Supramolecular tuning of thioflavin-T aggregation hosted by polystyrene sulfonate.

Tunable and controllable emission is an extremely desirable feature for advanced functional materials that finds usage in optoelectronic utilization, fluorescence probing/sensing, drug-delivery monitoring, etc. In the present contribution, we have employed a macrocyclic host molecule, sulfobutyl ether-ß-cyclodextrin (SBE-ß-CD), as a tuning agent for an intensely emissive aggregate assembly of a molecular rotor dye, thioflavin-T (ThT), in the presence of an anionic polyelectrolyte, polystyrene sulfonate (PSS). The macrocyclic host breaks the PSS templated ThT aggregates and leads to encapsulation of released ThT molecules, tailoring the emission response of the system in terms of intensity and wavelength. Utilizing the established selectivity of the cyclodextrin-adamantane system, reverse control of this tunable emission has been further achieved. The controllable fluorescence system has been extensively investigated using ground-state absorption, steady-state and time-resolved emission spectroscopy. This kind of supramolecular tailoring of self-assembled aggregate emission has enormous potential in the field of fluorescence sensors and probes, and imaging and tracking in biological systems.

Supramolecular Control on the Optical Properties of a Dye-Polyelectrolyte Assembly.

Control of fluorescent molecular assemblies is an exciting area of research with large potential for various important applications, such as, fluorescence sensing/probing, cell imaging and monitoring drug-delivery. In the present contribution, we have demonstrated control on the extent of aggregation of a dye-polyelectrolyte assembly using a macrocyclic host molecule, sulfobutylether-ß-cyclodextrin (SBE-ß-CD). Initially, a cationic molecular rotor based organic dye, Auramine-O (AuO), undergoes aggregation in the presence of an anionic polyelectrolyte, polystyrene sulfonate (PSS), and displays a broad intense new emission band along with large variation in its absorption features and excited-state lifetime. A manipulation of the monomer-aggregate equilibrium of the dye-polyelectrolyte assembly has been achieved by introducing a cyclodextrin based supramolecular host, SBE-ß-CD, which leads to relocation of AuO molecules from polyelectrolyte (PSS) to supramolecular host cavity, owing to the formation of a host-guest complex between AuO and SBE-ß-CD. A reversible control on this manipulation of monomer-aggregate equilibrium is further achieved by introducing a competitive guest for the host cavity i. e., 1-Adamantanol. Thus, we have demonstrated an interesting control on the dye-polyelectrolyte aggregate assembly using a supramolecular host molecule which open up exciting possibilities to construct responsive materials using a repertoire of various host-specific guest molecules.

TADF and exciplex emission in a xanthone-carbazole derivative and tuning of its electroluminescence with applied voltage.

Materials showing white light emission have found applications in a variety of solid state devices especially in display technology. For white light emission, doping of red (R), green (G) and blue (B) emitters in a host matrix is commonly practised. However, finding RGB emitters of similar stability with homogenous doping is challenging. Furthermore, such devices suffer from color purity in the long run. Small organic light emitters, capable of colour tuning and having a broad emission spectrum are in high demand as they provide colour stability, reproducibility, a simple device geometry and high efficiency. Recently, it has been shown that the efficiency of OLEDs can be enhanced by employing thermally activated delayed fluorescence (TADF) materials. Here, we designed and synthesised a xanthone-carbazole based D-A-D material (Xan-Cbz) for TADF properties. Blue TADF emission, in neat thin films, at 470 nm was observed and further investigated by studying delayed fluorescence and lifetime measurements. In addition, a blend of Xan-Cbz with NPD shows exciplex emission at 525 nm in thin film. OLEDs based on Xan-Cbz were fabricated using several device configurations. OLEDs having the device configuration ITO/PEDOT:PSS/NPD/Xan-Cbz/Bphen/LiF-Al showed a luminance of 1.96 × 104 Cd m-2 (at a current density of 50 mA cm-2) and V ON at ∼6 V. Electroluminescence showed the features of both neat emission (470 nm) of Xan-Cbz and its exciplex (525 nm) with NPD. Further, colour tuning was observed as a function of applied voltage and the ratio of light intensity (I 525/I 470) of neat and exciplex emission was found to decrease with increasing voltage. Greenish-blue emission (CIE coordinates: 0.202, 0.382) from Xan-Cbz OLEDs was obtained. Xan-Cbz showed its neat emission (at 470 nm) in ITO/PEDOT:PSS/CBP/Xan-Cbz/Bphen/LiF-Al and pure exciplex emission (at 525 nm) in ITO/PEDOT:PSS/NPD:Xan-Cbz/Bphen/LiF-Al device configurations. Thus in this article we showed blue TADF emission, exciplex emission and voltage dependent color tuning in OLEDs based on a small organic emitter.

Proton Transfer Reaction Dynamics of Pyranine in DMSO/Water Mixtures.

