A Remarkable Fluorescence Quenching Based Amplification in ATP Detection through Signal Transduction in Self-Assembled Multivalent Aggregates

Article abstract of DOI:10.1002/chem.202002648

Signal transduction is essential for the survival of living organisms, because it allows them to respond to the changes in external environments. In artificial systems, signal transduction has been exploited for the highly sensitive detection of analytes. Herein, a remarkable signal transduction, upon ATP binding, in the multivalent fibrillar nanoaggregates of anthracene conjugated imidazolium receptors is reported. The aggregates of one particular amphiphilic receptor sensed ATP in high pm concentrations with one ATP molecule essentially quenching the emission of thousands of receptors. A cooperative merging of the multivalent binding and signal transduction led to this superquenching and translated to an outstanding enhancement of more than a millionfold in the sensitivity of ATP detection by the nanoaggregates; in comparison to the “molecular” imidazolium receptors. Furthermore, an exceptional selectivity to ATP over other nucleotides was demonstrated.

Full text of DOI:10.1002/chem.202002648

Accepted Article
Accepted Article
Title: A Remarkable Fluorescence Quenching Based Amplification in
ATP Detection through Signal Transduction in Self-assembled
Multivalent Aggregates
Authors: Rakesh Biswas, Sumit Naskar, Surya Ghosh, Mousumi Das,
and Supratim Banerjee
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202002648
Link to VoR: https://doi.org/10.1002/chem.202002648
01/2020

10.1002/chem.202002648
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A Remarkable Fluorescence Quenching Based Amplification in
ATP Detection through Signal Transduction in Self-assembled
Multivalent Aggregates
Rakesh Biswas, Sumit Naskar, Surya Ghosh, Mousumi Das,* and Supratim Banerjee*
R. Biswas, S. Naskar, S. Ghosh, Prof. Dr. M. Das and Prof. Dr. S. Banerjee
Department of Chemical Sciences
Indian Institute of Science Education and Research Kolkata
Mohanpur, West Bengal, India
E-mail: supratim.banerjee@iiserkol.ac.in, mousumi@iiserkol.ac.in
Supporting information for this article is given via a link at the end of the document
Abstract: Signal transduction is essential for the survival of living
organisms as it allows them to respond to the changes in external
environments. In artificial systems, signal transduction has been
exploited for the highly sensitive detection of analytes. Herein, we
report a remarkable signal transduction, upon ATP binding, in the
multivalent fibrillar nanoaggregates of anthracene conjugated
imidazolium receptors. The aggregates of one particular amphiphilic
receptor sensed ATP in high pM concentrations with one ATP
molecule essentially quenching the emission of thousands of
receptors. A cooperative merging of the multivalent binding and signal
transduction led to this superquenching and translated to an
outstanding enhancement of more than a million-fold in the sensitivity
of ATP detection by the nanoaggregates; in comparison to the
“molecular” imidazolium receptors. Furthermore, an exceptional
selectivity to ATP over other nucleotides was demonstrated.
The bio-analyte of our choice was ATP, a molecule with
prime importance in cell biology. It is the universal energy
currency in cells and plays pivotal roles in many cellular
processes including active transport and cell division.[14] The
synthetic probes employed for ATP detection typically relies on
electrostatic interactions and/or H-bonding.[15] A number of metal
ion-based receptors,[15,16] metal-free pure organic receptors[15,17]
and aptamers[18] have been developed for ATP detection. In
addition to these “molecular” receptors, multivalent binding of
ATP and other phosphates have been reported on the micellar
and vesicular interfaces, monolayers, etc.[19]
Imidazolium-based luminescent cyclophanes, podands and
tweezers are known for ATP binding[20] by utilizing a combination
of electrostatic as well as (C-H)+…O- hydrogen bonds. These
receptors were predominantly “molecular” in nature with multiple
imidazolium groups connected at different positions of anthracene,
pyrene, etc. The cavity/cleft created by the arrangement of the
imidazolium groups in space led to the binding of the nucleotides
through multiple electrostatic interactions. Additionally, the
aromatic moieties in the receptors presented stacking interactions
with the nucleobases to further stabilize the complexes. We
present here a fundamentally different approach in which rather
than covalently linking the imidazolium receptors, they are
organized through supramolecular self-assembly. Towards this
goal, we employ a series of imidazolium-based receptors (AImN,
N = the number of carbons in the alkyl chain, Figure 1) for ATP
binding. The self-assembly and photophysical properties of the
AImN receptors in aqueous media were governed by the length
of the hydrophobic n-alkyl segment. Supramolecular nano-fibrillar
aggregates were formed with N≥10 chains (Figure 1), whereas
the smaller chain derivatives (N≤6) remained in non-assembled
states. The aggregates exhibited greenish excimeric emissions
which underwent pronounced quenching in the presence of ATP.
Although the quenching was noted for all the three amphiphilic
Nature utilizes multivalency[1] to govern molecular
recognition events[2] which are key to many essential biological
functions including cellular adhesion and signal transduction.[3] In
signal transduction, a selective and amplified chemical response
is generated in the presence of a particular stimulus.[4] Inspired by
the high efficiency of the natural signal transduction processes,
artificial systems have been developed and exploited for analyte
detection at ultralow concentrations. The signal amplification in
artificial systems is typically accomplished either through enzyme
catalyzed reactions or by employing multivalent binding in which
a
single binding event affects the properties of multiple
receptors.[5] The chemo-sensing by conjugated polymer
electrolytes (CPEs), macromolecules with π-conjugated
backbone and ionic side groups, represents one of the prominent
examples of signal transduction by multivalent binding.[6] The
conjugated backbone in these “molecular wires” helps in
amplifying the binding event through an efficient exciton
migration.[7] We were interested in designing modular self-
assembled systems which would integrate the features of
multivalency and signal amplification for the detection of bio-
analytes. The self-assembly route reduces the tedious and time-
consuming protocols often required for the synthesis of CPEs to
a great extent and also offers modularity in terms of the
morphology. Because of these beneficial features, self-
assembled multivalency,[8] in which nano-scale, high affinity
multivalent arrays are created through the self-assembly of
smaller components, has emerged as a key technique for the
detection and binding of DNA,[9] heparin,[10] proteins,[11]
carbohydrates[12] and other analytes.[13]
Figure 1. Structure of the compounds and nucleotides
1
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Scheme 1. A schematic representation of the self-assembly of AIm14 and the amplified quenching by exciton migration upon ATP binding in its aggregates.
derivatives (N≥10), AIm14, in particular, showed an exceptionally
amplified quenching leading to ATP detection at high picomolar
concentrations. On the contrary, the non-assembled derivatives
(AIm1, AIm6, AIm8), did not sense ATP even at hundreds of
micromolar concentrations. Thus, in comparison to these
“molecular” receptors, the multivalent nanofibers of AIm14
exhibited more than a million-fold higher sensitivity in ATP
detection. Although such an amplified fluorescence quenching or
superquenching has been known for CPEs,[21] what is truly
remarkable is that in case of AIm14, the signal transduction
occurred through non-covalently stacked chromophores in a
supramolecular aggregate (Scheme 1). In addition, the
multivalent nanofibers of AIm14 also demonstrated an
exceptional selectivity towards ATP over several other nucleotide
tri-phosphates and pyrophosphate.
The AImN derivatives displayed attributes of monomeric
anthracenes in their absorption and emission spectra in DMSO
(Figure S3). However, in aqueous buffer (5 mM TRIS, 10 mM
NaCl, pH 7.4), noticeable differences in the spectral features were
observed depending on the chain-length (Figure 2). The
derivatives with N≤8 chains (AIm1, AIm6 and AIm8), exhibited
similar spectral features as observed in DMSO (Figures 2 and S3),
except small solvatochromic shifts. However, a new sharp, red-
shifted absorption peak at 403 nm and an additional broad
emission peak at 490 nm (Figures S6, S7 and S8) started to
appear for AIm10, AIm12 and AIm14 in specific concentration
ranges (1-10 μM for AIm10 and AIm12 and <1μM for AIm14).
