Translation of dicarboxylate structural information to fluorometric optical signals through self-assembly of guanidinium-tethered oligophenylenevinylene

Article abstract of DOI:10.1002/chem.201404028

Although self-assembly has realized the spontaneous formation of nanoarchitectures, the nanoscopic expression of chemical structural information at the molecular level can alternatively be regarded as a tool to translate molecular structural information with high precision. We have found that a newly developed guanidinium-tethered oligophenylenevinylene exhibits characteristic fluorescence (FL) responses toward L- and meso-tartarate, wherein the different self-assembly modes, termed J- or H-type aggregation, are directed according to the molecular information encoded as the chemical structure. This morphological difference originates from the geometric anti versus gauche conformational difference between L- and meso-tartarate. A similar morphological difference can be reproduced with the geometric C=C bond difference between fumarate and maleate. In the present system, the dicarboxylate structural information is embodied in the inherent threshold concentration of the FL response, the signal-to-noise ratio, and the maximum FL wavelength. These results indicate that self-assembly is meticulous enough to sense subtle differences in molecular information and thus demonstrate the potential ability of self-assembly for the expression of a FL sensory system. Self-assembly married to molecular recognition: A novel assembly-based fluorescence (FL) sensory system exhibits characteristic FL responses toward L- and meso-tartarate, wherein different self-assembly processes are directed according to the molecular structural information (see figure). This utilization of self-assembly substantiates its potential ability to translate molecular information and thus opens up a new avenue of molecular recognition.

Full text of DOI:10.1002/chem.201404028

DOI: 10.1002/chem.201404028
Full Paper
&
Fluorescent Chemosensors
Translation of Dicarboxylate Structural Information to
Fluorometric Optical Signals through Self-Assembly of
Guanidinium-Tethered Oligophenylenevinylene
[a, b]
[a]
[b]
[b]
Takao Noguchi,*
Bappaditya Roy, Daisuke Yoshihara, Youichi Tsuchiya,
[b]
[a, b, c]
Tatsuhiro Yamamoto, and Seiji Shinkai*
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Abstract: Although self-assembly has realized the spontane-
ous formation of nanoarchitectures, the nanoscopic expres-
sion of chemical structural information at the molecular level
can alternatively be regarded as a tool to translate molecular
structural information with high precision. We have found
that a newly developed guanidinium-tethered oligophenyle-
nevinylene exhibits characteristic fluorescence (FL) responses
toward l- and meso-tartarate, wherein the different self-as-
sembly modes, termed J- or H-type aggregation, are direct-
ed according to the molecular information encoded as the
chemical structure. This morphological difference originates
from the geometric anti versus gauche conformational differ-
ence between l- and meso-tartarate. A similar morphological
difference can be reproduced with the geometric C=C bond
difference between fumarate and maleate. In the present
system, the dicarboxylate structural information is embodied
in the inherent threshold concentration of the FL response,
the signal-to-noise ratio, and the maximum FL wavelength.
These results indicate that self-assembly is meticulous
enough to sense subtle differences in molecular information
and thus demonstrate the potential ability of self-assembly
for the expression of a FL sensory system.
[17]
Introduction
angle.
Yagai et al. also demonstrated that characteristic
nanoarchitectures consisting of rings and rods are formed by
just regioisomerism in self-assembling naphthalene chromo-
By applying the fundamental principles and methodologies of
[
1]
[18]
supramolecular chemistry, a wide variety of molecules have
been designed and self-assembled into well-ordered nanoarch-
itectures to create soft materials with sophisticated func-
phores. These studies clearly exemplify that self-assembly is
able to amplify a subtle difference in the molecular structure
(information) into a big difference in the resulting self-assem-
bled structure (output). Thus, one can regard self-assembly as
a function to convert information programmed as a molecular
structure into a superstructure output.
[
2–9]
tions.
