9-diphenylaminoacridines as molecular fluorescent chemosensors for determining polar solvent and amine vapors

Article abstract of DOI:10.1134/S0018143913060076

The results of study of the photophysical properties of three fluorophores from the 9-diphenylaminoacridine series in solutions are presented. It has been shown that the photoinduced synthesis of 9-diphenylaminoacridines in polymer films and on the surfac

Full text of DOI:10.1134/S0018143913060076

ISSN 0018ꢀ1439, High Energy Chemistry, 2013, Vol. 47, No. 6, pp. 339–345. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.A. Sazhnikov, V.M. Aristarkhov, S.K. Sazonov, A.I. Vedernikov, S.P. Gromov, M.V. Alfimov, 2013, published in Khimiya Vysokikh Energii, 2013, Vol. 47,
No. 6, pp. 490–496.
PROCESSES AND MATERIALS FOR OPTICAL
INFORMATION SYSTEMS
9ꢀDiphenylaminoacridines as Molecular Fluorescent Chemosensors
for Determining Polar Solvent and Amine Vapors
V. A. Sazhnikov, V. M. Aristarkhov, S. K. Sazonov, A. I. Vedernikov, S. P. Gromov, and M. V. Alfimov
Photochemistry Center, Russian Academy of Sciences, ul. Novatorov 7a, Moscow, 119421 Russia
eꢀmail: sazhnikov@yandex.ru
Received April 26, 2013; in final form, May 13, 2013
Abstract—The results of study of the photophysical properties of three fluorophores from the 9ꢀdiphenyꢀ
laminoacridine series in solutions are presented. It has been shown that the photoinduced synthesis of
9ꢀdiphenylaminoacridines in polymer films and on the surface of polymeric microꢀ and nanoparticles can be
used for detection of polar solvent and amine vapors.
DOI: 10.1134/S0018143913060076
Studying the properties of acridine and its derivaꢀ
In this paper, we show that 9ꢀdiphenylamiꢀ
tives, in particular 9ꢀaminoacridine and 9ꢀanilinoꢀ noacridines, introduced into a polymer film or proꢀ
acrine, is of interest largely because of their numerous duced in a film by photoinduced synthesis, are molecꢀ
applications as bioactive molecules in biology and ular chemosensors useful as fluorescent indicators of
medicine owing to the ability of the acridine cycle to electronꢀ or protonꢀacceptor compounds, in particuꢀ
form ꢀcomplexes with nucleic acid bases [1–3]. It lar chlorinated solvents, ammonia, and pyridine, in
π
was found that the formation of ternary 9ꢀanilinoacriꢀ the vapor phase.
dine/DNA/enzyme complexes via further complexꢀ
ation of the aniline moiety with proteins is also possiꢀ
ble [4].
EXPERIMENTAL
All the solvents (Aldrich) were of the grade “for UV
spectroscopy” and were used without further purificaꢀ
tion. The reactants used for the photoinduced syntheꢀ
sis of 9ꢀdiphenylaminoacridine fluorophores in soluꢀ
tions and polymer layers were diphenylamine and its
derivatives that bear the methyl (ditolylamine) or the
dimethylbenzyl (4,4'ꢀbis(alpha,alphaꢀdimethylbenꢀ
zyl)diphenylamine) group in the paraꢀposition. Tetraꢀ
Much attention has been given to the spectralꢀandꢀ
luminescent properties of 9ꢀarylaminoacridine derivꢀ
atives and the acridinium ion characterized by
intramolecular electron transfer from the donor moiꢀ
ety (e.g., dimethylaniline) to acridine, which acts as
the acceptor moiety, upon electronic excitation [5, 6].
The dependence of the fluorescence spectra of such
donor–acceptor compounds on the polarity of the
medium was used to design sensors for determining
small amounts of water in organic solvents [7]. It
should also be noted that the feasibility of the formaꢀ
tion of intramolecular electronꢀtransfer states with a
very long lifetime was proved for the 9ꢀmesitylꢀ10ꢀ
methylacridinium ion [8–10].
bromomethane (TBM), diphenylamine (DPA), diꢀpꢀ
tolylamine (DTA), and (4,4'ꢀbis(alpha,alphaꢀdimethꢀ
ylbenzyl)diphenylamine) (DMBDPA) (Fluka, Aldꢀ
rich, Merck) was used without further purification.
