 2007 project. Opto-active molecular systems, conju-
gated polymers, and nanoparticles for the development of new
chemical sensors.
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