In the chromophoric self-assemblies, for example, the
relative arrangements of chromophores, termed J and H type,
[
10,11]
predetermine the photophysical phenomena
and thus
result in optoelectronic materials with unique light-harvesting,
In this case, when a characteristic fluorescence (FL) signaling
is achieved as an output of self-assembly through interaction
with the concerned target, the FL signaling will reflect detailed
structural information about the target molecule. This process
is fundamentally regarded to be a translation of molecular
structural information into FL through self-assembly. In this
context, such an assembly-based system is intrinsically differ-
ent from the conventional sensory system based on molecular
[12–15]
energy/charge-transporting, and light-emitting properties.
The exploitation of such properties is one of the reasons why
the relationship between the molecular structure and its self-
assembly morphology has long been studied through appro-
priate molecular design. From this context, self-assembly has
been recognized as a tool to realize the spontaneous forma-
tion of functional nanoarchitectures. Therein, a small change in
the molecular structure fatefully alters the resulting self-assem-
bly structure. For example, Oda et al. reported that twisted
multilamellar superstructures are formed by the self-assembly
of a gemini surfactant in the presence of l-tartarate as a coun-
terion, whereas the molecule lacking one hydroxy group, that
[19]
recognition through receptor–guest binding. To the best of
our knowledge, the application of self-assembly to a FL senso-
ry system has rarely been explored, in spite of its potential
[20]
ability to read out molecular information.
In order to realize a synergistic marriage of self-assembly
and FL sensing, we have focused on aggregation-induced
[16]
is, the l-malate anion, generates flat bilayer structures. Fujita
and co-workers described how the structure of multicompo-
nent coordination polyhedra self-assembled from metal ions
and bridging ligands is determined critically by the ligand bent
[21]
emission (AIE). The advantage of AIE-based FL sensing is to
switch on FL emission accompanied via self-assembly induced
by target binding. We have already reported that selective FL
detection of biologically important phosphates, adenosine tri-
phosphate (ATP) and reduced nicotinamide adenine dinucleo-
tide phosphate (NADPH), is possible by a steep nonlinear FL in-
crease induced by self-assembly of guanidinium-tethered tetra-
[a] Dr. T. Noguchi, Dr. B. Roy, Prof. S. Shinkai
Institute for Advanced Study, Kyushu University
7
44 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan)
Fax: (+81)92-805-3814
E-mail: tnoguchi@mail.cstm.kyushu-u.ac.jp
shinkai_center@mail.cstm.kyushu-u.ac.jp
[22]
phenylethene (TPE-G). Indeed, this result seems to be a strik-
ing demonstration of FL translation through self-assembly, be-
cause the targeted phosphate selectively drives self-assembly
of TPE-G, which leads to a specific FL increase. The most nota-
ble point is that ATP or NADPH is selectively distinguishable
from their structural analogues by the inherent threshold con-
[b] Dr. T. Noguchi, Dr. D. Yoshihara, Dr. Y. Tsuchiya, Dr. T. Yamamoto,
Prof. S. Shinkai
Nanotechnology Laboratory
Institute of Systems, Information Technologies
and Nanotechnologies (ISIT)
[
22a]
4
–1 Kyudai-Shinmachi, Nishi-ku, Fukuoka 819-0388 (Japan)
centration of the FL response (the FL threshold)
and the FL
[22b]
[c] Prof. S. Shinkai
intensity (the signal-to-noise (S/N) ratio).
In other words, the
Department of Nanoscience
Faculty of Engineering, Sojo University
intrinsic information integrated within the nucleotides is ex-
pressed by the unique FL threshold and S/N ratio in the self-as-
sembly process. In addition, the FL wavelength (color) of cer-
tain fluorophores changes in response to the aggregation
4
-22-1 Ikeda, Kumamoto 860-0082 (Japan)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201404028.