The choice of DTA and DBMDFA as reactants was
based on the fact that the synthesis of nonfluorescent
triphenylmethane dyes is blocked in this case [11–13].
According to the reaction mechanism described [11–
13], HBr is released during the photoinduced syntheꢀ
sis and results in protonation of the photoreaction
products.
Previously [11], it was found that UV irradiation of
diphenylamine and tetrabromomethane solutions in
toluene or hexane yields 9ꢀdiphenylaminoacridine
along with triphenylmethane dyes. It was also shown
that the use of tetrabromomethane and various dipheꢀ
nylamine derivatives allows for the photoinduced synꢀ
thesis of acridine, phenylacridine, 9ꢀditolylamiꢀ
noacridine (9ꢀDTAA), etc. in solutions [12]. A possiꢀ
ble reaction mechanism of the photoinduced synthesis
of these compounds is described in [11–14].
The synthesis procedure described in [11–13, 15]
comprises irradiating a solution of an appropriate
amine and TBM in hexane with full light from a
DRShꢀ1000 lamp for 4–6 h, dissolving the precipitate
in benzene, washing with an aqueous sodium bicarꢀ
bonate solution, evaporating in a vacuum, and purifyꢀ
The compounds synthesized, in particular 9ꢀDTAA, ing the product by recrystallization or column chroꢀ
exhibit wellꢀdefined solvatofluorochromic properties matography. The structural formulas of synthesized
[15].
compounds 1–3 are shown in Fig. 1. The melting
339

340
SAZHNIKOV et al.
CH3
CH3
H3C
H3C
H3C
H3C
CH3
CH3
H3C
H3C
CH3
CH3
N
N
N
N
N
N
1
2
3
Fig. 1. Structural formulas of synthesized 9ꢀdiphenylaminoacridines.
points of crystalline
(9ꢀdiphenylaminoacridine, 9ꢀDPAA,
thylꢀ ꢀdimethylꢀ ꢀdiꢀ ꢀtolylacridineꢀ9ꢀamine
(9ꢀditolylaminoacridine, 9ꢀDTAA, ), and 2,7ꢀbis(2ꢀ the films was 20–40
phenylpropanꢀ2ꢀyl)ꢀ ꢀbis(4ꢀ(2ꢀphenylpropanꢀ2ꢀ prepared by the spin coating technique using an SCS
) are 225, 261, 6720D device.
N
,
N
ꢀdiphenylacridineꢀ9ꢀamine ene were mixed with a 10% polymer solution in toluꢀ
), 2,7ꢀdimeꢀ ene and the mixture was applied onto a glass substrate
with a dispenser and dried. The average thickness of
m. Thin polystyrene films were
1
N,N
N,N
p
2
μ
N,N
yl)phenyl)acridineꢀ9ꢀamine (DBAA,
and 179°C, respectively.
3
The substrates with the samples were placed in a
saturated solvent vapor atmosphere, and a change in
the fluorescence signal intensity was monitored using
an SDꢀ2000 fiberꢀoptic spectrofluorimeter and Ocean
Optics fluorescent probes. A lightꢀemitting diode with
The absorption spectra of solutions of 1–3 were
recorded on a Shimadzu UVꢀ3101 PC spectrophoꢀ
tometer, and the fluorescence spectra were measured
with a Shimadzu RFꢀ5301 PC spectrofluorometer.
The standards used for measuring the fluorescence
quantum yields were fluorescein and Rhodamine 123;
their quantum yields were assumed to be 0.9. The fluꢀ
orescence lifetime was measured by the phase moduꢀ
lation technique with a Fluorologꢀ3 instrument (Jobin
Yvon, France).
λ
= 375 nm was used as a light source.
To run the photoinduced synthesis of
compounds 1–3 in polystyrene layers, solutions of the
reactant amines and tetrabromomethane in toluene
(10–1 mol/L) were applied onto a glass substrate with a
dispenser or by spin casting and irradiated with UV
light.
