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The combination of supramolecular chemistry and aggregation-induced emission-based luminogens (AIEgens) has recently attracted tremendous attention because of its ability to offer large emission enhancement even in substantially dilute solutions. In this work, a new aggregation-induced emission (AIE)-based supramolecular assembly has been reported, which consists of a polyanionic cyclodextrin derivative and a tetracationic tetraphenylethylene (TPE) derivative. Ionic cyclodextrins have attracted significant attention in host-guest supramolecular chemistry and pharmaceutical industry. However, ionic derivatives of β-cyclodextrins have not been explored to establish noncovalent interactions-based aggregation assembly of the most popular class of AIEgens, i.e., tetraphenylethylene derivatives. The current report demonstrates AIE of a tetracationic methyl pyridinium derivative of tetraphenylethylene (TPy-TPE) induced by a polyanionic sulfated β-cyclodextrin (S-βCD). The AIE-based supramolecular assembly has been thoroughly investigated using steady-state fluorescence, ground-state absorbance, and time-resolved fluorescence measurements. Further, the response of the supramolecular assembly towards external stimuli, such as, ionic strength, pH, and temperature, has been investigated. In addition, the complexation behavior of the TPE derivative has also been compared with the native neutral β-cyclodextrin derivative, which delineates the important role of the negatively charged portal of S-βCD in inducing aggregation of the TPy-TPE. The stoichiometry of the complex has been found to be 3:1 for TPy-TPE:S-βCD, using Job's plot analysis. Finally, to get insights into the underlying interactions between the supramolecular assembly components, molecular docking calculations have been performed.

The change in the color of chromophore upon being embedded in a biological tissue is known as metachromasia. Basic Orange 21 (BO21) is a cationic polymethine dye that has been implied as a supravital dye, which produces metachromasia in leukocytes. An improved differential counting of leukocytes has been achieved in the clinical setup based on characteristic metachromatic expressions of BO21 for different types of leukocytes. Although BO21 has been utilized as a chromatic indicator for leukocyte counting, there are limited number of investigations that focus on the factors that may be responsible for the spectral shift in absorption and emission spectra of BO21, which leads to its metachromatic behavior. In this work, we have investigated the effect of a synthetic anionic polyelectrolyte, polystyrene sulfonate (PSS), on the photophysical properties of BO21, using steady-state emission, ground-state absorption, and time-resolved emission measurements, to get an understanding of the factors that may be responsible for the spectral shift of BO21 in the cellular environment. PSS induces aggregation of BO21 molecules with large changes in its photophysical properties; this appears to be most likely the mechanism of spectral shift for BO21 reported in the cellular environment. The employment of external stimulus reveals BO21 aggregates to be significantly responsive toward external stimuli, for example, temperature and presence of salt in the medium, which further strengthens the proposal of aggregate formation. Further, we have also employed fluorescence upconversion spectroscopy with subpicosecond time resolution to estimate the excited-state lifetime of BO21.

Proton transfer reactions on biosurfaces play an important role in a myriad of biological processes. Herein, the excited-state proton transfer reaction of 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) has been investigated in the presence of an important therapeutic protein, Protamine (PrS), using ground-state absorption, steady-state, and detailed time-resolved emission measurements. HPTS forms a 1:1 complex with Protamine with a high association constant of 2.6 × 104 M–1. The binding of HPTS with Protamine leads to a significant modulation in the ground-state prototropic equilibrium causing a downward shift of 1.1 unit in the acidity constant (pKa). In contrast to a large number of reports of slow proton transfer of HPTS on biosurfaces, interestingly, HPTS registers a faster proton transfer event in the presence of Protamine as compared to that of even the bulk aqueous buffer medium. Furthermore, the dimensionality of the proton diffusion process is also significantly reduced on the surface of Protamine tha...

Recently, Auramine O (AuO) has been projected as a fluorescent fibril sensor, and it has been claimed that AuO has an advantage over the most extensively utilized fibril marker, Thioflavin-T (ThT), owing to the presence of an additional large red-shifted emission band for AuO, which was observed exclusively for AuO in the presence of fibrillar media and not in protein or buffer media. As fibrils are very rich in β-sheet structure, a fibril sensor should be more specific toward the β-sheet structure so as to produce a large contrast between the fibril form and native protein form, for efficient detection and in vitro mechanistic studies of fibrillation. However, in this report, we show that AuO interacts significantly with the native form of bovine serum albumin (BSA), which is an all-α-helical protein and lacks the β-sheet structure, which are the hallmarks of a fibrillar structure. This strong interaction of AuO with the native form of BSA leads to a large emission enhancement of AuO for the native protein itself, and leads to a low contrast between the BSA protein and its fibrils. More importantly, the large red-shifted emission band of AuO, reported in the presence of human insulin fibrils, and which was projected as its major advantage over ThT, is not observed in the presence of BSA fibrils as well as fibrils from other proteins, such as lysozyme, human serum albumin, and β-lactoglobulin. Thus, our results provide information on the universal applicability of the distinctive and claimed-to-be-advantageous photophysical features reported for AuO in human insulin fibrils towards fibrils from other proteins. Time-resolved fluorescence measurements also support the proposition of a strong interaction of AuO with native BSA. Additionally, tryptophan emission of the protein has been explored to further elucidate the binding mechanism of AuO with native BSA. Evaluation of thermodynamic parameters revealed that the binding of AuO with native BSA involved positive enthalpy and entropy changes, suggesting dominant contributions from hydrophobic and electrostatic interactions toward the association of AuO with native BSA. Molecular docking calculations have been performed to identify the principal binding location of AuO in native BSA.

