A chalcone-based highly selective and sensitive chromofluorogenic probe for trivalent metal cations

Article abstract of DOI:10.1002/cplu.201500042

A new chalcone-based probe for the chromofluorogenic sensing of trivalent (Al³⁺, Fe³⁺, Cr³⁺, Ga³⁺, In³⁺ and As³⁺) over mono- and divalent cations and anions is reported. In the presence of

Full text of DOI:10.1002/cplu.201500042

DOI: 10.1002/cplu.201500042
Communications
A Chalcone-Based Highly Selective and Sensitive
Chromofluorogenic Probe for Trivalent Metal Cations
[
a, b, c, d]
[a, b, c]
[a, b, c]
Luis E. Santos-Figueroa,
Antoni Llopis-Lorente,
Santiago Royo,
[a, b, c]
[a, b, c]
[a, e]
[a, e]
Fꢀlix Sancenꢁn,[
Ramꢁn Martꢂnez-MꢃÇez,*
Ana M. Costero,*
Salvador Gil,
and
a, e]
Margarita Parra
A new chalcone-based probe for the chromofluorogenic sens-
associated with several diseases, such as anemia; hemochro-
matosis; diabetes; Parkinson’s disease; and dysfunction of all
principal human organs, such as the heart, pancreas, and
3
+
3+
3+
3+
3+
3+
ing of trivalent (Al , Fe , Cr , Ga , In and As ) over
mono- and divalent cations and anions is reported. In the pres-
ence of trivalent metal cations, the probe was able to display
a remarkable color change from yellow to colorless that was
clearly visible to the naked eye. Also, the initial strong yellow
emission was gradually quenched and substituted by a weakly
shifted band.
[3]
liver. On the other hand, aluminum is the third most abun-
dant element on earth and the most abundant metallic ele-
ment. Aluminum is used in several commercial applications,
such as water treatment, food additives, medicines, and metal-
lic devices. In addition, some studies indicate that abnormal
[
4]
levels of aluminum ions in certain human tissues and cells
[5]
[6]
3+
could induce Alzheimer’s and Parkinson’s diseases. The Cr
Recently, increasing interest in the recognition and sensing of
transition-metal cations has been boosted owing to better un-
derstanding of their biological and environmental roles in sev-
eral fundamental natural and physiologic process, as well as
their widespread use in industrial applications and in organic
cation is one of the most important nutrients in human and
animal diets and plays a fundamental role in the metabolism
[7]
of carbohydrates, proteins, lipids, and nucleic acids. Deficien-
3
+
cy of Cr is associated with the development of diabetes and
[
8]
3+
some cardiovascular diseases. Similar to Al , an overdose of
[
1]
3+
3+
3+
3+
[9]
synthesis protocols. Among metal cations, Al , Fe , Cr
Cr
cations could induce serious toxic effects; moreover,
3
+
3+
3+
Ga , In , and As play crucial roles in biological processes
and their detection is a timely topic. For instance, iron is the
most abundant transition metal in cellular systems. More spe-
their use in the metal industry has resulted in increased levels
of chromium in the environment, and today it has come to be
[10]
regarded as a pollutant element. Gallium does not exist in
3
+
cifically, the Fe cation is an essential element in the growth
and development of living systems, as well as in many bio-
the free form in nature, but is found primarily in its 3+ oxida-
3
+
tion state. Several Ga salts are used for the preparation of
semiconductors and as radiopharmaceutical agents in several
[
2]
chemical processes at the cellular level, and its deficiency is
[11]
imaging procedures. Indium is also only found in the earth’s
3
+
crust in the form of In
compounds. Similar to gallium,
[
a] Dr. L. E. Santos-Figueroa, A. Llopis-Lorente, Dr. S. Royo, Dr. F. Sancenꢀn,
Prof. R. Martꢁnez-MꢂÇez, Prof. A. M. Costero, Prof. S. Gil, Prof. M. Parra
Centro de Reconocimiento Molecular y Desarrollo Tecnolꢀgico (IDM)
Unidad Mixta Universidad Politꢃcnica de Valencia
[12]
3+
indium is used for electronics and in several alloys. In , sim-
3
+
[13]
ilarly to Al , can be toxic to the kidney. Finally, elemental ar-
3+
[14]
senic and As compounds are toxic and its poisoning is
linked with a variety of neurologic, cardiovascular dermatologic
Universidad de Valencia, Camino de Vera, s/n
4
6022 Valencia (Spain)
[
15]
and carcinogenic effects. In spite of this acute toxicity, arsen-
ic is essential as a trace element in birds and in several mam-
[b] Dr. L. E. Santos-Figueroa, A. Llopis-Lorente, Dr. S. Royo, Dr. F. Sancenꢀn,
Prof. R. Martꢁnez-MꢂÇez
Departamento de Quꢁmica
[16]
mals.