As a polymer matrix for preparing sensor layers
based on neutral fluorophores 1–3, unplasticized
polystyrene (
M = 280000, Aldrich) was used. To preꢀ
pare samples, solutions of 1–3 (10–3 mol/L) in toluꢀ
RESULTS AND DISCUSSION
The absorption spectrum of
orescence spectra in a number of solvents are given in
[15]. The absorption spectra of and in hexane are
almost identical to the spectrum of , which has
2 in hexane and its fluꢀ
0.30
1
1
3
2
0.25
absorption maxima at 290, 360, and 450 nm. All the
three compounds are characterized by a small bathoꢀ
chromic shift (of 300 to 500 cm–1) of the longꢀwaveꢀ
length band on passing to a polar solvent (THF, aceꢀ
tone, DMSO). The molar absorption coefficients at
maximum of the longꢀwavelength band in all solvents
2
1
0.20
0.15
0.10
0.05
0
2
3
are about 11000 L mol–1 cm–1 on average for
1 and 2
and about 15000 L mol–1 cm–1 for
3.
3
The absorption spectra of the protonated forms of
1–3 were prepared by adding hydrochloric acid to
dilute solutions in methanol (Fig. 2). It can be seen that
the maxima of the longꢀwavelength bands for the protoꢀ
nated forms 1+ 3+ lie in the region of 520–540 nm.
–
350 400 450 500 550 600 650 700
Wavelength, nm
Thus, the protonation of the nitrogen atom in the acriꢀ
dine cycle leads to quite a strong bathochromic shift
(about 80 nm) of the longꢀwavelength absorption bands
Fig. 2. Absorption spectra of protonated 9 diphenylamiꢀ
noacridines
+
+
–5
of
for
1
1
–
and
3
. The molar absorption coefficient is increased
1 –3 in acidified methanol (с = 10 mol/L,
с(HCl ) = 0.5 mol/L, the arrows show band assignment).
2
(to 19000 and 16000 L mol–1 cm–1, respecꢀ
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9ꢀDIPHENYLAMINOACRIDINES AS MOLECULAR FLUORESCENT CHEMOSENSORS
341
tively) and decreased for
protonation.
3
(to 7000 L mol–1 cm–1) by
515 537
580 586
800
600
400
200
0
Unlike the case of absorption spectra, the fluoresꢀ
cence maxima of neutral 9ꢀdiphenylaminoꢀ
acridines 1–3 are bathochromically shifted to a sigꢀ
nificant extent (by 3000 to 5000 cm–1) on passing from
cyclohexane (λmax = 470 nm) to polar solvents. As an
example, Fig. 3 shows the fluorescence spectra of 2 in
1
2
3
4
the chlorinated solvents tetrachloromethane (TCM),
trichloromethane (TrCM), and dichloromethane
(DCM). For comparison, the spectrum in toluene is
also shown. As seen from Fig. 3, the fluorescence band
of 9ꢀDTAA in nonpolar TCM is shifted toward shorter
wavelengths (λmax = 515 nm) relative to weakly polar
toluene (λmax = 537 nm), whereas there are significant
bathochromic shifts (65–70 nm) for TrCM and DCM
having a large dipole moment. In [15] it was shown
480
520
560
600
640
680
Wavelength, nm
that the strong solvatochromic effect for
2 can be
explained in terms of an increase in the dipole
moment from 2 to 12 debyes upon the transition to the
first singlet excited state. It is obvious that a similar
change in the dipole moments by excitation should be
Fig. 3. Normalized fluorescence spectra of a 9ꢀDTAA (
solution in tetrachloromethane, toluene,
) trichloromethane, and ( ) dichloromethane. The figꢀ
ures refer to the position of the band maxima.
2)
(1)
(2)
(
3
4
assumed for compounds
The table presents data on the quantum yields and
the fluorescence lifetimes of in different solvents.
