Surfactant-based supramolecular dye assembly: A highly selective and economically viable platform for quantification of heparin antidote.

Herein, we have employed a supramolecular assembly of a cationic dye, LDS-698 and a common surfactant sodium dodecyl sulfate (SDS) as a turn-on fluorescent sensor for protamine (Pr) detection. Addition of cationic Pr to the solution of dye-surfactant complex brings negatively charged SDS molecules together through strong electrostatic interaction, assisting aggregation of SDS way before its critical micellar concentration (CMC). These aggregates encapsulate the dye molecules within their hydrophobic region, arresting non-radiative decay channels of the excited dye. Thus, the LDS-698•SDS assembly displays substantial enhancement in fluorescence intensity that follows a nice linear trend with Pr concentration, providing limit of detection (LOD) for Pr as low as 3.84(±0.11) nM in buffer, 124.4(±6.7) nM in 1% human serum and 28.3(±0.5) nM in 100% human urine. Furthermore, high selectivity, low background signal, large stokes shift, and emission in the biologically favorable deep-red region make the studied assembly a promising platform for Pr sensing. As of our knowledge it is the first ever Pr sensory platform, using a very common surfactant (SDS), which is economically affordable and very easily available in the market. This innovative approach can replace the expensive, exotic and specialized chemicals considered for the purpose and thus showcase its potential in practical applications.

G-Quadruplex selectivity and cytotoxicity of a guanidine-encapsulated porphyrin-cyclodextrin conjugate.

G-Quadruplex DNAs represent out-of-the-way nucleic acid conformations, frequently formed by guanine-rich sequences. They have emanated as cancer-associated targets for designed small molecules. The variation in the binding affinity of the synthesized compounds to duplex and quadruplex structures is an intriguing quest, solved by spectroscopic analysis. In this paper, we report the synthesis of a porphyrin-cyclodextrin conjugate, characterized by utilizing FT-IR, NMR, and mass spectrometry. Further, two benzimidazolylguanidines are synthesized which form host: guest complexes with the porphyrin-cyclodextrin conjugate. The structure of the complexes is optimized by analyzing their 2D ROESY spectra. The interactions of the host, guest, and the host: guest complexes with the duplex (calf thymus DNA) and quadruplex (kit22) nucleic acids are investigated employing UV-vis, fluorescence, circular dichroism, and DNA melting experiments. The calculated strengths of the compounds' binding with kit22 are in the order of 106, which is larger than those observed for the duplex DNA binding. The significant G-quadruplex selectivity of the host: guest complex of anthracenyl-benzimidazolylguanidine is discussed in detail. Further, the in vitro cytotoxicity of the compounds on MCF-7 cell lines is examined. The host: guest complexes show enhanced half-maximal inhibitory concentration values compared to the un-complexed compounds.

An overview from simple host-guest systems to progressively complex supramolecular assemblies.

Supramolecular chemistry involving macrocyclic hosts is a highly interdisciplinary and fast-growing research field in chemistry, biochemistry, and materials science. Host-guest based supramolecular assemblies, as constructed through non-covalent interactions, are highly dynamic in nature, and can be tuned easily using their responses to various external stimuli, providing a convenient approach to achieve excellent functional materials. Macrocyclic hosts, particularly cyclodextrins, cucurbit[n]urils, and calix[n]arenes, which have unique features like possessing hydrophobic cavities of different sizes, along with hydrophilic external surfaces, which are also amenable towards easy derivatizations, are versatile cavitands or host molecules to encapsulate diverse guest molecules to form stable host-guest complexes with many unique structures and properties. Interestingly, host-guest complexes possessing amphiphilic properties can easily lead to the formation of various advanced supramolecular assemblies, like pseudorotaxanes, rotaxanes, polyrotaxanes, supramolecular polymers, micelles, vesicles, supramolecular nanostructures, and so on. Moreover, these supramolecular assemblies, with varied morphologies and responsiveness towards external stimuli, have immense potential for applications in nanotechnology, materials science, biosensors, drug delivery, analytical chemistry and biomedical sciences. In this perspective, we present a stimulating overview, discussing simple host-guest systems to complex supramolecular assemblies in a systematic manner, aiming to encourage future researchers in this fascinating area of supramolecular chemistry to develop advanced supramolecular materials with superior functionalities, for their deployment in diverse applied areas.