Ultrafast spectroscopy on solutes, whose dynamics is very sensitive to the friction in its local environment, has strong potential to report on the microenvironment existing in complex fluids such as ionic liquids. In this work, the torsional relaxation dynamics of Thioflavin-T (ThT), an ultrafast molecular rotor, is investigated in two fluoroalkylphosphate ([FAP])-based ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM][FAP]) and 1-(2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([OHEMIM][FAP]), using ultrafast fluorescence up-conversion spectroscopy. The emission quantum yield and the excited-state fluorescence lifetime measurement suggest that the torsional relaxation of Thioflavin-T, in this class of ionic liquids, is guided by the viscosity of the medium. The temporal profile of the dynamic Stokes' shift of ThT, measured from time-resolved emission spectrum (TRES), displays a multiexponential behavior in both ionic liquids. The long time dynamics of the Stokes' shift is reasonably slower for the hydroxyethyl derivative as compared to the ethyl derivative, which is in accordance with their measured shear viscosity. However, the short time dynamics of Stokes' shift is very similar in both the ionic liquids, and seems to be independent of the measured shear viscosity of the ionic liquid. We rationalize these observations in terms of different locations of ThT in these ionic liquids. These results suggest that despite having a higher bulk viscosity in the ionic liquid, they can provide unique microenvironment in their complex structure, where the reaction can be faster than expected from their measured shear viscosity.

Photoinduced intermolecular electron transfer (ET) dynamics between various 7-aminocoumarin acceptors and N,N-dimethylaniline (DMAN) donor has been studied in copolymer-surfactant supramolecular assemblies prepared in aqueous 1% P123 triblock copolymer micellar solution with varying concentration of surfactants (sodium dodecyl sulfate (SDS), cetyl trimethyl ammonium chloride (CTAC), and triton-X-100 (TX100)). The aim of the present study is to modulate the reaction environment, especially the degree of micellar hydration inside the P123 micelle by the addition of the surfactants, which can modulate the ET reaction through the changes in the ET rates and the reaction exergonicity. Within the limited surfactant to copolymer molar ratios (n) used in the present study, fluorescence spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS) investigations indicate that the copolymer-surfactant supramolecular assemblies retain their micellar structure, although the micellar size gradually decreases with n. The redox potentials of the electron donor and acceptors are also found to change with n, although the extent of the effect is different for SDS, CTAC, and TX100 cosurfactants. In the presence of CTAC, the estimated exergonicity (-ΔG(0)) of the ET reaction is found to increase with an increase in n compared with that in pure P123, whereas it decreases marginally with SDS and remains almost the same for TX100. Substantial quenching of coumarin fluorescence is observed in the presence of DMAN in all copolymer-surfactant micellar aggregates because of ET reaction. The ET rate is seen to increase gradually with an increase in SDS and CTAC concentration in the supramolecular assembly, although it remains unaffected on the addition of TX100. The increased ionic strength in the Corona region of the copolymer-surfactant supramolecular aggregates due to the addition of the ionic surfactants has been envisaged for the increase in the ET rates. A correlation of the quenching rate constants with the free-energy changes (ΔG(0)) of the ET reactions shows the typical bell-shaped curve as predicted by Marcus outersphere ET theory. A substantial shift along the exergonicity axis (~0.3 eV) for the appearance of the Marcus correlation is observed in some cases, although the extent of such shift depends on both the nature of the cosurfactant and the amount of cosurfactant used in the copolymer-surfactant supramolecular assembly. Therefore, these preliminary results suggest a possibility of not only modulating the ET rates but also tuning the appearance of Marcus inversion along the exergonicity scale by suitably tuning the reaction environment inside the copolymer-surfactant supramolecular assemblies with a relatively more hydrophilic cosurfactant.