Similar data were obtained for and . It is seen that
an increase in solvent polarity, which is characterized
by the Reichardt index T(30) [16], leads to a decrease
in both the quantum yield and the lifetime of fluoresꢀ
cence of . Calculation by the conventional relationꢀ
ships kr ϕF τF and nr = (1 – ϕF)/τF shows that the
observed changes in ϕF and τF with the increasing of
solvent polarity correlate with the decrease in the radiꢀ
ative transition rate constant kr and the increase in the
nonradiative transition rate constant knr, which is the
1 and 3.
of the fluorescence band, the decrease in the probabilꢀ
ity of radiative transitions with the increasing waveꢀ
length (Strickler–Berg equation [18]) and the increase
in the probability of the nonradiative decay of the first
excited state by the enhancement of vibronic interacꢀ
tions with the ground state on reducing the energy gap
between the states [19]. The contribution of intersysꢀ
tem crossing processes to the decay of the first singlet
2
1
3
E
2
=
/
k
state of 9ꢀdiphenylaminoacridines
arate investigation.
1–3 calls for a sepꢀ
Note that no appreciable fluorescence in the red
sum of the internal conversion and intersystem crossꢀ region of the spectrum could be detected in the case of
ing rate constants. By analogy with the case of solꢀ excitation to the longꢀwavelength absorption band of
vatofluorochromic Nile Red [17], this behavior can be protonated molecules 1+ 3+ in acidified methanol
–
qualitatively explained in terms of two basic factors solutions. Most likely, this is a consequence of both
resulting from the bathochromic shift of the maximum relatively low quantum yields of fluorescence and its
Quantum yields of fluorescence, fluorescence lifetimes, and rate constants of radiative and nonradiative transitions for
compound
2
kr
knr
Solvent
E
T(30), kcal/mol
ϕF
τ
F, ns
107 s–1
Cyclohexane
Toluene
30.9
33.9
36.0
36.2
39.1
42.2
45.1
45.6
48.4
0.57
0.30
0.27
0.15
0.13
0.06
0.02
0.03
0.008
29.3
27.0
24.2
18.9
18.0
12.5
10.2
7.8
1.95
1.11
1.12
0.79
0.72
0.48
0.20
0.38
0.11
1.47
2.59
3.02
4.50
4.83
7.52
9.61
Dioxane
THF
Chloroform
Acetone
DMSO
Acetonitrile
Propanol
12.4
13.78
7.2
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1800
SAZHNIKOV et al.
515
2700
2400
2100
1800
1500
1200
900
515
1600
1400
1200
1000
800
600
400
200
0
537
564
600
300
0
460 480 500 520 540 560 580 600 620 640 660 680
460 480 500 520 540 560 580 600 620 640 660 680
Wavelength, nm
Wavelength, nm
Fig. 5. Change with time of the fluorescence spectrum of a
PS film doped with 9ꢀDTAA (2) during holding in saturated
Fig. 4. Change with time of the fluorescence spectrum of a
trichloromethane vapor (curves were recorded at 3ꢀs interꢀ
vals).
PS film doped with 9ꢀDTAA (2) during holding in satuꢀ
rated toluene vapor (curves were recorded at 3ꢀs intervals).
additional quenching due to hydrogen bonding with of the band to shorter wavelengths is fast enough (30 s)
alcohol molecules.
only for the region from 560 to 530 nm and the final
comeback from 530 nm to the initial spectrum with
the maximum at 515 nm takes a longer time (to 100–
300 s). This is presumably due to the fact that the
energy of interaction of the 9ꢀDTAA molecule with
one or two TrCM molecules remaining in the solvation
shell has a relatively large value.
The spectral change processes and the rate curves
for dichloromethane are similar to those for trichloꢀ
romethane. The maximum of the 9ꢀDTAA fluoresꢀ
cence band is shifted stronger (to 574 nm) by saturaꢀ
tion with DCM vapor than in the case of TrCM, but
the observed shift is also smaller than that in the DCM
solution (586 nm).
Unlike the case of polar TrCM and DCM, holding
the PS–DTAA film in vapor of nonpolar tetrachloꢀ
romethane (TCM) only leads to a uniform decrease in
fluorescence intensity without changing the position
of the fluorescence band maximum. By itself, this
finding is of interest in relation to the sensor properties
It was found that polystyrene (PS) films doped with
compounds
1–3 exhibit quite bright fluorescence
peaked at 510–520 nm when excited with LED at
375 nm.
The data presented in Fig. 4 show that holding
these films in saturated toluene vapor leads to a shift of
the fluorescence maximum to 537 nm, which correꢀ
sponds to the maximum of fluorescence of
toluene (Fig. 3). The observed changes most likely
reflect the process of completion of the solvation shell
λ
=
2 in pure
about the molecules of
2 to the shell characteristic of
pure toluene by toluene molecules diffusing into the
film. The fluorescence variation process is fully reversꢀ
ible: after removing the sample from the toluene vapor
atmosphere, the spectrum is quickly (20 s) and fully
restored.
Figure 5 shows the change in the fluorescence
spectrum of the PS film after its holding for several
minutes in a saturated trichloromethane vapor atmoꢀ
sphere. It can be seen that as CHCl3 molecules diffuse
into the film, the fluorescence intensity decreases and
the maximum of the fluorescence band simultaꢀ
neously shifts to a significant extent toward longer
wavelengths (from 515 to 564 nm), although the shift
is smaller than in the chloroform solution (shifting to
580 nm). Note that the shift to 580 nm cannot be
attained even upon a very long exposure. The intensity
decay kinetics is almost linear in character.
of PS layers doped with 1–3 because it means that any
TCM vapor present in air can be distinguished from a
DCM or TrCM vapor by the character of change in the
fluorescence spectrum.
As noted above, the photoinduced synthesis of
compounds 1–3 from DMF, DTA, and DMBDFA
with TBM can be carried out in hexane or toluene
solutions at room temperature [11]. It was also found
that the photoinduced synthesis reactions occur in
It is obvious that this behavior can be explained in polystyrene films as well if they contain the reactant
terms of partial solvation of fluorophore by polar amine and TBM in sufficient concentrations. More
2
TrCM molecules. The observed spectral changes as a recently, this process was studied in more detail by
whole are reversible too. However, during the evaporaꢀ Budyka et al. [14]. Figure 6 shows that the spectral
tion of TrCM molecules from the film, the reverse shift changes during the reactions resulting from the UV
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1.2
1.0
0.8
0.6
0.4
0.2
0
645
300
670
200
2
3
100
1
550
600
650
Wavelength, nm
700
400
500
600
700
800
Wavelength, nm
Fig. 7. Change with time of the fluorescence spectrum of
+
3
in the PS film containing the reactants DMBDPA
(10⎯ mol/L) and TBM (10 mol/L) during irradiation
with a lightꢀemitting diode at = 375 nm. The curves
were recorded at intervals of 10 s.
1
–1
Fig. 6. Absorption spectra of a PSꢀfilm containing DPA
and tetrabromomethane ( ) before and after ( ) irradiation
with UV light and ( ) holding in ammonia vapor.
1
2
λ
max
3
irradiation of PS films containing DPA and TBM with
concentrations of 10–2–10–1 mol/L are similar to
those that occur in the solutions [11–13].
The reactants in the PS films form DPA/TBM
chargeꢀtransfer complexes, which have the absorption
spectrum at wavelengths shorter than 400 nm. By UV
irradiation, the film is colored as a result of the formaꢀ
tion of both primary photoproducts having an absorpꢀ
tion maximum at 670 nm and, apparently, protonated
9ꢀDPAA 1+ with an absorption maximum at about
results in almost complete conversion of green into red
fluorescence.
The most likely explanation is the assumption that
the red luminescence is due to the appearance of the
protonated form 2+, which readily gives up the proton
to ammonia or an organic base having a higher proton
affinity compared with
via the addition to of the HCl molecule that is genꢀ
erated by the reaction of photoinduced electron transꢀ
2
. Protonated 2+ can be formed
2
fer from 2 to CCl4 and the subsequent irreversible disꢀ
sociation of the radical anion CCl4 to the Cl– ion and
the CCl3 radical.
530 nm. Over time, the initial spectrum (curve
transforms into a spectrum characteristic of neutral
9ꢀDPAA (curve ). This process can be greatly accelꢀ
2)
3
Thus, when Cl– is a counterion for +, fluorescence
2
erated by warming the samples with hot air or exposing
them to ammonia vapor.
in the red region of the spectrum is easy to detect and
can be used for analytical purposes. Figure 9 shows the
conversion of the initial weak red fluorescence of the
film into bright green fluorescence by the action of satꢀ
urated pyridine vapor.
It should be noted that the protonated products
9ꢀDPAA+ 1+ and 9ꢀDTAA+ 2+
( ) ( ) seem to have a relꢀ
atively low fluorescence quantum yield in the case
when the counterion is the anion Br–. However, it was
found that 9ꢀDBAA+ 3+
( ) bearing bulky substituents
These data indicate that the synthesized comꢀ
pounds 1–3 can form chargeꢀtransfer complexes with
TCM, like the reactant arylamines. This in turn means
in the paraꢀposition has quite a high quantum yield
under these conditions. Figure 7 shows time changes
in the fluorescence intensity of the PS film in which
the photoinduced synthesis of 3+ takes place under
exposure to light. In the presence of amine or pyridine
vapor, this film changes the fluorescence color from
red to green.
that the reactions of formation of photoproducts 1–3
from arylamines and tetrabromomethane are selfꢀsenꢀ
sitized, since the photoreaction products themselves
are sensitizers of the subsequent formation of moleꢀ
cules
1–3.
It should be noted that in the above case of
It was shown that the effect of selfꢀsensitization
the action of TCM vapor on the PS layers with neutral leads to an exponential increase in the amount of the
9ꢀDTAA, a new, though less intense fluorescence band photoproducts formed at the site of irradiation of the
appears in the red region of the spectrum with a maxiꢀ film with visible light (e.g., 630ꢀnm light from a
mum at 630 nm along with the reduction in the intenꢀ helium–neon laser). In principle, this effect can be
sity of green fluorescence (Fig. 8). The longꢀterm used to dramatically increase the local fluorophore
exposure of PS films to TCM vapor (10 min or more) concentration in the required place of the film.
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200
SAZHNIKOV et al.
2800
2400
2000
1600
1200
800
515
150
100
50
630
400
0
0
480
520
560
600
640
680
480
520
560
600
640
680
Wavelength, nm
Wavelength, nm
Fig. 8. Fluorescence spectrum of the PSꢀfilm with
9ꢀDTAA ( ) after irradiation with a lightꢀemitting diode at
= 375 nm for a few minutes in tetrachloromethane
Fig. 9. Change in the fluorescence spectrum of the PS film
2
+
+
with 9ꢀDTAA (
2 ) in pyridine vapor (spectra recorded at
λ
max
intervals of 5 s).
vapor.
eties in molecules of 1–3 and the diversity of their fluꢀ
orescent properties are their additional advantage.
It is noteworthy that the photoinduced synthesis of
compounds 1–3 can be accomplished not only in thin
polymer layers, but also on the surface of polymeric
microꢀ and nanoparticles, which can be further used
to fabricate matrices for sensor elements by means of a
jet printing device [20].
ACKNOWLEDGMENTS
The authors are grateful to A.A. Khlebunov for
assistance in the measurement of the spectral characꢀ
teristics of the compounds and the preparation of samꢀ
ples of sensor materials.
CONCLUSIONS
This work was supported by the Ministry of Educaꢀ
tion and Science of the Russian Federation, state conꢀ
tract no. 11.519.11.3018.
It has been shown that the 9ꢀdiphenylaminoacriꢀ
dine compounds 9ꢀDPAA, 9ꢀDTAA, and 9ꢀDBAA
(1–3) immobilized in polymer films can be used as a
fluorescent molecular sensors whose fluorescence
intensity and color vary in the presence of polar
organic solvents or amines. The reactions of the phoꢀ
toinduced formation of fluorophores 1–3 can be used
for designing specialty sensor materials, since the forꢀ
mation of an indicator fluorophore in the polymer
layer can be initiated immediately before the measureꢀ
ment to obtain the indicator fluorophore at the desired
site in the desired concentration. It is also possible to
fabricate sensor layers suitable for visual indication by
change of fluorescence color in the presence of an
analyte.
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Translated by S. Zatonsky
HIGH ENERGY CHEMISTRY
Vol. 47
No. 6
2013