Host-Assisted Aggregation-Induced Emission of a Tetraphenylethylene Derivative and Its Responses toward External Stimuli.

Aggregation-induced emission (AIE) of fluorogenic dyes offers many opportunities as smart materials, fluorescence sensing of analytes, bioimaging, molecular electronics, and many others. AIE dyes (called AIEgens) produce emission through aggregation, which are more advantageous than conventional emission of monomeric fluorophores, as the latter is unduly susceptible toward various quenching processes. Here, we report AIE enhancement of a polyanionic sulfonato-tetraphenylethylene (SuTPE) derivative, achieved through supramolecularly assisted dye aggregation, as SuTPE interacts with a multicationic amino-ß-cyclodextrin (AßCD) host. Aggregation of the dye is induced mainly because of strong electrostatic interaction of SuTPE with AßCD, causing a significant extent of charge neutralization for the polyanionic dyes, helping their assemblage at the multicationic host portal. Job's plot studies suggest preferential formation of 2:1 dye-to-host stoichiometric complexes in the present system. Ionic-strength-dependent studies nicely support the involvement of electrostatic interaction in the present system through salt-induced disintegration of the SuTPE-AßCD complexes. The AIE enhancement for the SuTPE-AßCD system is very sensitive to the external stimuli, such as pH and temperature, suggesting its prospects in various stimuli-responsive applications. Furthermore, the SuTPE-AßCD system can suitably quantify an important bioanalyte, ATP, following a competitive binding strategy, suggesting its potential application as a supramolecular biosensor.

Stimuli Responsive Confinement of a Molecular Rotor Based BODIPY Dye inside a Cucurbit[7]uril Nanocavity.

Present study reports the interaction of a molecular rotor based BODIPY dye, 8-anilino-BODIPY (ABP), with a versatile macrocyclic molecule, cucurbit[7]uril (CB7), investigated through various techniques such as ground-state absorption, steady-state fluorescence, time-resolve emission, proton NMR, and quantum chemical studies. Although BODIPY dyes have widespread applications due to their intriguing photochemical properties, studies on their noncovalent interactions with different macrocyclic hosts, especially regarding their supramolecularly induced modulations in photophysical properties are very limited. The investigated BODIPY dye, especially its protonated ABPH+ form (pH ∼ 1), shows a large fluorescence enhancement on its interaction with the CB7 host, due to large reduction in the structural flexibility for the bound dye, causing a suppression in its nonradiative de-excitation process in the excited state. Unlike ABPH+, the neutral ABP form (pH ∼ 7) shows considerably weaker interaction with CB7. For ABPH+-CB7 system, observed photophysical results indicate formation of both 1:1 and 1:2 dye-to-host complexes. Plausible geometries of these complexes are obtained from quantum chemical studies which are substantiated nicely from 1H NMR results. The response of the ABPH+-CB7 system toward changing temperature of the solution have also been investigated elaborately to understand the potential of the system in different stimuli-responsive sensor applications.

Supramolecular and suprabiomolecular photochemistry: a perspective overview.

In this perspective review article, we have attempted to bring out the important current trends of research in the areas of supramolecular and suprabiomolecular photochemistry. Since the spans of the subject areas are very vast, it is impossible to cover all the aspects within the limited space of this review article. Nevertheless, efforts have been made to assimilate the basic understanding of how supramolecular interactions can significantly change the photophysical and other related physiochemical properties of chromophoric dyes and drugs, which have enormous academic and practical implications. We have discussed with reference to relevant chemical systems where supramolecularly assisted modulations in the properties of chromophoric dyes and drugs can be used or have already been used in different areas like sensing, dye/drug stabilization, drug delivery, functional materials, and aqueous dye laser systems. In supramolecular assemblies, along with their conventional photophysical properties, the acid-base properties of prototropic dyes, as well as the excited state prototautomerization and related proton transfer behavior of proton donor/acceptor dye molecules, are also largely modulated due to supramolecular interactions, which are often reflected very explicitly through changes in their absorption and fluorescence characteristics, providing us many useful insights into these chemical systems and bringing out intriguing applications of such changes in different applied areas. Another interesting research area in supramolecular photochemistry is the excitation energy transfer from the donor to acceptor moieties in self-assembled systems which have immense importance in light harvesting applications, mimicking natural photosynthetic systems. In this review article, we have discussed varieties of these aspects, highlighting their academic and applied implications. We have tried to emphasize the progress made so far and thus to bring out future research perspectives in the subject areas concerned, which are anticipated to find many useful applications in areas like sensors, catalysis, electronic devices, pharmaceuticals, drug formulations, nanomedicine, light harvesting, and smart materials.

Multimode binding and stimuli responsive displacement of acridine orange dye complexed with p-sulfonatocalix[4/6]arene macrocycles.

Interaction of acridine orange (AOH+) dye with water soluble anionic p-sulfonatocalix[n]arene (SCXn) hosts, SCX4 and SCX6, having different cavity dimensions, has been investigated using multispectroscopic techniques. Intriguing modulation in the photophysical properties of AOH+ upon interaction with SCXn hosts indicate the formation of different host-guest complexes at different regions of the host concentrations. At lower host concentrations, AOH+ undergoes SCXn assisted aggregation, causing a drastic reduction in fluorescence intensity. At higher host concentrations, aggregated-AOH+-SCXn complexes disintegrate and monomeric-AOH+-SCXn exo and inclusion complexes are eventually formed, leading to a huge fluorescence enhancement finally. Observed effects are more pronounced with SCX6 as compared to SCX4 host. Time-resolved fluorescence studies indicate that at very high host concentrations, there is also a diffusion-controlled dynamic quenching for both monomeric-AOH+-SCXn exo and inclusion complexes, caused by the free SCXn present in the solution, a phenomenon not reported before for such host-guest systems. The aggregated-AOH+-SCXn complexes at lower host concentration were employed to investigate displacement study using an antiviral drug, 1-adamantanamine (AD) and a neurotransmitter, acetylcholine (AcCh), as the competitive binders cum external stimuli, which resulted in a drastic recovery of the fluorescence reduced initially due to aggregation process. Though both the AOH+-SCXn systems act as efficient supramolecular assemblies in sensing AD and AcCh as the analytes through fluorescence "OFF-ON" mechanism, the effect is more pronounced for AOH+-SCX4 system as compared to AOH+-SCX6. SCXn induced interesting modulation in the photophysical properties of AOH+ and the stimulus responsive dye displacement observed for aggregated-AOH+-SCXn systems can expectedly find applications in fluorescence OFF-ON sensing, supramolecular functional materials and similar others.

Does the degree of substitution on the cyclodextrin hosts impact their affinity towards guest binding?

Although cyclodextrins have been extensively utilized in various branches of supramolecular chemistry due to their numerous attractive attributes, however, to achieve even advanced applications, they often need structural modification through substitutions of suitable functional groups at their rims. A systematic investigation on how the degree of substitution on the cyclodextrin rims affects the binding affinity for a given guest molecule has however rarely been reported, especially from the perspective of photophysical studies. Herein, we report the non-covalent interaction of a styryl based dye, LDS-798, with three different sulfobutylether beta cyclodextrin (SBEnßCD) derivatives bearing varying degrees of substitution (n), using ground state absorption, steady-state emission, excited-state lifetime and time-resolved fluorescence anisotropy measurements. The dye-host binding constant values indicate that the strength of the interaction between LDS-798 and SBEnßCD derivatives follows an increasing trend with an increasing number of tethered sulfobutylether substituents on the cyclodextrin rims, which is attributed to the gradual increase of the electrostatic interaction between the negatively charged sulfobutylether groups and the positively charged LDS-798. Excited state lifetime measurements and ionic strength dependent studies on the dye-SBEnßCD complexes further support the increased affinity between the dye and the host in the supramolecular complexes, with an increasing number of sulfobutylether substituents on the ßCD rims. The obtained results suggest that the molecular recognition of LDS-798 with SBEnßCD derivatives can be tuned very effectively by varying the number of sulfobutylether substituents on the cyclodextrin rims. Considering that SBE7ßCD is one of the FDA approved agents for drug formulations, the obtained results with other SBEnßCD hosts may be useful in designing selective drug delivery applications, drug formulations, and effective fluorescence on-off switches.

A comprehensive insight on H-type aggregation in Congo red-surfactant systems revealed through spectroscopic and electrochemical study unified with a simulation framework.

Interaction of an anionic diazo dye, Congo red (CR), with conventional surfactants: cetyltrimethylammonium bromide (CTAB) and Gemini surfactant: N,N'-dihexadecyl-N,N,N',N'-tetramethyl-N,N'-ethanediyl-diammonium dibromide (16-2-16), in their pre-micellar and post-micellar concentration regions has been investigated using conductometry, surface tensiometry, UV-visible spectroscopy, fluorescence spectroscopy, dynamic light scattering (DLS), cyclic voltammetry (CV) and linear sweep voltammetry (LSV) techniques. Various interfacial, micellar, band gap and electrochemical parameters are estimated at 303.15 K. The observed results are explained in terms of critical micelle concentration (CMC) of the individual surfactants and their ability to undergo aggregation in the presence of dianionic CR. It is found that the CMC of both the surfactants decreases in the presence of CR, which is attributed to the electrostatic attraction, short-range π-π stacking of CR molecules, and the hydrophobic forces operating between CR and the surfactant molecules. The spectral results for CR showed a hypsochromic (blue) shift below the CMC for both the surfactants, which indicates the resultant CR-surfactant complexation through ion-pair formation, which further inferred H-aggregation of CR in the pre-micellar region. Above the CMC, CR reverts back to its monomeric state and gets bound to the micelle. Job's method is employed to determine the stoichiometric ratio between CR and the individual surfactant. The size distribution of surfactants in the presence of CR is determined by DLS. The CV and LSV measurements were performed in the absence and presence of a varying concentration of surfactants to support the spectral findings. Diffusion coefficient (D) calculated by LSV confirmed the successive interaction between CR and surfactants. Furthermore, the CR-surfactant interaction is also elucidated by the computational simulation using the Gauss View 5.0.9 package to validate the obtained experimental findings.

A styryl based fluorogenic probe with high affinity for a cyclodextrin derivative.

Supramolecular host-guest pairs, with a very high association constant, represent excellent molecular recognition motifs, and serve as useful building blocks for numerous exciting supramolecular functional materials. Cyclodextrins, an important class of glucopyranose-based hosts, generally, suffer from low affinity for most guest molecules (102-104 M-1). Herein, we report a styryl-based fluorogenic probe which registers a very high association constant of 7.84 × 105 M-1 with sulfobutylether substituted ß-cyclodextrin in contrast to a low association constant of 1.89 × 102 M-1 with unmodified ß-cyclodextrin (ß-CD). This exceptionally high binding affinity of the fluorogenic probe with the sulfobutylether substituted ß-CD has been attributed to the strong electrostatic interactions between the cationic guest and the polyanionic host along with improved hydrophobic interactions due to the extended butylether groups present on the rims of the cyclodextrin cavity. The significant modulations in the photophysical properties of guest molecule, upon interaction with host molecule, have been investigated, in detail, using ground-state absorption, steady-state fluorescence and time-resolved emission measurements. The effect of temperature and ionic strength of the medium have been employed to investigate the nature of the underlying interactions in the present host-guest system. The possibility of indicator displacement assay involving the present host-guest system has also been demonstrated using a competitive binder.

Kinetics and Energetics of Ultrafast Bimolecular Photoinduced Electron Transfer Reactions in Pluronic-Surfactant Supramolecular Assemblies.

Understanding the kinetics and energetics of photoinduced electron transfer (PET) reactions in constrained media has attracted considerable research interest, as constrained media provide a handle to tune the microenvironments and consequently the mechanisms of PET reactions. In this study, PET reactions between excited 7-aminocoumarin acceptors and ground-state N,N-dimethylaniline (DMAN) donor have been investigated in mixed micellar media composed of triblock copolymer, P123, and anionic surfactant, sodium dodecyl sulfate (SDS), with varying SDS-to-P123 molar ratios (n values). The objective is to elucidate the role of the n values in the rates and energetics of PET reactions over the entire time range from the subpicosecond to the subnanosecond domain, especially in regard to the applicability of the two-dimensional ET (2DET) mechanism. It is observed that by changing the n values, there is a significant change in the hydration characteristics of the SDS-P123 mixed micelles, which in turn changes the kinetics to energetic correlations for the PET reactions. Fluorescence from the excited coumarin acceptors undergoes substantial quenching due to PET from DMAN donor in all of the studied micelles as evidenced from steady-state, subnanosecond time-resolved (TR) and ultrafast (subpicosecond/femtosecond) fluorescence up-conversion measurements. The quenching rate constants (kq), estimated from subnanosecond TR fluorescence studies, and the individual component-wise decay rates (τi-1), estimated from up-conversion measurements, increase gradually with increasing n value, corroborating well with the sequentially increased micropolarity of the mixed micelles. Interestingly, it is observed that the correlations of either kq (from subnanosecond studies) or τi-1 (from femtosecond studies) with the reaction exergonicity (-ΔG°) show the noteworthy Marcus inversion (MI) behavior in a very consistent and similar manner for the entire time window, from subpicoseconds to subnanoseconds. The onset of MI always appears at an exergonicity (-ΔG°MI) much lower than solvent reorganization energy (λs), suggesting the involvement of 2DET mechanism throughout the subpicosecond to subnanosecond time domains. The present results thus provide a comprehensive picture of the kinetics and energetics of the PET reactions in constrained media for the whole time span and unequivocally establish the applicability of 2DET mechanism for the PET reactions in constrained media, eliminating any apprehensions about the effect of time resolution of the subnanosecond setup on the observed Marcus inversion behavior. This is indeed an important finding, providing valuable insights for PET reactions in constrained media, which has not been explored explicitly in any of the previous studies. Observation of MI behavior and the modulations in the PET reactions by simply changing the composition of SDS in the SDS-P123 mixed micelles are noteworthy findings of the present study and are expected to find suitable applications for better utilization and outcome of the PET reactions.

An insight into the molecular and surface state photoluminescence of carbon dots revealed through solvent-induced modulations in their excitation wavelength dependent emission properties.

This study explores the intriguing modulations in the excitation wavelength dependence of carbon dot photoluminescence (PL), induced by the solvent medium. Our results indicate that different emissive states of carbon dots are stabilized to different extents by the surrounding solvent environment. Consequently, in some solvents, such as ethyl acetate and acetonitrile, the PL of the carbon dots is strongly dependent on the excitation wavelength, while in other solvents, like water, the PL of the same carbon dot becomes independent of the excitation wavelength. These observations contribute to the enhancement of our understanding of the photophysics and PL mechanisms of this important class of luminescent materials, especially to discriminate between the PL arising from the "molecular state" and the "surface state".

Photophysics and luminescence quenching of carbon dots derived from lemon juice and glycerol.

During the past decade, carbon dots have emerged as a fascinating class of luminescent nanomaterials with versatile application potentials in bioimaging, labeling, photocatalysis and optoelectronics. Currently, intensive research is concentrated on understanding the intriguing optical properties of these promising materials and their utility as luminescence sensors. In this article, we describe the photoluminescence of carbon dots obtained from a bioresource (lemon juice) and from a small molecule precursor (glycerol), especially the quenching of their emission by nitrobenzene and Hg2+ ions, as representative cases. Stern-Volmer analysis using steady-state and time-resolved emission measurements, suggests the involvement of both transient quenching and dynamic quenching mechanisms in the interaction of the carbon dots with nitrobenzene. The radius of the quenching sphere is estimated to be slightly greater than the contact distances between the respective carbon dots and nitrobenzene, which is in reasonable agreement with the "sphere of action" model for transient quenching. In the interaction with Hg2+ ions, electrostatic attraction plays a major role, and the quenching mechanism involves predominantly static and dynamic quenching. The static quenching constant matches well with the binding constant of the carbon dots with the metal ion.

Effect of Ionic Liquids as Cosurfactants on Photoinduced Electron Transfer in Tetronic Micelles.

This study investigates the role of varying alkyl chain lengths of a series of surface-active 1-alkyl-3-methylimidazolium tetrafluoroborate ([C nMIm][BF4], n = 4, 6, and 10) ionic liquids (ILs) as cosurfactants in modifying the micellar characteristics of a tetronic star-block copolymer, T1304, and the consequent effects on bimolecular photoinduced electron transfer (PET) reactions carried out in these T1304-IL mixed micellar systems. Using coumarin 153 as the probe dye and following ground-state absorption, steady-state fluorescence, and time-resolved emission measurements, the micropolarity, microviscosity, and solvent relaxation dynamics in the micellar palisade layer have been revealed both in pure T1304 and in T1304-IL systems. With increasing alkyl chain length of the ILs, the palisade layer of the micelles gradually becomes more polar and less viscous, suggesting better incorporation of the longer alkyl chain length ILs as cosurfactants into the T1304 micelles. The bimolecular PET reactions, involving 7-aminocoumarins as acceptors and N, N-dimethylaniline as the donor, are considerably modulated in T1304 micelles by the presence of the ILs, the effect being more prominent for ILs with longer alkyl chain lengths. In all of the micellar systems, correlations of the electron transfer (ET) kinetics with the reaction exergonicity (-Δ G0) show clear Marcus inversion (MI) behavior where onsets of MI invariably appear at significantly lower exergonicities, suggesting the involvement of a two-dimensional ET mechanism. Interestingly, the Marcus correlations display significant variations, namely, enhanced reaction rates and gradual shift in the onset of MI toward higher exergonicity, as longer alkyl chain length ILs are sequentially introduced as cosurfactants. From the observed results, it is convincingly realized that 1-alkyl-3-methylimidazolium-based ILs can be used satisfactorily as cosurfactants in tetronic star-block copolymer solutions to modulate PET reactions very significantly for their better utilizations in suitable applied areas.

Excited-state prototropism of 7-hydroxy-4-methylcoumarin in [Cnmim][BF4] series of ionic liquid-water mixtures: insights on reverse micelle-like water nanocluster formation.

This study explores the excited state prototropic behavior of the fluorophore, 7-hydroxy-4-methylcoumarin (7H4MC), in the [Cnmim][BF4] (n = 2, 4, 6, 8, 10) series of ionic liquid (IL)-water mixtures at low water contents. In pure IL media, 7H4MC exists in the neutral form in both ground and excited states. However, on addition of water to the ILs, the excited neutral form of the dye is gradually converted to the anionic and the tautomeric species, leading to characteristic changes in the emission spectra. The similarity in the spectral features of 7H4MC in the IL-water system with that in a conventional reverse micelle system rather than with organic solvent-water mixtures, suggests that in the presence of water, the ILs are organized into reverse micelle-like structures with the consequent formation of confined water pockets. The results further suggest that formation of water nanoclusters and the ensuing changes in excited state prototropic behavior of the dye, is facilitated by increase in the alkyl chain length of the IL cation. These propositions are supported by time-resolved fluorescence studies. To the best of our knowledge this is the first report on proton transfer reaction in IL-water mixtures at low water contents. Considering that ILs are useful as solvents and surfactants, and IL-water mixtures in particular have applications in chemical extractions and biocatalysis, an understanding of the structural organization and water pool formation in these systems is quite important. The insights obtained from the prototropic transformations of 7H4MC are significant not only for fundamental self-assembly studies, but also for the development of ILs as chemical reaction media.

A highly fluorescent turn-on probe in the near-infrared region for albumin quantification in serum matrix.

Developing sensitive and selective near-infrared fluorescent bio-probes for serum albumin detection is an ambitious and highly rewarding task. Herein, we report a styryl based fluorophore for serum albumin detection, which displays an exceptional turn-on emission enhancement of ∼500 fold, the highest reported so far in the near-infrared region, and more importantly enables quantification of albumin in the complex serum matrix.

Inhibition of the prototropic tautomerism in chrysazine by p-sulfonatocalixarene hosts.

This study explores the interesting effect of p-sulfonatocalix[n]arene hosts (SCXn) on the excited-state tautomeric equilibrium of Chrysazine (CZ), a model antitumour drug molecule. Detailed photophysical investigations reveal that conversion of CZ from its more dipolar, excited normal form (N*) to the less dipolar, tautomeric form (T*) is hindered in SCXn-CZ host-guest complexes, which is quite unexpected considering the nonpolar cavity of the hosts. The atypical effect of SCXn is proposed to arise due to the partial inclusion or external binding of CZ with the hosts, which facilitates H-bonding interactions between CZ and the sulfonate groups present at the portals of the hosts. The intermolecular H-bonding subsequently leads to weakening of the pre-existing intramolecular H-bond network within CZ, and thus hinders the tautomerizaion process. Our results suggest that rather than the binding affinity, it is the orientation of CZ in the SCXn-CZ complexes, and its proximity to the portals of the host that plays a predominant role in influencing the tautomeric equilibrium. These observations are supported by quantum chemical calculations. Thermodynamic studies validate that SCXn-CZ interaction is essentially enthalpy driven and accompanied by small entropy loss, which is consistent with the binding mechanisms.

Excited State Interaction of Ruthenium (II) Imidazole Phenanthroline Complex [Ru(bpy)2 ipH]2+ with 1,4-Benzoquinone: Simple Electron Transfer or Proton-Coupled Electron Transfer?

The unidirectional proton coupled electron transfer (PCET) from the excited state of Ru(II) imidazole phenanthroline complex [Ru(bpy)2 ipH]2+ to 1,4-benzoquinone, was studied by steady-state (SS) and time-resolved (TR) fluorescence and transient absorption (TA) measurements. The pKa (9.7) and pKa * (8.6) values of the complex suggest that it behaves as a photoacid on excitation. The difference in the quenching rates obtained from SS and TR fluorescence studies indicate participation of both dynamic quenching and static quenching involving the hydrogen bonded ipH ligand of [Ru(bpy)2 ipH]2+ with the 1,4-benzoquinone quencher, formed in the ground state. Within the hydrogen bonded complex, the ruthenium centre acts as the electron donor, while the ipH ligand acts as the proton donor to the hydrogen bonded 1,4-benzoquinone that acts simultaneously both as the electron and proton acceptor. It is proposed that the static quenching in the hydrogen bonded [Ru(bpy)2 ipH]2+ -1,4-benzoquinone pairs occurs involving the PCET mechanism, while the dynamic quenching occurs through the simple ET mechanism, on diffusional encounter of the isolated 1,4-benzoquinone with the excited [Ru(bpy)2 ipH]2+ complex. The occurrence of broad TA bands around 420-430 nm suggests formation of both 1,4-benzoquinone radical anion as well as the 1,4-benzosemiquinone radical by the interaction of excited [Ru(bpy)2 ipH]2+ with 1,4-benzoquinone, thus supporting the ET process in the studied system.

Tetronic Star Block Copolymer Micelles: Photophysical Characterization of Microenvironments and Applicability for Tuning Electron Transfer Reactions.

Detailed photophysical investigations have been carried out using a probe dye, coumarin-153 (C153), to understand the microenvironments of micelles formed by the newly introduced Tetronic star block copolymers, T1304 and T1307, having the same poly(propylene oxide) (PPO) block size but different poly(ethylene oxide) (PEO) block sizes. Ground state absorption, steady-state fluorescence, and time-resolved fluorescence measurements have been used to estimate the micropolarity, microviscosity, and solvation dynamics within the two micelles. To the best of our knowledge, this is the first report on these important physicochemical parameters for this new class of the star block copolymer micelles. Our results indicate that T1307 micelle offers a relatively more polar and less viscous microenvironment in the corona region, compared to T1304. The effect of the two micellar systems has subsequently been investigated on the bimolecular photoinduced electron transfer (ET) reactions between coumarin dyes (electron acceptors) and aromatic amines (electron donors). On correlating the energetics and kinetics of the ET reactions, clear Marcus inversion (MI) behavior is observed in both of the micellar media. Interestingly, the ET rates for all of the donor-acceptor pairs are much higher in T1307 than in T1304, and the onset of MI also appears at a relatively higher exergenocity (-Δ G0) in the former micelle (∼0.45 eV for T1307) than the latter (∼0.37 eV for T1304). The effect of added NaCl salt studied selectively in T1307 micelle shows that the ET rate decreases significantly along with a shift in the onset of MI toward lower exergenocity region, so that in the presence of 2 M NaCl the system becomes quite comparable to T1304. On the basis of the observed results, it is realized that the micropolarity and hence the dynamics of the ET process can be tuned very effectively either by changing the constitution of the star block copolymer or by using a suitable additive as a modifier of the micellar microenvironment.

Complexation induced aggregation and deaggregation of acridine orange with sulfobutylether-ß-cyclodextrin.

The present study reports a contrasting interaction behaviour of a biologically important dye, acridine orange (AOH+), with a highly water soluble anionic host, based on a ß-cyclodextrin (ßCD) scaffold, i.e. sulfobutylether-ß-cyclodextrin (SBEßCD), in comparison to native ßCD. AOH+ shows striking modulation in its photophysical properties, representing sequential changes in the modes of interaction with increasing SBEßCD concentration. At lower SBEßCD concentrations, AOH+ preferentially binds in dimeric forms at the negatively charged SBEßCD portals, leading to strong fluorescence quenching. At higher SBEßCD concentrations, the dimeric dyes convert to monomeric forms and subsequently undergo both inclusion and exo complex formation with 1 : 1 stoichiometry, resulting in a large fluorescence enhancement. The intriguing observation of sequential fluorescence switch off and switch on for an AOH+-SBEßCD system is clearly facilitated by the presence of butylether chains with SO3- end groups at the portals of SBEßCD, providing an additional ion-ion interaction and much enhanced hydrophobic interaction for cationic AOH+ compared to the native ßCD host. To the best of our knowledge, such fluorescence off/on switching through multistep host-guest binding has not been reported so far in the literature. The present study not only provides a detailed insight into the unique binding interactions of AOH+ with the SBEßCD host, but the findings of this study are also expected to be useful in designing supramolecular based drug formulations, drug delivery systems, sensors, and so on.