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Hexa-BODIPY Linked-Triazole Based on a

Cyclotriphosphazene Core as a Highly Selective
and Sensitive Fluorescent Sensor for Fe2+ Ions
Article in Journal of Fluorescence April 2016
Impact Factor: 1.93 DOI: 10.1007/s10895-016-1797-0

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J Fluoresc
DOI 10.1007/s10895-016-1797-0

ORIGINAL ARTICLE

Hexa-BODIPY Linked-Triazole Based on a Cyclotriphosphazene

Core as a Highly Selective and Sensitive Fluorescent Sensor
for Fe2+ Ions
Seda etindere 1 & Sreyya O. Tmay 1 & Adem Kl 1 & Mahmut Durmu 1 &
Serkan Yeilot 1

Received: 10 January 2016 / Accepted: 27 March 2016

# Springer Science+Business Media New York 2016

Abstract A new type of fluorescent chemosensor based on

tethered hexa-borondipyrromethene cyclotriphosphazene
platform (HBTC) linked via triazole groups was designed
and synthesized. Its sensing behavior toward metal ions was
investigated by ultraviolet-visible and fluorescence spectroscopies. Addition of a Fe2+ ion to a tetrahydrofuran solution of
HBTC gave a visual color change as well as a significantly
quenched fluorescence emission, while other tested 19 metal
ions induced no color or spectral changes. This compound
was found to be highly selective and sensitive for Fe2+ with
a low limit of detection (2.03 M) which is, to the best of our
knowledge, the superior than the previously studied
chemosensors for Fe2+.
Keywords Cyclotriphosphazene . Borondipyrromethene .
Iron (II) . Fluorescent Sensor

Introduction
The development of selective and sensitive analytical methods
for detection of metal cations is important research area because of their important roles in environmental, biological and
industrial processes [15]. Up to now, countless analytical
methods that are used for the detection of metals such as
atomic absorption spectroscopy (AAS), inductively coupled
plasma atomic emission or inductively coupled plasma mass
spectroscopy (ICP-AES, ICP-MS), ion sensitive electrodes,
* Serkan Yeilot
yesil@gtu.edu.tr

Department of Chemistry, Gebze Technical University, P.O.Box:

141, 41400 Gebze, Kocaeli, Turkey

electron microprobe analysis, neutron activation analysis,

etc. These methods are expensive and requires large size of
samples. In the past two decades, detection of metal cations by
fluorescence methods has taken attention because of their significant advantages such as sensitivity, selectivity, rapid response time, local observation and lower detection limits
[610]. Fluorescence sensor applications for metal detection
can be carried out through the change of emission or absorption peak intensities. Numerous fluorescence sensor studies
for metal detection were performed to obtain high selectivity
while getting lower detection limits. Among various metal
elements, iron, can exist as Fe2+ and Fe3+ oxidation states
and both of them plays an important role and vital element
in living organisms because numerous enzymes and proteins
include iron in their structures. Also, in biological systems,
oxidation states (Fe2+ and Fe3+) of iron are one of the important redox pairs [1114].
The deficiency or excess amount of iron can damage cellular metabolism and some kind of diseases such as cancer,
hepatitis, Perkinson and Alzheimer may occur for this reason
[1517]. In living cells, most of chelatable iron ions available
as Fe2+ rather than Fe3+ because of higher water solubility of
Fe2+ and reductive environment of cells [1820]. Due to challenging the separation of Fe2+ from Fe3+, a large number of
fluorescence sensors have been detected Fe3+ and Fe2+ ions
simultaneously [15, 2126], but, a few Fe2+ selective fluorescence based sensors have been designed and synthesized until
now [2729]. Due to deficiency of Fe2+ fluorescence sensors,
the design of a new selective and sensitive Fe2+ fluorescent
sensor is still important.
Hexachlorocyclotriphosphazene is a hard inorganic ring
containing six labile groups that can be substituted with the
desired groups. Their physical and chemical properties can be
tailored by the choice of appropriate substituted (R) groups on
phosphorus atoms [30]. For example, it is possible to design