Photoinduced intermolecular excited-state proton transfer (ESPT) reactions are ubiquitous in chemistry and biology. ESPT reactions are extremely sensitive to the nature of water molecules in its microenvironment and thus serve as a sensitive reporter for the water structure and dynamics in a system. Herein, the photoinduced intermolecular ESPT reaction of 8-hydroxypyrene-1,3,5-trisulfonic acid (HPTS, also known as pyranine) has been investigated in various DMSO/water mixtures by using steady-state and time-resolved emission spectroscopy. The DMSO/water binary mixture yields an interesting and anomalous behavior for the proton transfer reaction dynamics of HPTS at a mole fraction of DMSO (XDMSO ) of 0.41-0.51, which has also been previously investigated and projected as an anomalous region by molecular dynamics simulation and other experimental techniques. The extreme slowdown of the proton transfer reaction observed at XDMSO =0.41-0.51 has been attributed to the slow solvation dynamics, as well as the non-availability of free water molecules at this composition, which are required to solvate the newly generated proton. These observations have been also corroborated by time-resolved area-normalized emission spectra. The dimensionality of the proton diffusion process has been investigated by analyzing the geminate recombination process, and is found to be significantly different in DMSO/water mixtures (XDMSO =0.41-0.51) compared with three-dimensional proton diffusion in neat water.

Excited-State Proton Transfer on the Surface of a Therapeutic Protein, Protamine.

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 that is in contrast to the behavior of HPTS in the bulk aqueous buffer medium, where the proton diffusion process is three-dimensional. The effect of ionic strength on the binding of HPTS toward PrS suggests a predominant role of electrostatic interaction between anionic HPTS and cationic Protamine, which is further supported by molecular docking simulations which predict that the most preferable binding site for HPTS on the surface of Protamine is surrounded by multiple cationic arginine residues.

Stimulus-Responsive Supramolecular Aggregate Assembly of Auramine O Templated by Sulfated Cyclodextrin.

Self-aggregation of organic molecules is rarely seen with macrocyclic hosts like ß-cyclodextrin, as they preferentially involve the formation of inclusion complexes with the guest molecule. In this contribution, we report the self-aggregation of a guest molecule induced by negatively charged sulfated ß-cyclodextrin (SCD) to yield highly emissive aggregates of a recently projected amyloid marker dye, Auramine O (AuO). The SCD templated AuO aggregates display very different photophysics when compared to its reported behavior in a wide range of various chemical and biological environment but show a remarkable similarity with the recently reported photophysical behavior of AuO in human insulin fibrillar media, thus providing important insights into the molecular form of AuO responsible for its amyloid sensing ability. The self-assembled AuO aggregates formed in the presence of SCD display a significantly long excited-state lifetime, suggesting the retardation of the torsional relaxation of dye in the aggregated state, which otherwise leads to a very short excited-state lifetime for the monomeric form of the dye in the isolated form. Detailed time-resolved emission spectra (TRES) measurements show a dynamic Stokes shift suggesting excitonic migration within the AuO aggregates. The supramolecular aggregate assembly displays remarkable sensitivity to important external stimuli like temperature or ionic strength of the medium, pitching for its possible application in designing stimuli-responsive sensing schemes for important analytes.

On the Molecular Form of Amyloid Marker, Auramine O, in Human Insulin Fibrils.

Designing extrinsic fluorescence sensors for amyloid fibrils is a very active and important area of research. Recently, an ultrafast molecule rotor dye, Auramine O (AuO), has been projected as a fluorescent amyloid marker. It has been claimed that AuO scores better than the most extensively utilized gold-standard amyloid probe, Thioflavin-T (ThT). This advantage arises from the fact that AuO, in addition to its usual emission band (∼500 nm), also displays a large red-shifted emission band (∼560 nm), exclusively in the presence of human insulin fibril medium and not in the native protein or buffer media. On the contrary, for ThT, the emission maximum (∼490 nm) largely remains unchanged while going from protein to fibril. This otherwise unknown large red-shifted emission band of AuO, observed in the presence of human insulin fibrils, was tentatively attributed to a species formed upon fast proton dissociation from excited AuO. It was proposed that because of the long excited-state lifetime (∼1.8 ns) of AuO upon association with human insulin fibrils, this fast proton dissociation from excited AuO could be observed, which is otherwise not observed in buffer or native protein media, owing to its very short excited-state lifetime (∼1 ps). Herein, we show that despite the long excited-state lifetime of AuO in other fibrillar media (human serum albumin and lysozyme), the new red-shifted emission band at 560 nm is not observed, thus possibly suggesting a different origin of the red-shifted emission band of AuO in human insulin fibril medium. We convincingly show that this red-shifted band of AuO (∼560 nm) could be observed under conditions that promote dye aggregation, such as a premicellar concentration of surfactants and polyelectrolytes. These AuO aggregates display strong emission wavelength dependence of transient decay traces, similar to that for AuO in human insulin fibril medium. Detailed time-resolved emission spectral (TRES) measurements suggest that the AuO/premicellar surfactant and AuO/human insulin fibril system share similar features, such as a dynamic red-shift in TRES and an isoemissive point in the time-resolved area-normalized emission spectra, suggesting that the characteristic red-shifted emission band of AuO in human insulin fibril medium may arise from AuO aggregates.