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[
23]
mode, so the FL wavelength is also regarded as the output
of the molecular information expressed through molecular as-
sembly. Herein, we have made a new-perspective approach
toward an assembly-based FL sensory system in which the mo-
lecular information is expressed by the following three key pa-
rameters; the FL threshold, the S/N ratio, and the maximum
wavelength. In order to establish this concept, we decided to
elucidate the assembly-based FL sensory system for dicarboxy-
make OPV-G soluble homogeneously in water. The dicarboxy-
late targets used to test the selection ability of OPV-G are
shown in Figure 1b and can be categorized into the following
three types: i) diastereomeric l- and meso-tartarates, ii) trans/
cis-isomeric fumarate and maleate, and iii) normal dicarboxy-
lates bearing different spacer methylene numbers. The pur-
pose of the present study is to evaluate whether a subtle dif-
ference in the molecular information such as the chirality, ge-
ometry, and charge density encoded in the molecular structure
of the dicarboxylates can critically direct the self-assembly su-
perstructures of OPV-G and lead to characteristic FL responses.
This cascade can alternatively be regarded as translation of the
molecular information into FL optical signals by utilizing self-
assembly phenomena (Figure 2). In this study, we demonstrate
that the molecular information
[
24a]
late sensing,
ers and we can procure dicarboxylate derivatives with varia-
because dicarboxylates are important biomark-
[
24b–e]
tions from chirality to different methylene spacers.
Herein, we wish to report a novel assembly-based FL sensor,
guanidinium-tethered oligophenylenevinylene derivative
a
(
OPV-G, Figure 1a). This OPV-G has three unique features:
embodied in the dicarboxylates
is translated into the characteris-
tic FL threshold, S/N ratio, and
maximum wavelength. We pro-
pose herein that
a
sensory
system coupled with molecular
assembly phenomena will actu-
alize its potential ability to read
out the dicarboxylate structural
information.
Results and Discussion
Differentiation between l- and
meso-tartarate by the FL re-
sponse of OPV-G
Although OPV-G is virtually non-
fluorescent, the addition of the
tartarates can make it turn on,
with a FL intensity observable by
our naked eyes (Figure 3a, [OPV-
G]=10 mm, [tartarate]=5.0 mm).
The FL emission maximum ap-
peared at 518 nm with excitation
at 388 nm, but a significant dif-
ference in FL intensity was ob-
served between the tartarate
isomers; the intensity for l-tarta-
rate was 2.5-fold higher than
that for meso-tartarate (Fig-
ure 3b). The excitation spectra
Figure 1. Chemical structures of a) assembly-based fluorescent sensor OPV-G and b) target dicarboxylic acids cate- showed two characteristic peaks
gorized into the three types: i) diastereomers, ii) trans/cis isomers, and iii) normal dicarboxylic acids.
(
358 and 388 nm for the l form
and 348 and 388 nm for the
meso form) with a shoulder com-
1
) The OPV-based fluorophore exhibits FL emission in response
ponent (425 nm for both). These results are in good agreement
with those observed in the absorption spectra (Figure S1 in
the Supporting Information). This finding indicates that the FL
emission undoubtedly originates from OPV-G. Particularly inter-
esting is the finding that the relative intensity of the excitation
and absorption bands at 388 nm is different between l- and
[
25]
to the formation of p-stacked aggregates, a mechanism that
is clearly different from that of the TPE system based on rota-
[
26]
[27]
tional restriction, 2) the guanidinium groups used as rec-
ognition sites can bind with oxo anions through specific ionic
[
28]
hydrogen bonding even in water, and 3) the ethereal spacers
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One fundamental question arises: what kind of effect is op-
erating on the FL response? An insight is found in the above-
mentioned excitation and UV/Vis spectra, in which different
spectral changes are observed upon addition of l- and meso-
tartarate (Figure 3b and Figure S1 in the Supporting Informa-
tion). We can address the question from the following three
viewpoints: 1) the self-assembly behavior of OPV-G with l- and
meso-tartarate, 2) the morphological studies of the aggregates
formed by the self-assembly, and 3) the structural origin in the
tartarates that exclusively dominates the FL emission, the self-
assembly, and the morphological properties. Each factor is
evaluated in the following sections.