J Fluoresc

materials with special properties such as flame retardants [31],

antimicrobial agents [32], lithium-ion batteries [33], liquid
crystals [34], organic light emitting diodes [35] and fluorescent sensors [26]. There are lots of fluorescent organic compounds reported in the literature. Although these dyes are
known, borondipyrromethene (BODIPY) dyes have
steadily become famous and increased their popularity
over the past two decades because of their remarkable
properties such as high absorption coefficients, high fluorescence quantum yields, long excited state lifetimes, and
good solubility in organic solvents [3638].
Triazoles formed through copper (I) catalysed "click"
chemistry have become an increasingly common motif in
chemical sensors [39]. Furthermore, there are many examples in literature that triazoles are utilized as binding sites
for metal ions or anions [4043]. For examples, Fe2+-triazole complexes consists of linear chains in which the
neighboring iron atoms are triply bridged by the triazole
ligands through the nitrogen donor atoms [4447]. We
hypothesized that this linear arrangement of the Fe2+tris(triazole) complexation should be applied to
cyclotriphosphazene platform, which is chosen because
of its suitability to a preferred conformation having three
substituted groups on phosphorus atoms positioned above
and below to the plane of the phosphazene ring [4852],
in order to prepare the chemosensor for iron ions.
Thus with these considerations, hexa-BODIPY
substitued triazole linked cyclotriphosphazene (HBTC)
was synthesized as shown in Scheme 1. HBTC was
synthesized as a result of the Bclick^ reaction between
compound 1 [53] and BODIPY-based alkyne derivative
[54] in the presence of copper (I) catalyst, respectively
(Scheme 1). This novel compound was fully characterized by the standard spectroscopic techniques such as
1
H, 13C and 31P NMR, mass spectrometry (MALDI-

Scheme 1 Synthetic pathway for HBTC

TOF) and FT-IR spectroscopy and elemental analysis

as well.

Experimental
Materials and Reagents
All the reactions were performed under an atmosphere of
argon. Hexachlorocyclotriphosphazene(trimer), was purified
by fractional crystallization from n-hexane. Tetrahydrofuran
(THF) was distilled from sodium benzophenone. Analytical
thin layer chromatography (TLC) was performed on Silica
gel plates (Merck, Kieselgel 60, 0.25 mm thickness) with
F254 indicator. Chromatographic purifications were performed on silica gel (Merck, Kieselgel 60, 230400 mesh)
columns with the indicated eluents. The deuterated solvent
(CDCl3) for NMR spectroscopy and the following chemicals
were obtained from Merck; 4-hydroxybenzaldehyde,
triethylamine, boron trifluoride diethyl ether complex
(BF3OEt2), K2CO3, sodium azide, sodium hydride, N,N,N
,N,N-pentamethyldiethylenetriamine (PMDTA), dichloromethane, acetonitrile, n-hexane and tetrahydrofuran. 2,4Dimethyl-1H-pyrrole, trifluoroaceticacid (TFA) and 2,3dichloro-5,6-dicyano-p-benzoquinone (DDQ) were obtained
from Sigma-Aldrich. 2-Bromoethanol, copper(I) bromide,
propargyl bromide (80 % in toluene, stab. with MgO) was
obtained from Alfa-Aesar. 2,5-dihydroxy benzoic acid for
MALDI matrix were obtained from Fluka. All other reagents
and solvents were reagent grade quality and obtained from
commercial suppliers.
Instruments
Elemental analyses were carried out using Thermo
Finnigan Flash 1112 Instrument. UV/Vis spectra were
recorded with a Shimadzu 2101 UV spectrophotometer.
Fluorescence excitation and emission spectra were recorded on a Varian Eclipse spectrofluorometer using
1 cm pathlength cuvettes at room temperature. Infrared
spectra were recorded on a Perkin Elmer Spectrum 100
FT-IR spectrophotometer. Mass spectra were acquired in
linear modes with average of 50 shots on a Bruker
Daltonics Microflex mass spectrometer (Bremen,
Germany) equipped with a nitrogen UV-Laser operating
at 337 nm. Many different MALDI matrices such as 1,
8,9-antracenetriol, 3,5-dimethoxy-4-hydroxycinnamic acid, -cyano-4-hydroxycinnamic acid and 2,5-dihydroxy
benzoic acid were tried to find an intense molecular ion
peak and low fragmentation under the MALDI-MS conditions for these compounds. 2,5-dihydroxy benzoic acid
MALDI matrix yielded the best MALDI-MS spectra. 2,
5-dihydroxy benzoic acid (20 mg/mL in tetrahydrofuran)