Universidad Politꢃcnica de Valencia
Camino de Vera, s/n, 46022 Valencia (Spain)
E-mail: rmaez@qim.upv.es
Consequently, trivalent cation detection is now a focus of in-
terest and a timely topic of research. In this context, the devel-
opment of optical probes that are able to selectively recognize
trivalent cations are highly appealing owing to the possibility
of their detection through widely available low-cost instrumen-
tation, and also because optical probes offer the possibility of
developing simple tests to sense these target species with de-
[
c] Dr. L. E. Santos-Figueroa, A. Llopis-Lorente, Dr. S. Royo, Dr. F. Sancenꢀn,
Prof. R. Martꢁnez-MꢂÇez
CIBER de Bioingenierꢁa
Biomateriales y Nanomedicina (CIBER-BBN) (Spain)
[
d] Dr. L. E. Santos-Figueroa
Instituto de Investigaciꢀn y Evaluaciꢀn Educativas y Sociales (INIEES)
Universidad Pedagꢀgica Nacional Francisco Morazꢂn
Tegucigalpa (Honduras)
[17]
tection by the naked eye. Some selective fluoro- and chro-
3
+ [18]
3+ [19]
3+ [20]
mogenic probes for the detection of Fe
,
Al
cations have been reported. How-
ever, only a few probes that are able to recognize simultane-
,
Cr ,
3
+ [21]
3+ [22]
3+[23]
[
e] Prof. A. M. Costero, Prof. S. Gil, Prof. M. Parra
Departamento de Quꢁmica Orgꢂnica, Facultad de Ciencias Quꢁmicas
Universidad de Valencia, Dr. Moliner 50
Ga
,
In
,
and As
[24]
[25]
ously two or three trivalent cations have been described
in the literature. This lack of multiresponsive probes is, in most
cases, due to severe interference from mono- and divalent
metal cations.
4
6100 Burjassot, Valencia (Spain)
E-mail: ana.costero@uv.es
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cplu.201500042.
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Communications
Taking into account the above mentioned facts and our in-
terest in the development of new chromofluorogenic chemo-
with a remarkable quantum yield of F=0.63ꢁ0.02 (calculated
[27]
by using fluorescein in 0.1m NaOH as a standard).
[
17a,b,26]
sensors,
we report herein a simple to prepare, new
The charge-transfer character of the visible band was as-
sessed by quantum chemical calculations at the semiempirical
level by using the PM3 model (with a root-mean-square (RMS)
gradient of 0.001) in HyperChem software. As seen in Figure 2,
the HOMO orbital was mainly centered in the N,N-dimethylani-
line donor fragment, whereas the LUMO orbital was located in
the acceptor phenylthiourea moiety.
probe that is able to selectively detect the trivalent cations
3
+
3+
3+
3+
3+
3+
Fe , Al , Cr , Ga , In , and As
through remarkable
changes in the UV-visible and fluorescence spectra. Moreover,
low detection limits, in the nanomolar range when fluores-
cence was used, were determined.
Probe 2 was readily synthesized by a two-step procedure
(see Scheme 1). The first step consisted of the synthesis of thi-
ourea derivative 1 by the reaction of commercially available 4-
Figure 2. HOMO and LUMO orbitals for probe 2.