Scanning electron microscopy (SEM) images revealed the
presence of entangled nano-fibrillar networks in these samples
(Figures 3e and S23) which were absent for the smaller chain
derivatives. These observations clearly suggested the self-
assembly of N≥10 derivatives. The red-shifted absorption band
suggested a J-like arrangement[22] of the stacked anthracenes
whereas the large Stokes shift (87 nm) coupled with the broad
feature of the emission band at 490 nm indicated that it was
excimeric in origin. This was supported by its comparatively
higher life-time than the monomeric emission (Table S2). The
excitation spectra (λem = 490 nm) for these three derivative
matched well with their absorption spectra (Figure S4) indicating
Table 1. Average size and zeta potential (ζ) of the self-assembled
nanoaggregates of AIm10, AIm12 and AIm14 before and after addition of
ATP in aqueous buffer from DLS measurements.
AImN
Size (nm)
before ATP
addition
Size (nm)
after ATP
(5 µM)
ζ (mV) before
ATP addition
ζ (mV) after
ATP (5 µM)
addition
addition
AIm10
(50 µM)
211 ± 21
456 ± 35
567 ± 23
354 ± 19
639 ± 84
868 ± 98
22.3 ± 2.8
50 ± 3.1
9.5 ± 0.2
16.5 ± 0.2
3.21±0.63
AIm12
(50 µM)
Figure 2. (a) Absorption and (b) emission spectra of AIm1, AIm6 and AIm8
(λex 365 nm) and AIm10, AIm12 and AIm14 (λex 400 nm) in buffer. The
concentration of each derivative was 50 µM.
AIm14
10.62±1.1
(10 µM)
2
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Figure 3. Fluorescence spectral changes of (a) AIm1 (100 µM) and (b) AIm14 (10 µM) upon addition of ATP and (c) AIm14 (10 μM) upon addition ATP, PPi,
ADP, AMP, UTP, CTP and GTP, (λex 400 nm); (d) Comparative I0/I values for AIm10 (100 µM), AIm12 (50 µM) and AIm14 (10 µM) upon ATP (50 nM) addition;
SEM images of AIm14 (e) without ATP and (f) With ATP (5 µM).
that the excimers originated from the stacked anthracenes in the
aggregates. The extent of aggregation, expectedly, was
dependent on the ionic strength of the medium (Figure S5).
The nano-aggregates of all the three amphiphilic derivatives
exhibited positive zeta potential values which decreased upon
addition of ATP (Table 1). Also, the size of the nanoaggregates
increased considerably upon ATP addition (Table 1) indicating the
formation of larger co-aggregates. A visible morphological change
was also observed in the SEM image (Figure 3f). These results,
thus, clearly pointed out a multivalent mode of ATP binding. Most
notably, ATP binding led to a quenching of both the monomer-like
and excimeric emissions of the aggregates (Figure S13). This
suggested that the monomer-like emission also resulted from the
anthracenes in the stacks and not from the free monomers (vide
infra). As the relative quenching of the excimer emission was
comparatively higher, its emission changes were monitored. From
a preliminary screening, the best response for each of the
amphiphiles was obtained with the following concentrations:
AIm10: 100 µM, AIm12: 50 µM and AIm14: 10 µM. Among them,
the best sensitivity was exhibited by AIm14 as ATP was detected
at a concentration of 100 pM. The limit of detection (LOD) was 54
pM (Figure S20). The amplified quenching was illustrated by the
fact that upon addition of 1 and 5 nM ATP (ATP/AIm14 ratios of
1:10000 and 1:2000, respectively), around 40% and 60% excimer
quenching[23] was observed (Figure 3b and S15. See Table S1 for
the relative standard deviation (RSD) values). In case of AIm10
and AIm12, the extent of quenching was noticeably lower (Figure
3d). For example, <10% quenching was observed with 5 nM of
ATP for AIm10 and AIm12 (Figures S10, S11 and S14). We also
studied the ATP-induced quenching in other buffer solutions such
as PBS and it was observed that although in comparison to TRIS
the response was slightly lower, nevertheless an efficient
quenching was also observed in this case (Figure S18). In
comparison to the multivalent aggregates, the smaller chain
derivatives AIm1, AIm6 and AIm8 either showed negligible or no
change in their monomeric emissions even after adding ATP till
200 µM (Figure 3a and S9). Therefore, in terms of the lower limit
of detection, more than a million-fold increase in the sensitivity
was demonstrated by the multivalent aggregates of AIm14
compared to the “molecular” receptors. The lack of quenching in
the monomeric receptors clearly indicated that multivalency and
signal transduction played decisive roles in the ATP sensing by
the aggregates. In case of conjugated polymers, amplified
quenching or superquenching typically occurs through electron or
energy transfer,[6] aggregation or conformational changes of the
polymer upon analyte binding.[24] Amplified quenching was also
reported for aggregated non-conjugated polymers with pendant
dyes.[25] We believe that, the multivalent ATP binding induced a
local co-aggregation of the supramolecular aggregates and this
effect was more pronounced with the most hydrophobic AIm14.[26]
The aggregation facilitated interchain migrations of the excitons
which led to the amplification of the binding event. The quenching
efficiency was found to be dependent on the concentration of
AIm14 in the aggregates and an optimum concentration (10 µM)
gave the best results. At lower concentrations, the quenching was
noticeably less (Figure S16). Also, above 10 µM, the extent of
quenching remained almost same. These results thus indicated
that the co-aggregate formation was the key to ATP induced
quenching and an optimum concentration of the amphiphile was
important. This was further supported by the studies at pH 3.5 in
which the quenching was comparatively less than that observed
at pH 7.4 (Figure S17). At a more acidic pH, the amount of
negative charge on ATP was less and this would have hindered
the formation of electrostatically driven co-aggregates to some
extent. Notably, in terms of the lower limit of ATP detection, to our
knowledge, the AIm14 aggregates are superior not only to the
reported multivalent self-assembled systems[19] but also those
reported with CPEs.[27]
The multivalent aggregates of AIm14 were subsequently
employed to examine the binding selectivity of ATP compared to
ADP and AMP, other nucleotide triphosphates (GTP, UTP and
CTP) and pyrophosphate (PPi) (Figure S2). In electrostatic charge
density driven binding events, it is often difficult to achieve a high-
level of selectivity between the nucleotide triphosphates. A plot of
3
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Figure 4. Optimized structure of (a) AIm6 with ATP and (b) AIm6 with GTP. Color coding: C: grey, H: white, N: blue, O: red, P: orange.
I0/I (I0 and I are the excimer intensities before and after the
addition of phosphates) against concentration revealed that the
AIm14 nanoaggregates, in fact, showed an exceptional selectivity
towards ATP in the nanomolar (Figure 3c. The error bars are
shown in Figure S14) and as well as in the micromolar
concentrations (Figure S12). Interestingly, the observed
selectivity towards ATP by AIm14 was not observed in other
amphiphilic derivatives (see Figure S19 for AIm12). Although, the
selectivity over ADP and AMP can be explained in terms of a
comparatively weaker electrostatic binding, it was really intriguing
to observe the binding selectivity of ATP over other nucleotide
triphosphates having similar number of negative charges. In the
literature, the selectivity of imidazolium based “molecular”
receptors towards a particular nucleotide is typically attributed to
the π-π stacking interactions between the nucleobase and the
aromatic moieties.[20d,e, 28] In order to identify the existence of any
such interaction in our case, we carried out computational
anthracene rings (Figure S22b, Table S2) in AIm6 dimer/ATP.
However, no such interaction was found for the guanine and
anthracene in AIm6 dimer/GTP. A couple of important points thus
emerged from these studies: a) in the AIm6 dimer, the slip-
stacked arrangement of anthracenes correlated well with the
observed J-band in the aggregates and b) the presence of an
additional interaction between the adenine and anthracene might
have contributed to the observed binding selectivity for ATP by
the multivalent aggregates.