J Fluoresc

matrix for HBTC was prepared. MALDI samples were

prepared by mixing compounds (2 mg/mL in tetrahydrofuran) with the matrix solution (1:10 v/v) in a 0.5 mL
Eppendorf micro tube. Finally 1 L of this mixture was
deposited on the sample plate, dried at room temperature and then analyzed. Analytical thin layer chromatography (TLC) was performed on Silica gel plates (Merck,
Kiesel gel 60, 0.25 mm thickness) with F254 indicator.
Column chromatography was performed on silica gel
(Merck, Kiesel gel 60, 230400 mesh; for 3 g. crude
mixture, 100 g silica gel was used in a column of 3 cm
in diameter and 60 cm in length) and preparative thin
layer chromatography was performed on silica gel 60 P
F254. 1H, 13C and 31P NMR spectra were recorded in
CDCl3 on a Varian 500 MHz spectrometer.

Synthesis
Compound 1 [53] and BODIPY-based alkyne derivative [54]
were prepared and purified according to the literature
procedures.

Synthesis of HBTC
A solution of trimeric compound (1) (20 mg,
0.031 mmol), BODIPY-based alkyne derivative
(143 mg, 0.22 mmol), copper (I) bromide (44 mg,
0.31 mmol) and PMDTA (53 mg, 0.32 mmol) in dry
dichloromethane (5 mL) in a sealed tube was stirred for
24 h at room temperature under an argon atmosphere.
The reaction mixture was poured into water and then
extracted with dichloromethane. The extract was washed
with water and brine and dried over anhydrous Na2SO4.
Evaporation of the solvent followed by silica gel column
chromatography (eluent: n-hexane:THF (3:2)) affords
compound (HBTC) as a red-orange solid (50 mg,
0.02 mmol) in 31 % yield. (Found: C 60.10, H 5.19, N
15.28 %, C144H150B6F12N33O12P3 (2920.7) requires C
59.22, H 5.18, N 15.83 %). FT-IR (ATR, cm 1) 2955
2870 (CH str), 1607 (C = N-), 1544 (N = N-), 1433
(N-N-), 1233 (P-N-P-), 1245 (P = N str), 1155 (PO-), 1084 (C-O-C str), 1025, 980 (P-O-C str). 1H NMR
(CDCl3) = 7.27 (s, 6H, pyrrole-H), = 7.227.08 (m,
30H, Ar-CH), = 6.10 (s, 6H, pyrrole-H), = 5.31 (s,
12H, O-CH2), = 4.77 (d, 24H, H2C-CH2-), = 2.56
(s, 36H, CH3), = 1.43 (s, 36H, CH3), 13C NMR
(CDCl3) = 158.6, 148.0, 143.6, 137.7, 135.6, 133.9,
132.0, 126.0, 124.4, 114.3, 113.5, 107.4, 65.9, 64.1,
57.5, 55.9, 49.8, 19.5, 15.9, 14.2, 14.1, 31 P NMR
(CDCl3), = 17.13 (s). MS (MALDI) m/z: 2901.3 [MF]+ calculated for C144H150B6F12N33O12P3.

Result and Discussion

Synthesis
HBTC was synthesized according to Scheme 1. Firstly,
trimeric compound 1 was prepared by the reaction of
hexachlorocyclotriphosphazene and 2-azido-1-ethanol in
the presence of NaH in THF at 0 C. Secondly, BODIPYbased alkyne derivative was prepared by treating 2,4dimethylpyrrole with 4-(prop-2-ynyloxy)benzaldehyde
via sequential condensation, oxidation and complexation
reactions. Finally, HBTC (Fig. 1) was prepared as a result
of the Bclick^ reaction between compound 1 and BODIPYbased alkyne derivative in the presence of copper (I) catalyst. This novel compound was fully characterized by the
standard spectroscopic techniques such as 1H, 13C and 31P
NMR, mass spectrometry (MALDI-TOF) and FT-IR spectroscopy and elemental analysis as well. All the results
were consistent with the predicted structure as shown in
the experimental section.
Photophysical Characteristics
Photophysical properties of HBTC were investigated by UVvis absorption and fluorescence experiments. The absorption
and fluorescence properties of HBTC have been studied in
different solvents such as water, cyclohexane, dichloromethane, dimethyl sulfoxide (DMSO), DMSO/water, THF/water
and THF. According to Fig. 2, the maximum absorption and
fluorescence signals of HBTC were obtained in THF. For this
reason we have chosen THF, which is also water miscible
organic solvent, to use in our study. The absorption and emission maxima of HBTC were observed at 502 and 513 nm

Fig. 1 Chemical structure of HBTC

J Fluoresc
Fig. 2 Fluorescence spectra of
HBTC (5 M) in different solvents. (Excitation
wavelength = 475 nm)

Fig. 3 Absorption and

fluorescence spectrum of HBTC
(5 M) in THF (Excitation
wavelength = 475 nm)

Fig. 4 Fluorescence emission

spectra of HBTC (5 M in THF)
after addition of 10 L of 0.1 M
different metal ions (Fe2+, Al3+,
Ba2+, Ca2+, Co2+, Ag+, Cd2+,
Cr3+, Cs+, Cu2+, Fe3+, Hg2+, K+,
Li+, Mg2+, Mn2+, Na+, Ni2+, Pb2+,
Zn2+, HBTC + other metals
except Fe2+, HBTC + metal
mixture). (Excitation
wavelength = 475 nm)

J Fluoresc

Fig. 5 Color change of HBTC (5 M in THF) under 365 nm light source

(a) absence of Fe2+ (b) presence of 100 eq. Fe2+

respectively, when excited at 475 nm in THF attributed to

BODIPY moiety Fig. 3 [55]. The chemosensor properties of
HBTC against to metal ions were investigated using UV-vis
and fluorescence spectroscopies. The stock solution of HBTC
was prepared in THF and nitrate salts of metal solutions were
prepared in water. All of the spectral measurements were carried out in a spectroscopic cuvette by using a micropipet at
25 C. A 29.3 L HBTC from stock solution (341 M) and
10 L metal ions were mixed then total volume of solutions
were adjusted to 2 mL with THF. For investigation competitive metal ions effect on optic properties of HBTC, 10 L
from 0.1 M of different metal ions (Fe2+, Al3+, Ba2+, Ca2+,
Co2+, Ag+, Cd2+, Cr3+, Cs+, Cu2+, Fe3+, Hg2+, K+, Li+, Mg2+,
Mn2+, Na+, Ni2+, Pb2+ and Zn2+) were added to solution of
(5 M in THF). As can be seen Fig. 4, on the contrary Fe2+
ions, competitive metal ions including Fe3+ cause meaningless
change in the fluorescence emission of HBTC when excited
at 475 nm. Only Fe2+ ions cause fluorescence quenching of
Fig. 6 UV-Vis titration of HBTC
(5 M in THF) with different
amount of Fe2+. Inset: Calibration
curve of absorption of HBTC
(5 M in THF) with Fe2+
concentration

emission band at 513 nm which attributed BODIPY moiety.

Figure 5 shows color changes of HBTC with absence and
presence of 100 eqv. Fe2+ in THF. After addition of 100 eqv.
Fe2+, color of HBTC turns yellow to brown because of
quenching of BODIPY moiety emission under 365 nm light
source.
In order to evaluate spectral changes of HBTC, titration
experiments with Fe2+ were carried out using both UV-vis and
fluorescence spectroscopies. Spectral changes of HBTC
which containing different concentrations (0100 M and
050 M) of Fe 2+ were shown in Fig. 6 and Fig. 7.
According to the fluorescence titration curve (Fig. 7), the peak
maxima at 513 nm for HBTC versus Fe2+ concentration were
plotted and a good linear fluorescence response and regression
coefficient (R2 = 0.9918) was observed ranging from 2.0 to
50 M (Fig. 8).
The detection limit which is one of the most important
parameter for fluorescence sensor applications calculated
using 3/k equation where is standard deviation of the
blank signal and k is slope of calibration curve (2.03 M
(0.114 ppm) for Fe2+) [5661]. The permitted maximum
level of iron ions (Fe2+ and Fe3+) in drinking water is
0.3 ppm according to The Environmental Protection
Agency (EPA) and World Health Organization (WHO)
[62, 63]. The detection limit found in this study is lower
than permissible level of iron ions in drinking water. For
this reason, HBTC can be used as a fluorescent sensor for
Fe2+ in environmental samples. Precision is an important
analytical parameter for sensor application. For this reason,
ten measurements were performed for 5 M of Fe2+ under
the same conditions. The relative standard deviation (%
RSD) was calculated as %1.18. According to these results,
high reproducibility can provided for selected sensor. To
evaluate the interaction and stoichiometry of HBTC and
Fe2+, the combination of Benesi-Hildebrand analysis and

J Fluoresc
Fig. 7 Fluorescence titration of
HBTC (5 M in THF) with
different amount of Fe2+.
(Excitation
wavelength = 475 nm)

Fig. 8 Calibration curve of

fluorescence intensity for HBTC
(5 M in THF) and Fe2+ (250 M)

Fig. 9 Jobs plot of fluorescence

of Fe2+ + HBTC complex in THF

J Fluoresc
Scheme 2 Proposed Fe2+
sensing mechanism of HBTC

the Continuous Variation (Jobs) method was used. As can

be seen in Fig. 9, when mole fraction of Fe2+ was 0.5,
emission of complex reached maximum value which demonstrates complex stoichiometry of HBTC to Fe2+ is 1:1
(Scheme 2). According to the BenesiHildebrand equation,
the association constant Ka of the Fe2+-HBTC complex
was calculated as 8.20x106 M1:
1
1
1

F F 0 K a  F max F 0  Fe2  F max F 0

where F is fluorescence response of sensor at 513 nm at
different Fe2+ concentration, Fo is fluorescence response of
free sensor, Fmax is maximum fluorescence intensity of sensor at 513 nm with Fe2+, in this equation, plotting 1/(F-Fo)
versus 1/[Fe2+] gave graphically the association constant Ka
(Fig. 10) [64, 65]. This Ka value was also supported the
Job's plot.

Fig. 10 BenesiHildebrand Plot

of 1/F0-F against 1/[Fe2+] in THF

Conclusion
In this paper, hexa-BODIPY substituted
cyclotriphosphazene linked by triazole ring (HBTC) was
synthesized and characterized. Its chemosensor behavior
against to the different metal ions (Fe2+, Al3+, Ba2+, Ca2+,
Co2+, Ag+, Cd2+, Cr3+, Cs+, Cu2+, Fe3+, Hg2+, K+, Li+,
Mg2+, Mn2+, Na+, Ni2+, Pb2+ and Zn2+) was investigated
in THF and this novel cyclotriphosphazene compound was
found excellent selective and sensitive fluorescence
chemosensor for Fe 2+. The complex stoichiometry of
HBTC and Fe2+ was determined as 1:1 (L/M) (Scheme 2)
using the method of continuous variation (Jobs plot). Also,
the detection limit of HBTC for Fe2+ was calculated as
2.03 M (0.114 ppm). According to these results, HBTC
is a potential selective and sensitive fluorescence
chemosensor for imaging Fe2+ in living cell and our studies
about this topic is underway.

J Fluoresc

References
1.
2.

3.

4.

5.
6.

7.
8.
9.

10.

11.

12.

13.
14.
15.

16.
17.

18.
19.

20.

21.

Carter KP, Young AM, Palmer AE (2014) Fluorescent sensors for

measuring metal ions in living systems. Chem Rev 114:45644601
Wu J, Liu W, Ge J, Zhang H, Wang P (2011) New sensing mechanisms for design of fluorescent chemosensors emerging in recent
years. Chem Soc Rev 40:34833495
Zhang JF, Zhou Y, Yoon J, Kim JS (2011) Recent progress in
fluorescent and colorimetric chemosensors for detection of precious
metal ions (silver, gold and platinum ions). Chem Soc Rev 40:
34163429
Kim HN, Guo Z, Zhu W, Yoon J, Tian H (2011) Recent progress on
polymer-based fluorescent and colorimetric chemosensors. Chem
Soc Rev 40:7993
Harris ZL, Gitlin JD (1996) Genetic and molecular basis for copper
toxicity. Am J Clin Nutr 63:836S841S
Czarnik AW (ed) (1993) Fluorescent chemosensors for ion and
molecular recognition, ACS Symposium Series, vol 358. ACS,
Washington, DC
Lakowicz JR (ed) (1994) Topics in fluorescence spectroscopy, vol
4. Probe Design and Chemical Sensing. Plenum Press, New York
Fabbrizzi L, Poggi A (1995) Sensors and switches from supramolecular chemistry. Chem Soc Rev 24:197202
Desvergne JP, Czarnik AW (eds) (1997) Chemosensors of ion and
molecule recognition, NATO ASI Series. Kluwer Academic
Publishers, Dordrecht
De Silva AP, Gunaratne HQN, Gunnlaugsson T, Huxley AJM,
McCoy CP, Rademacher JT, Rice TE (1997) Chem Rev 97:1515
1566
Frausto da Silva JJR, Williams RJP (1991) The biological chemistry of the elements: the inorganic chemistry of life. Oxford
University Press, New York
Matsumiya H, Iki N, Miyano S (2004) Sulfonylcalix
[4]arenetetrasulfonate as pre-column chelating reagent for selective
determination of aluminum(III), iron(III), and titanium(IV) by ionpair reversed-phase high-performance liquid chromatography with
spectrophotometric detection. Talanta 62:337342
Lippard SJ, Berg JM (1994) Principles of Bioinorganic chemistry.
University Science Books, Mill Valley
Kaim W, Schwederski B (1995) Bioinorganic chemistry, 2nd edn.
Wiley, New York
Fakih S, Podinovskaia M, Kong X, Collins HL, Schaible UE, Hider
RC (2008) Targeting the lysosome: fluorescent iron(III) chelators to
selectively monitor endosomal/lysosomal labile iron pools. J Med
Chem 51:45394552
McRae R, Bagchi P, Sumalekshmy S, Fahrni C (2009) In situ imaging of metals in cells and tissues. Chem Rev 109:47804827
Zecca L, Youdim MBH, Riederer P, Conner JR, Crichton RR
(2004) Iron, brain ageing and neurodegenerative disorders. Nat
Rev Neurosci 5:863873
Breuer W, Shvartsman M, Cabantchik ZI (2008) Intracellular labile
iron. Int J Biochem Cell Biol 40:350354
Petrat F, De Groot H, Rauen U (2001) Subcellular distribution of
chelatable iron: a laser scanning microscopic study in isolated hepatocytes and liver endothelial cells. Biochem J 356:6169
Richardson DR, Lane DJ, Becker EM, Huang ML, Whitnall M,
Rahmanto YS, Sheftel AD, Ponka P (2010) Mitochondrial iron
trafficking and the integration of iron metabolism between the mitochondrion and cytosol. Proc Natl Acad Sci U S A 107:10775
10782
Esposito BP, Epsztejn S, Breuer W, Cabantchik ZI (2002) A review
of fluorescence methods for assessing labile iron in cells and biological fluids. Anal Biochem 304:118

22.

23.

24.

25.

26.

27.

28.

29.

30.
31.

32.

33.

34.

35.

36.
37.
38.

39.

40.
41.

Ma Y, Luo W, Quinn PJ, Hider RC (2004) Design, synthesis, physicochemical properties, and evaluation novel iron chelators with
fluorescent sensors. J Med Chem 47:63496362
Fakih S, Podinovskaia M, Kong X, Schaible UE, Collins HL,
Hilder RC (2009) Monitoring intracellular labile iron pools: a novel
fluorescent iron(III) sensor as a potential non-invasive diagnosis
tool. J Pharm Sci 98:22122226
Queiros C, Silva AMG, Lopes SC, Ivanova G, Gameiro P, Rangel
M (2012) A novel fluorescein-based dye containing a catechol chelating unit to sense iron(III). Dyes and Pigm 93:14471455
Mei Q, Jiang C, Guan G, Zhang K, Liu B, Liu R, Zhang Z (2012)
Fluorescent graphene oxide logic gates for discrimination of iron
(3+) and iron (2+) in living cells by imaging. Chem Commun 48:
74687470
Kagt R, Yildirim M, Ozay O, Yesilot S, Ozay H (2014)
Phosphazene based multicentered naked-eye fluorescent sensor
with high selectivity for Fe3+ ions. Inorg Chem 53:21442151
Petrat F, Rauen U, De Groot H (1999) Determination of the chelatable iron pool of isolated rat hepatocytes by digital fluorescence
microscopy using the fluorescent probe, phen green SK.
Hepatology 29:11711179
Petrat F, Weisheit D, Lensen M, De Groot H, Sustmann R, Rauen U
(2002) Selective determination of mitochondrial chelatable iron in
viable cells with a new fluorescent sensor. Biochem J 326:137147
Rauen U, Springer A, Weisheit D, Petrat F, Korth HG, De Groot H,
Sustmann R (2007) Assessment of chelatable mitochondrial iron by
using mitochondrion-selective fluorescent iron indicators with different iron-binding affinities. Chem Bio Chem 8:341352
Mark JE, Allcock HR, West R (1992) Inorganic polymers.
Englewood Cliffs, NJ, Prentice Hall
Tao K, Li J, Xu L, Zhao X, Xue L, Fan X, Yan Q (2011) A novel
phosphazene cyclomatrix network polymer: design, synthesis and
application in flame retardant polylactide. Polym Degrad Stab 96:
12481254
Dallas P, Sharma VK, Zbori R (2011) Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic
paths, applications, and perspectives. Adv Colloid Interface Sci
166:119135
Sazhin SV, Harrup MK, Gering KL (2011) Characterization of low
flammability electrolytes for lithium-ion batteries. J Power Sources
196:34333438
Jimenez J, Laguna A, Molter AM, Serrano JL, Barbera J, Oriol L
(2011) Supramolecular liquid crystals with a six-armed
cyclophosphazene core: from columnar to cubic phases. Chem
Eur J 17:10291039
Soh MS, Santamaria SAG, Williams EL, Perez-Morales M, Bolink
HJ, Sellinger A (2011) Solution processable high band gap hosts
based on carbazole functionalized cyclic phosphazene cores for
application in organic light-emitting diodes. J Polym Sci Part B:
Polym Phys 49:531539
Aurore L, Kevin B (2007) BODIPY dyes and their derivatives:
syntheses and spectroscopic properties. Chem Rev 107:48914932
Ziessel R, Ulrich G, Harriman A (2007) The chemistry of bodipy: A
new El Dorado for fluorescence tools. New J Chem 31:496501
Ulrich G, Ziessel R, Harriman A (2008) The chemistry of fluorescent bodipy dyes: Versatility unsurpassed. Angew Chem Int Ed 47:
11841201
Lau YH, Rutledge PJ, Watkinson M, Todd MH (2011) Chemical
sensors that incorporate click-derived triazoles. Chem Soc Rev 40:
28482866
Elliott PIP (2014) Chapter 1: Organometallic complexes with 1,2,3triazole-derived ligands. Organomet Chem 39:125
Hanni KD, Leigh DA (2010) The application of CuAAC click
chemistry to catenane and rotaxane synthesis. Chem Soc Rev 39:
12401251

J Fluoresc
42.

Hua Y, Flood AH (2010) Click chemistry generates privileged CH

hydrogen-bonding triazoles: the latest addition to anion supramolecular chemistry. Chem Soc Rev 39:12621271
43. Struthers H, Mindt TL, Schibli R (2010) Metal chelating systems
synthesized using the copper(I) catalyzed azide-alkyne cycloaddition. Dalton Trans 39:675696
44. Ferrer AS, Braunlich I, Ruokolainen J, Bauer M, Schepper RI,
Smith P, Caseri W, Mezzenga R (2014) Gels, xerogels and films
of polynuclear irn(II)-aminotriazole spin-crossover polymeric
complexes. RSC Adv 4:6084260852
45. Kuroiwa T, Shibata T, Sasaki S, Ohba M, Takahara A, Kunitake TI,
Kimizuka N (2006) Supramolecular control of spin-crossover phenomena in lipophilic Fe(II)-1,2,4-triazole complexes. J Polym Sci:
Part A: Polym Chem 44:51925202
46. Rubio M, Lopez D (2009) Effect of solvent on the gelation properties of metallo-organic polymer of [Fe(II) (4-octadecyl-1,2,4triazole)3(ClO4)2]n. Eur Polym J 45:33393346
47. Fujigaya T, Jiang DL, Aida T (2007) Spin-crossover physical gels:
a quick thermoreversible response assisted by dynamic self-organization. Chem Asian J 2:106113
48. Cosut B, Yesilot S (2012) Synthesis, thermal and photopysical
properties of naphthoxycyclotriphosphazenyl-substituted
dendrimeric cyclic phosphazenes. Polyhedron 35:101107
49. Badetti E, Lloveras V, Wurst K, Sebastian RM, Caminade AM,
Majoral JP, Veciana J, Ganceda JV (2013) Synthesis and structural
characterization of a dendrimer model compound based on a
cyclotriphosphazene core with TEMPO radicals as substituents.
Org Lett 15:34903494
50. Keller M, Colliere V, Reiser O, Caminade AM, Majoral JP, Ouali A
(2013) Pyrene-tagged dendritic catalysts noncovalently grafted onto magnetic Co/C nanoparticles:an efficient and recyclable system
for drug synthesis. Angew Chem Int Ed 52:36263629
51. Caminade AM, Majoral JP (2013) Positively charged phosphorus
dendrimers. an overview of their properties. New J Chem 37:3358
3373
52. Yeilot S, Cosut B, Alida HA, Hacveliolu F, zpnar GA, Kl
A (2014) Intramolecular;excimer formation in
hexakis(pyrenyloxy)cyclotriphosphazene: photophysical properties, crystal structure, and theoretical investigation. Dalton Trans
43:34283433
53. Un I, Ibiolu H, Un SS, Cosut B, Klc A (2013) Syntheses,
characterisations, thermal and photopysical properities of
cyclophosphazene containing adamantine units. Inorg Chim Acta
399:219226

54.

Atilgan S, Ozdemir T, Akkaya EU (2010) Selective Hg(II) sensing

with improved stokes shift by coupling the internal charge transfer
process to excitation energy transfer. Org Lett 12:47924795
55. Liu JY, Yeung HS, Xu W, Li X, Ng DKP (2008) Highly efficient
energy transfer in Subphthalocyanine BODIPY Conjugates. Org
Lett 10:54215424
56. Joshi S, Kumari S, Bhattacharjee R, Sarmah A, Sakhuja R, Pant DD
(2015) Experimental and theoretical study: determination of dipole
momentof synthesized coumarintriazole derivatives and application as turnoff fluorescence sensor: high sensitivity for iron(III)
ions. Sensors Actuators B Chem 220:12661278
57. Choi YW, Park GJ, Na YJ, Jo HY, Lee SA, You GR, Kim C (2014)
A single schiff molecule for recognizing multiple metal ions: A
fluorescence sensor for Zn(II) and Al(III) and colorimetric sensor
for Fe(II) and Fe(III). Sensors Actuators B Chem 194:343352
58. Beltrn OG, Cassels BK, Prez C, Mena N, Nez MT, Martnez
NP, Pavez P, Aliaga ME (2014) Coumarin-based fluorescent probes
for dual recognition of copper(II) and iron(III) ions and their application in bio-imaging. Sensors 14:13581371
59. Shi D, Ni M, Luo J, Akashi M, Liu X, Chen M (2015) Fabrication
of novel chemosensors composed of rhodamine derivative for the
detection of ferric ion and mechanism studies on the interaction
between sensor and ferric ion. Analyst 140:13061313
60. Chen BY, Kuo CC, Huang YS, Lu ST, Liang FC, Jiang DH (2015)
Novel highly selective and reversible chemosensors based on dualratiometric fluorescent electrospun nanofibers with pH- and Fe3 +
modulated multicolor fluorescence emission. ACS Appl Mater
Interfaces 7:27972808
61. Saithongdee A, Praphairaksit N, Imyim A (2014) Electrospun
curcumin-loaded zein membrane for iron(III) ions sensing.
Sensors Actuators B Chem 202:935940
62. World Health Organization, Guidelines for Drinking Water Quality,
4th ed., Geneva, (2011) http://www.who.int/water_sanitation_
health/publications/dwq_guidelines/en/
63. United States Environmental Protection Agency. National Primary
Drinking Water Regulations, 816-F-09-0004, Washington DC,
(2009) http://www.epa.gov/safewater/
64. Li Z, Zhou Y, Yin K, Yu Z, Li Y, Ren J (2014) A new fluorescence
Bturn-on^ type chemosensor for Fe3+based on naphthalimide and
coumarin. Dyes Pigments 105:711
65. Liu SR, Wu SP (2012) New water-soluble highly selective fluorescent chemosensor for Fe (III) ions and its application to living cell
imaging. Sensors Actuators B 171-172:11101116