Self-assembly behavior of OPV-G with l- and meso-tartarate
The UV/Vis titration of OPV-G with tartarates afforded signifi-
cantly different spectral changes between the l form and the
meso form. When the l-tartarate concentration was increased,
the original absorption maximum of OPV-G at 370 nm de-
creased, together with a conspicuous increase in the shoulder
component at 425 nm (Figure 5a). This spectral change is in
good agreement with that reported in previous literature, in
which the OPV chromophores were found to be ar-
Figure 2. Schematic illustration for the concept of FL translation of l- and
meso-tartarate through self-assembly of OPV-G.
ranged in a slip-stacked fashion with respect to the
[29]
direction of the molecular long axis.
Herein, we
classify this mode of arrangement as J-type stacking.
In sharp contrast, the addition of meso-tartarate led
to a sharp decrease in the original absorption maxi-
mum at 370 nm, together with a significant shorter
wavelength shift to 344 nm in the concentration
range of 0–500 mm (Figure 5b and Figure S2 in the
Supporting Information). This spectral change is as-
cribed to H-type stacking of the OPV chromophores,
[25b]
as reported previously.
Although many reports
have described J- or H-type aggregation in chromo-
Figure 3. a) Photograph of OPV-G (10 mm) in the presence of tartarates in 2-[4-(2-hydroxy-
ethyl)-1-1piperazinyl]ethanesulfonic acid (HEPES) buffer (10 mm, pH 7.4); left: no guest;
middle: l-tartarate (5.0 mm); right: meso-tartarate (5.0 mm). The image was obtained
under UV irradiation (lex =365 nm). b) Excitation (lem =518 nm) and fluorescence spectra
[30–33]
phoric self-assemblies,
our results reveal a novel
view that the self-assembly behaviors arising from
the stereochemical difference between l- and meso-
tartarate are clearly distinguishable according to the
difference between J- and H-type aggregation. It is
noteworthy that the increased concentration in the
ratiometric plot of e425/e370 is also different, from
250 mm for l-tartarte and 50 mm for meso-tartarate (Figure 5c).
The threshold concentrations of e425/e370 are indicative of the
critical aggregate concentration (CAC) and, most notably, are
in good agreement with those of the FL response (Figure 4c),
(
l
ex =388 nm) of OPV-G (10 mm) in the presence of tartarates (5.0 mm) in HEPES buffer
(10 mm, pH 7.4) at 258C; solid line: l-tartarate; dotted line: meso-tartarate.
meso-tartarate in spite of the measurements being made
under entirely the same experimental conditions. One can
regard, therefore, the difference in the FL intensity as a result
of the stereochemical difference between l- and meso-tarta-
rate. In order to understand the FL behavior more deeply, we
performed a FL titration experiment. Upon addition of l-tarta-
rate, a FL emission increase was observed from 250 mm and its
intensity reached a maximum above 1.0 mm, with the FL in-
crease being 45-fold that in the absence of l-tartarate (Fig-
ure 4a and c). By contrast, meso-tartarate switched on the FL
emission of OPV-G from 50 mm and the FL increase was only
[22b]
as demonstrated in our previous report.
It is clear, therefore,
that the difference in the self-assembly process (J or H type) is
manifested in the characteristic FL threshold and S/N ratio.
Morphological observation of OPV-G self-assembled with l-
and meso-tartarate
1
8-fold at the maximum (Figure 4b and c). It is surprising that
To visualize the morphologies of OPV-G self-assembled with l-
and meso-tartarate, atomic force microscopy (AFM) was con-
ducted for aqueous dispersion samples prepared by spin-coat-
ing on highly oriented pyrolytic graphite (HOPG). Figure 6a
such a big difference in the FL threshold and the S/N ratio is
induced by the stereochemical information of these two tarta-
rates (Figure 4c).