Interaction of cationic surfactant, cetyl trimethyl ammonium bromide (CTAB), with pluronics F88 (EO(103)-PO(39)-EO(103)) and P105 (EO(37)-PO(56)-EO(37)) micelles and its effect on modulating the location of an anionic solute in the mixed micelles have been investigated using time-resolved fluorescence and small angle neutron scattering (SANS) studies. SANS results indicate the formation of pluronic-CTAB supramolecular assemblies, in which the hydrophobic chains of CTAB occupy the hydrophobic core of the pluronic micelle while the positively charged head groups reside at the micellar core-corona interface. Rotational correlation time of the anionic probe in these supramolecular assemblies increases with an increase in the CTAB concentration, and the observed results are explained on the basis of the probe movement from the surface to the interior of the micelle due to the increased electrostatic attraction. Dynamic Stokes' shift measurements also support the movement of the probe due to the addition of the surfactant to the supramolecular assemblies. From the studies with different pluronics, it is indicated that the concentration of CTAB required to drag the probe molecule into the interior of the micelles is linearly correlated to the thickness of the corona region of the respective micelles.

Present results demonstrate that the redox potential and hence the chemical reactivity of a solute dissolved in a polymer-surfactant supramolecular assembly, considered as a nanoreactor, can be tuned substantially by changing the composition of the supramolecular assembly. It is understood from detailed study that, on changing the polymer-surfactant composition of the supramolecular assembly, the probe undergoes a change in its location in these nanoreactors and accordingly its physical and chemical properties can be modulated.

Effect of electrostatic interaction on the location of a solubilized molecular probe with ionic character in a supramolecular assembly composed of a triblock copolymer, P123 ((ethylene oxide) 20-(propylene oxide) 70-(ethylene oxide) 20) and a cosurfactant cetyltrimethylammonium chloride (CTAC) in aqueous medium has been studied using steady-state and time-resolved fluorescence measurements. Coumarin-343 dye in its anionic form has been used as the molecular probe. In the absence of the surfactant, CTAC, the probe C343 prefers to reside at the surface region of the P123 micelle, showing a relatively less dynamic Stokes' shift, as a large part of the Stokes' shift is missed in the present measurements due to faster solvent relaxation at micellar surface region. As the concentration of CTAC is increased in the solution, the percentage of the total dynamic Stokes' shift observed from time-resolved measurements gradually increases until it reaches a saturation value. Observed results have been rationalized on the basis of the mixed micellar structure of the supramolecular assembly, where the hydrocarbon chain of the CTAC surfactant dissolves into the nonpolar poly(propylene oxide) (PPO) core of the P123 micelle and the positively charged headgroup of CTAC resides at the interfacial region between the central PPO core and the surrounding hydrated poly(ethylene oxide) (PEO) shell or the corona region. The electrostatic attraction between the anionic probe molecule and the positively charged surface of the PPO core developed by the presence of CTAC results in a gradual shift of the probe in the deeper region of the micellar corona region with an increase in the CTAC concentration, as clearly manifested from the solvation dynamics results.

Ultrafast photoinduced bimolecular electron transfer (ET) dynamics between 7-aminocoumarin derivatives and N,N-dimethylaniline (DMAN) has been studied in neutral (TX100), cationic (DTAB) and anionic (SDS) micellar media. A very fast decay time constant (tau(fast)) shorter than approximately 10 ps has been observed for the coumarins in the presence of DMAN in all of the three micellar media. In this time scale, reactants in the micellar phase undergo ET interactions without involving diffusion or reorientation of the reactants and thus can be envisaged as equivalent to nondiffusive bimolecular ET reaction. The fastest ET rates estimated as the inverse of the shortest lifetime components of the fluorescence decay (k(et) congruent with tau(fast)(-1)) nicely follow the predicted Marcus inversion behavior with reaction exergonicity (-DeltaG degrees), irrespective of the nature of micelles considered. Onset of inversion in ET rates occur at approximately 0.61 eV lower exergonicity in SDS and TX100 micelles compared with that in DTAB micelle and are rationalized following two-dimensional ET (2DET) theory. These differences suggest the possibility of tuning Marcus inversion by proper selection of micelles. Interestingly, ET rates (k'(et)) obtained from the conventional Stern-Volmer analysis of the relatively longer time constants of the fluorescence decays also exhibit similar Marcus correlation with DeltaG degrees, showing clear inversion behavior. Fitting of Marcus correlation curves for k(et) and k'(et) indicate two largely different values for the electronic coupling parameters. In micellar media, as the interacting donor-acceptor molecules are on an average expected to be separated by an intervening surfactant chain and the reorientation rate of the reactants is quite slow, it is predicted that the ultrafast ET (k(et)) component arises because of the surfactant separated donor-acceptor pairs that are orientated perfectly to give the maximum electronic coupling. The slower ET (k'(et)) is predicted to arise because of those pairs where the donor-acceptor orientations are not very suitable but good enough to give a sizable electronic coupling.