Probe 2 contains, in its structure, two potential binding
units, namely, the thiourea moiety (for anion coordination) and
an aniline donor nitrogen atom (able to interact with cations).
Therefore, the chromo and fluorogenic behavior of solutions of
probe 2 in acetonitrile were tested in the presence of 10
Scheme 1. Synthesis of probe 2.
aminoacetophenone and ethylisothiocyanate. Finally, probe 2
was obtained by an aldol condensation between compound
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
equivalents of selected anions (F , Cl , Br , I , OH , AcO ,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1
and 4-dimethylaminobenzaldehyde (see the Supporting In-
BzO (Bz=benzoyl), CN , OCN , H PO HSO4 , and ClO )
2
3+
4
4
+
+
2+
2+
2+
3+
2+
3+
formation for further details).
and cations (K , Li , Mg , Co , Fe , Fe , Al , Hg , Cr ,
2
+
2+
2+
2+
2+
2+
2+
3+
3+
3+
Solutions of probe 2 in acetonitrile (see Figure 1) showed an
absorption band in the visible zone centered at l=414 nm
Pb , Cd , Ba , Ni , Zn , Ca , Cu , Ga , In , and As ).
The results obtained in the presence of cations are depicted in
4
ꢀ1
ꢀ1
3+
3+
3+
3+
3+
(
e=2.64ꢅ10 m cm ) and two less intense bands in the UV
Figure 3. Of all cations tested, only Al , Fe , Cr Ga , In ,
4
ꢀ1
ꢀ1
domain at l=317 (e=1.54ꢅ10 m cm ) and 257 nm (e=
4
ꢀ1
ꢀ1
1
.50ꢅ10 m cm ). As a consequence, solutions of 2 showed
an intense yellow color. Furthermore, when solutions of 2 in
acetonitrile were excited at l=412 nm, a very strong emission
ꢀ
1
band at l=538 nm (stokes shift=5567.23 cm ) was displayed
Figure 3. Photographs of color and fluorescence (lex =365 nm) modulation
ꢀ
4
ꢀ3
of 2 (acetonitrile, 1.0ꢅ10 moldm ) upon the addition of 10 equivalents of
selected cations.
3
+
and As induced remarkable and immediate color modula-
tions. In this respect, the color of solutions of probe 2 in aceto-
nitrile changed from yellow to colorless and the strong yellow
fluorescence was quenched and substituted with a weak blue
emission. Moreover, and despite the presence of a thiourea
moiety in the probe, compound 2 was unable to display sens-
ing features in the presence of the tested anions (see the Sup-
porting Information).
Figure 1. UV-visible and emission (lex =412 nm) spectra of probe 2 in aceto-
ꢀ
5
ꢀ3
Having assessed the highly selective response of 2 toward
trivalent metal cations, we studied the sensitivity of the probe
nitrile (1.0ꢅ10 moldm ). Inset: color and fluorescence (under UV lamp,
ex =365 nm) of solutions of 2 in acetonitrile observed by the naked eye.
l
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by monitoring the UV-visible and emission changes at 258C of
emission at l=406 nm (see Figure 4). The overall result is a re-
markable reduction of the quantum yield of probe 2 to
solutions in acetonitrile upon the addition of increasing quanti-
3
+
3+
3+
3+
3+
3+
3+
ties of Fe , Al , Cr , Ga , In , and As . The UV-visible
and emission profiles obtained in the presence of the six triva-
lent cations were similar and, as an example, the complete set
0.070ꢁ0.005 in the presence of Al cations.
From UV-visible and fluorescence titrations, the limits of de-
3
+
3+
3+
3+
3+
tection (LOD) of probe 2 for Al , Fe , Cr Ga , In , and
3
+
3+
of spectra obtained for probe 2 and the Al cation are shown
As cations were evaluated (see Table 1) by using the IUPAC
in Figure 4. As observed, the addition of increasing amounts of
Table 1. LOD values and logarithms of binding constants for the interac-
tion of probe 2 with trivalent cations.