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shows an AFM image of OPV-G J-type aggregates
prepared by association with l-tartarate. One can ob-
serve well-developed fibrous superstructures of at
least 35 nm in height. The formation of such a fibrous
structure is supported by a J-stacking mode, as pro-
posed by the FL microscopic observation of the
aqueous dispersion (Figure S3a in the Supporting In-
formation). In sharp contrast, an AFM image of OPV-
G H-type aggregates prepared by association with
meso-tartarate afforded a finite morphology (Fig-
ure 6b and Figure S3b in the Supporting Informa-
tion) of 50–120 nm in height. Obviously, such a mor-
phological difference stems from the difference in
stereochemical information integrated in the tarta-
rates (l form: 2R,3R; meso form: 2R,3S). It is surprising
that the stereochemical difference of only one chiral
carbon atom critically directs the self-assembled su-
perstructure.
Structural origin in the tartarates governing the FL
emission, self-assembly, and morphological proper-
ties
It has already been reported that the preferred con-
formations of l- and meso-tartarate in water are ex-
perimentally confirmed to be the anti and gauche
conformers, respectively (Figure S4 in the Supporting
Figure 4. Fluorescence titration of OPV-G upon addition of increasing concentrations of
a) l-tartarate and b) meso-tartarate. c) The FL titration result (lem =518 nm; *: l-tarta-
rate; ~: meso-tartarate) and an enlarged section of the lower concentration region (0–
[34]
Information). This conformational difference seems
to be the origin that governs the self-assembly pro-
cess leading to the characteristic FL response. In
order to confirm the effect of the conformation, we
employed trans/cis-isomeric dicarboxylates, that is,
fumarate and maleate, as target molecules (Fig-
ure 1b). Unexpectedly, we found that the FL maxi-
mum wavelength is different by 6 nm. This implies
that the differentiation of these isomers by FL color
is possible (Figure S5a in the Supporting Informa-
tion). The most important result is the finding that
the FL titration of OPV-G with these regioisomeric di-
carboxylates (Figure 7 and Figure S5b and c in the
Supporting Information) resulted in the same tenden-
cy as that observed with the tartarates (Figure 4),
which supported the idea that the preferred confor-
mations of l- and meso-tartarate (anti and gauche
conformations, respectively) in aqueous solution are
more or less similar with those of fumarate and male-
ate, respectively. This result affords a clear view that
the conformational difference encoded in the molec-
ular structures can direct the course of the self-as-
sembly. The self-assembly modes of OPV-G with l-
and meso-tartarate are schematically illustrated in
Figure 2: that is, self-assembly of OPV-G with l-tarta-
rate (anti conformation) forms a supramolecular poly-
mer with a fibrous superstructure in which the OPV
chromophores are arranged in a J-type stacking
manner that leads to an intense FL intensity, whereas
self-assembly of OPV-G with meso-tartarate (gauche
5
00 mm). Conditions: [OPV-G]=10 mm, [HEPES]=10 mm (pH 7.4), 258C, lex =388 nm. DF/
, in which F is the fluorescence
is the fluorescence intensity of OPV-G in the
F
0
indicates the fluorescence intensity change (DF=FÀF
0
intensity of OPV-G at a given point and F
absence of tartarates).
0
Figure 5. UV/Vis titration of OPV-G upon addition of increasing concentrations of a) l-tar-
tarate (0–5000 mm) and b) meso-tartarate (0–500 mm for clarity). c) Ratiometric plots of
e
425/e370 (*: l-tartarate; ~: meso-tartarate) and an enlarged section of the lower concen-
tration region (0–500 mm). Conditions: [OPV]=10 mm, [HEPES]=10 mm (pH 7.4), 258C.
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the FL titration curve and the individual molecular structures
of the dicarboxylates. Namely, the molecular information about
the dicarboxylates is well expressed by the characteristic FL
threshold and S/N ratio. Particularly noteworthy is the clear
tendency of the FL threshold and S/N ratio to increase with an
increase in the methylene spacer length of the dicarboxylates.