In conclusion, we have employed the self-assembly of
amphiphilic imidazolium receptors to create multivalent
supramolecular assemblies which showed a highly efficient signal
transduction capability upon binding to ATP. The binding of ATP
facilitated co-aggregate formation and quenched the excimeric
emission of the stacked anthracenes. These quenching sites
further acted as emission traps in the interconnected nanofibrillar
networks and through exciton migration, one binding event led to
analysis by comparing the interactions of AIm6 with ATP and GTP. the emission quenching of thousands of receptors. Apart from the
Although AIm6 did not show multivalent ATP binding, it was
chosen for computational feasibility. The ground state of AIm6
with ATP and GTP (1:1 stoichiometry) was first optimized
separately using Density Functional Theory (DFT) based on
ωB97XD exchange correlation functional[29] and 6-311G (d,p)
basis set[30] in Gaussian 09 program package.[31] A clear stacking
between the anthracene ring of AIm6 and the adenine ring of ATP
was found whereas, in case of GTP, the guanine ring and the
anthracene ring were quite apart from each other (Figure 4).
Natural bond orbital (NBO) analysis using NBO 3.0[32]
implemented in Gaussian 09 on these optimized structures
revealed that there were two profound n→π* interactions between
the adenine ring of ATP and the anthracene ring of AIm6 (nN75
→π*C5-C6: 0.11 kcal/mol and nN69→π*C11-C13: 0.13 kcal/mol,
Table S3). However, this interaction was absent in case of GTP.
Subsequently, considering the multivalent mode of binding, we
analyzed the interactions of AIm6 dimer with ATP and GTP. NBO
analysis on the optimized AIm6 dimer showed three significant π-
π* interactions between the anthracene rings (Figure S22a and
Table S4). Thereafter, the AIm6 dimer was optimized with ATP
and GTP separately using ωB97xD/6-31G (d,p). NBO analysis
on the composite structures of AIm6 dimer/ATP and AIm6
dimer/GTP showed that although there was a reduction in the π-
π* interactions between the anthracene rings compared to AIm6
dimer in both cases (Figures S22b and S22c and Table S4), an
n-π* interaction existed between the adenine and one of the
amplified quenching features leading to a highly sensitive ATP
detection, the other novel aspect of the multivalent aggregates
was their remarkable selectivity towards ATP over other
nucleotides. Our study shows that through the self-assembly of
easily synthesizable small organic receptors, it is possible to
create multivalent arrays which are equivalent to conjugated
polymers in terms of the signal transduction and detection
sensitivity and this approach thus offers an enormous potential for
creating modular multivalent nanostructures for the recognition of
many other biological targets. Furthermore, the presence of
anthracene moiety in the amphiphiles provides an opportunity to
tune the multivalent binding through photo-irradiation.
Anthracenes are known to undergo photocycloaddition reactions
in a reversible fashion and this can be utilized to control the
multivalent binding of the aggregates towards ATP.
Acknowledgements
We are thankful to Science and Engineering Research Board
(SERB), Department of Science and Technology (DST),
Government of India (project: EMR/2016/002838) and Indian
Institute of Science Education and Research Kolkata (Creation of
Facility Grant) for support of this work. R.B. acknowledges IISER
Kolkata for fellowship.
Conflict of Interest
4
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18057–18061; d) S. Jhaveri, M. Rajendran, A. D. Ellington, Nat. Biotechnol.
2000, 18, 1293-1297.
The authors declare no conflict of interest.
Keywords: ATP • multivalency • signal transduction• self-
assembly • sensors
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Anthracene tagged amphiphilic imidazolium receptors undergo self-assembly in aqueous media to form multivalent nano-aggregates
which bind ATP. The multivalent binding leads to an amplified quenching of the excimeric emission of the stacked anthracenes through
an efficient signal transduction. A highly sensitive detection of ATP was achieved along with an exceptional selectivity over several
other nucleotide triphosphates.
6
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