3
+
[a]
Cation
Limit of detection [M
]
logK
UV/Vis [mm]
Emission [nm]
UV/Vis
Emission
3
3
+
+
+
Al
Fe
0.81
0.43
0.34
0.34
0.33
0.34
3.27
2.87
2.44
2.59
3.68
3.88
13.10ꢁ0.043
12.79ꢁ0.047
14.02ꢁ0.007
13.12ꢁ0.006
14.98ꢁ0.010
12.67ꢁ0.018
12.35ꢁ0.039
12.70ꢁ0.034
15.21ꢁ0.071
10.79ꢁ0.042
10.02ꢁ0.015
11.25ꢁ0.074
3
Cr
3
+
+
Ga
3
As
3
+
In
[
a] LogK values for the formation of 2:1 probe–metal complexes [Eq. (1)].
regression approach (see the Supporting Information for de-
[28]
tails). When changes in the absorption bands were studied,
the LOD values were in the micromolar range, whereas when
fluorescence was used the LOD values were in the nanomolar
range (see the inset in Figure 4, bottom). The latter LOD values
are remarkable when considering that the LOD values for
other reported probes for trivalent metal cations are usually in
[18–25]
the micromolar range.
Moreover, to determine the binding stoichiometry between
probe 2 and the trivalent metal cations, Job’s plots were calcu-
[29]
lated. As an example, Figure 5 shows the Job’s plot deter-
Figure 4. UV-visible (top) and emission (bottom) profile of titrations of a solu-
ꢀ
5
ꢀ3
tion (1.0ꢅ10 moldm ) of probe 2 in acetonitrile upon the addition of in-
3
+
creasing quantities of Al cations. Inset: fluorescence changes of the emis-
sion band at l=537 nm in the nanomolar range.
3
+
Al
cations induced a progressive decrease in the visible
band at l=414 nm together with the simultaneous growth of
a
1
new blueshifted absorption at l=292 nm (e=1.39ꢅ
3
+
Figure 5. Job’s plot for complexation between probe 2 and Al cations, as
determined by UV-visible measurements at l=414 nm in acetonitrile with
[2]+[Al ]=1ꢅ10 moldm .
4
ꢀ1
ꢀ1
0 m cm ) with a clear isosbestic point at l=361 nm. The
3
+
ꢀ4
ꢀ3
disappearance of the absorption band at l=414 nm was re-
sponsible for the yellow-to-colorless color modulation ob-
served (see Figure 3).
3
+
On the other hand, upon excitation at the isosbestic point
observed in the course of the UV-visible titration between 2
and Al (l =361 nm), an intense emission at l=538 nm was
mined for Al , which clearly shows the formation of 2:1
probe–cation complexes. The same stoichiometries were deter-
3
+
3+
3+
3+
3+
3+
mined for probe 2 with Fe , Cr Ga , In , and As cations
(data not shown).
ex
3
+
observed. The addition of increasing amounts of Al cations
induced the progressive quenching of the fluorescence at l=
Based on the Job’s plots, the corresponding stability con-
3
+
538 nm together with the simultaneous growth of a new blue
stants for the formation of [M(2)2] complexes were deter-
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1
mined by using HypSpec software (V 1.1.18) and adjusting the
data to Equation (1):
As seen in the family of H NMR spectra shown in Figure 6,
3
+
the addition of increasing quantities of Al to a solution of
probe 2 in CD CN induced remarkable downfield shifts for pro-
3
3
þ
þ 2L Ð ½MðLÞ2ꢂ3þ
M
ð1Þ
tons Hh, Hd, and Hj. These protons are located in the N,N-di-
3
+
methylaniline ring and indicated coordination of Al with the
nitrogen donor nitrogen atom located in this fragment. A simi-
lar coordination mode is expected for the other trivalent metal
cations.
The estimated values of logK obtained by UV-visible and emis-
sion titration profile data are shown in Table 1.
The remarkable hypsochromic shift observed in the visible
3
+
3+
3+
band in the presence of the metals cations Al , Fe , Cr
,
Finally, the optical response of probe 2 was also studied in
a mixture of acetonitrile/water. However, it was found that the
addition of more than 5% water to acetonitrile disabled the
chromofluorogenic response observed upon the addition of
trivalent metal cations. This could be ascribed to the fact that
trivalent cations have high free solvation energies, and hence,
a strong affinity for coordinating with water molecules rather
than with probe 2.