As in the case of l-tartarate and meso-tartarate, the FL thresh-
old and S/N ratio are characterized by the self-assembly pro-
cess of J- or H-type aggregation. Actually, a discontinuous
change in the S/N ratio is observable for the FL response from
malonate to succinate (Figure 8b). This change is attributable
to the formation of different types of aggregates, H type from
malonate and J type from succinate, as supported by the spec-
tral and morphological data (Figure S6a and S7 in
the Supporting Information). The shift of the FL
threshold to the higher concentration is attributable
to the reduced charge density (charge per molecular
volume) of the dicarboxylates, which acts as the self-
assembly driving force by ion pairing. In addition, the
entropic factor of the longer methylene spacer might
act disadvantageously, especially in the formation of
fibrous superstructures, as illustrated in Figure 2.
These results clearly indicate that FL translation
through self-assembly is meticulous enough to sense
a difference in only one carbon atom. Therefore, we
wish to propose herein that self-assembly, which ap-
pears as an amplification result of the molecular
Figure 6. AFM images of OPV-G self-assembled with a) l-tartarate and
b) meso-tartarate. Conditions: [OPV-G]=100 mm, [tartarate]=5.0 mm.
Figure 7. Fluorescence titration result of OPV-G upon addition of increasing concentra-
tions of fumarate (*) and maleate (~) and an enlarged section of the lower concentra-
tion region (0–1000 mm). Conditions: [OPV-G]=10 mm, [HEPES]=10 mm (pH 7.4), 258C,
structure, can be utilized as a tool for molecular rec-
ognition.
l
ex =388 nm.
Conclusion
We have demonstrated that, by utilizing the self-as-
sembly process of OPV-G, the structural information of dicar-
boxylates is successfully translated into a characteristic FL re-
sponse. The FL response of OPV-G that appears through com-
plexation with l- and meso-tartarate reflected the different
types of self-assembly process, J and H type, with extended
and finite morphologies, respectively. The chirality difference
between l- and meso-tartarate was similarly reproduced with
the geometrical difference between fumarate and maleate, re-
spectively. As supported by the FL titration results toward
normal dicarboxylates, the molecular information is definitely
translated into the characteristic FL threshold, S/N ratio, and
maximum wavelength characterized by the self-assembly. This
FL translation is highlighted only through the self-assembly
process. The utilization of self-assembly for sensory systems is
going to open up a new opportunity for the design and appli-
cation of a molecular sensor. We believe that it will allow
a new biomedical application when an assembly-based sensor
that works under physiological conditions is realized.
conformation) forms an H-type stacked finite aggregate that
results in a modest FL intensity.
The possibility of self-assembly as an amplification tool for
precise molecular recognition
From the point of view of bottom-up self-assembly, it is desira-
ble that a small change in the molecular structure results in
a dramatically different self-assembled architecture. Indeed,
the present study has demonstrated that the stereochemical
difference in the tartarate structures affords different self-as-
sembled nanoarchitectures: a fibrous structure for l-tartarate
and a finite aggregate for meso-tartarate. One may consider,
therefore, that the stereochemical information about the tarta-
rates is converted into the characteristic morphologies through
self-assembly. We thus learned that such stereochemical infor-
mation expressed by the characteristic self-assemblies is even-
tually embodied as the unique FL responses. In order to evalu-
ate the performance level of the translation from stereochemi-
cal information to FL response through self-assembly, we
tested the FL response of OPV-G toward the normal dicarboxy- Acknowledgements
lates illustrated in Figure 1b. As shown in Figure 8 and Fig-
ure S6 in the Supporting Information, the FL response of OPV-
G was found to exhibit a one-to-one-type relationship between
This work was financially supported by a Grant-in-Aid for
Young Scientists (B) (grant no.: 25810051).
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Received: June 19, 2014
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Published online on September 18, 2014
Chem. Eur. J. 2014, 20, 13938 – 13944
www.chemeurj.org
13944
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim