American Journal of Analytical Chemistry, 2011, 2, 605-611
doi:10.4236/ajac.2011.25068 Published Online September 2011 (http://www.SciRP.org/journal/ajac)
Copyright © 2011 SciRes. AJAC
Determination of Mercuric Ion in Water Samples with a
LED Exciting and CCD Based Portable Spectrofluorimeter
Arsenio Muñoz de la Peña
1*
, María Isabel Rodríguez-Cáceres
1
, Diego Bohoyo Gil
1
,
María del Carmen Mahedero
1
, María del Carmen Hurtado-Sánchez
1
, Reyes Babiano
2
1
Department of Analytical Chemistry, University of Extremadura, Badajoz, Spain
2
Department of Organic and Inorganic Chemistry, University of Extremadura, Badajoz, Spain
E-mail:
*
arsenio@unex.es
Received March 29, 2011; revised June 3, 2011; accepted June 15, 2011
Abstract
The fluorescent characteristics of a fluorimetric chemosensor for mercuric ion, Hg
2+
, employing a synthe-
sized Rhodamine 6G derivative, have been analyzed. For that, a portable spectrofluorimeter composed of a
515 nm LED as excitation source, two fiber-optics and a CCD camera as detector, has been used, intended
for “in situ” analysis. A highly selective Rhodamine based probe for Hg
2+
, that is water soluble and gives a
positive response upon analyte binding, is reported. The reagent is bearing a monothiospirolactone group in a
Rhodamine 6G architecture and the thiol atom served for the direct attack of thiophilic Hg
2+
. The fluores-
cence enhancement is attributed to the spirolactone ring opening and the coordination of two sulphur atoms
to Hg
2+
giving a 2:1 reagent: Hg
2+
stoichiometry complex.
Keywords: Chemosensor, LED, Mercuric Ion, Water Analysis
1. Introduction
Mercury is widely distributed in the air, water and soil,
and is considered by the Environmental Protection Agency
(EPA) to be a highly dangerous element because of its
severe inmunotoxic, genotoxic and neurotoxic effects [1].
It is generated by volcanic emission and in several hu-
man activities as gold mining, combustion of solid waste
or burning of fossil fuels. The great time of residence of
mercury in vapour state and his easy oxidation to inor-
ganic species of Hg
2+
soluble in water have caused envi-
ronmental Hg
2+
levels. Mercury easily passes through
biological membranes such as skin, respiratory and gas-
trointestinal tissues. When absorbed in human body,
mercury causes damage to the central nervous and endo-
crine systems as well as neurological irreversible dam-
ages. The toxicity of mercury is known to be highly de-
pendent on its chemical form: organomercury is gener-
ally more toxic than inorganic mercury salts [2].
Recently, a variety of selective and sensitive fluores-
cent Hg
2+
chemosensors have been developed based on
fluorescein derivatives [3-6], NO
2
S
2
-donor macrocyle [7],
naphthalimide [8,9], BODIPY [10-12] or Rhodamine
derivatives [13-23].
BODIPY (boron dipyrromethene) fluorophores have
been widely used for the determination of Hg(II). Those
fluorophores have high absorption coefficient (ε > 50000
M
–1
cm
–1
), high fluorescence quantum yield (Φ > 0.5),
and high photostability [24]. Polyamide receptor photo-
electron transfer (PET) based fluorescent sensor mole-
cules could be used to detect Hg
2+
ions with either fluo-
rescence off-on response or fluorescence colour change
[8]. J. Wang et al. used a series of polyamide receptors
incorporating two, three and four amide arms to the
BODIPY fluorophore. They observed that a clear emis-
sion turn-on response when as low as 2 ppb (content
limit in drinking water set by EPA) of Hg(II) are present.
Thus, the sensor is practical as Hg
2+
ion “annunciator”
for drinking water [10]. On the other hand, J. Du et al.
synthesized a highly selective PET fluorescent sensor for
Hg
2+
containing a BODIPY fluorophore and a NS
2
O
2
pentachelating receptor. With this sensor the Hg
2+
could
be detected in a wide pH range [11]. Also, thiacrown and
crown ethers have been appended to BODIPY fluoro-
phores [12].
Rhodamines are classic dyes/fluorophores whose photo-
chemical properties have already been well studied. Be-
cause of their low cost, long-wavelength (> 500 nm) ab-
sorption/emission and high molar absorption coefficient
and quantum yield, these fluorophores are usually util-