3
+
3+
3+
Ga , In , and As appears to be indicative of the preferen-
tial coordination of these metals with the donor part of probe
2
, that is, the N,N-dimethylaniline moiety. Moreover, the selec-
tive response observed is most likely to be related to the small
size and high charge of the trivalent cations. Both characteris-
3
+
3+
3+
3+
3+
3+
tics endowed Al , Fe , Cr
Ga , In , and As
with
a strong polarization character that induced changes in the
electronic distribution of 2, and resulted in remarkable modu-
lations of the UV-visible and fluorescence spectra.
In summary, we reported herein a simple chromofluorogenic
probe with a chalcone-like structure that was able to selective-
3
+
3+
3+
3+
3+
3+
To confirm the binding mode of probe 2 with trivalent cat-
ly detect Al , Fe , Cr , Ga , In , and As over mono-
and divalent cations and anions. In the presence of trivalent
metal cations, the probe was able to display a remarkable
color change from yellow to colorless that was clearly visible
to the naked eye. Also, the initial strong yellow emission was
gradually quenched and substituted by a weakly shifted band.
Moreover, the new probe showed remarkable LOD values in
the nanomolar range when fluorescence changes were stud-
ied. The probe displayed a significant selectivity, a remarkably
low limit of detection, and a simple to detect by the naked
eye chromofluorogenic response; these features make it suita-
ble for the effective, sensitive, fast, and low-cost detection of
trivalent cations in organic solvents.
1
3+
ions, H NMR titration studies were performed with Al . The
most representative signal of probe 2 in the aliphatic zone was
a singlet centered at d=3.02 ppm, which was ascribed to the
methyl groups linked with the nitrogen atom of the aniline
ring (Hj protons in Figure 6). Dealing with the aromatic zone,
signals appeared as doublets at d=6.76 and 7.63 ppm (Hh
and Hd protons of the N,N-dimethylaniline 1,4-disubstituted
ring) and at d=7.54 and 8.04 ppm (He and Ha protons of the
1
,4-disubstituted aromatic ring with carbonyl and thiourea
moieties). Also, two doublets centered at d=7.48 and
.72 ppm with a coupling constant of 15.4 Hz, ascribed to the
7
trans-double bond, were observed.
Acknowledgements
Financial support from the Spanish Government (Project
MAT2012-38429-C04), the Generalitat Valencia (Project PROME-
TEOII/2014/047), and the CIBER de Bioingenierꢁa, Biomateriales y
Nanomedicina (CIBER-BBN) is gratefully acknowledged. A.L.L.
would like to thank the Fundaciꢀn la Caixa for his doctoral fel-
lowship. We are also grateful to the Carolina Foundation for
a doctoral grant to L.E.S.-F.
Keywords: anions
·
chalcone-based
probe
·
chromofluorogenic sensing · sensors · trivalent cations
[
[
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Published online on && &&, 0000
ChemPlusChem 0000, 00, 0 – 0
www.chempluschem.org
5
ꢄ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

COMMUNICATIONS
L. E. Santos-Figueroa, A. Llopis-Lorente,
S. Royo, F. Sancenꢀn, R. Martꢁnez-MꢂÇez,*
A. M. Costero,* S. Gil, M. Parra
Recognizing trivalent cations: A new
chalcone-containing probe has been de-
vised for the chromo-fluorogenic sens-
3
+
3+
3+
3+
3+
ing of Al , Fe , Cr , Ga , In , and
&& – &&
3
+
As cations over mono- and divalent
cations and several anions (see figure).
The limit of detection of this probe is in
the nm range.
A Chalcone-Based Highly Selective
and Sensitive Chromofluorogenic
Probe for Trivalent Metal Cations
&
ChemPlusChem 0000, 00, 0 – 0
www.chempluschem.org
6
ꢄ 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!