Banibrata Maity

Supramolecular Interaction between a Hydrophilic Coumarin Dye and Macrocyclic Hosts: Spectroscopic and Calorimetric Study

The photophysics of a hydrophilic molecule, 7-(diethylamino)-coumarin-3-carboxylic acid (7-DCCA), was studied in the presence of two macrocycles, (2-hydroxypropyl)-γ-cyclodextrin and cucurbit[7]uril. We have used steady-state absorption, fluorescence, and time-resolved fluorescence emission spectroscopy; Fourier transform infrared (FTIR) spectroscopy; (1)H NMR spectroscopy; and isothermal titration calorimetry (ITC) to confirm the supramolecular host-guest complex formation. The spectral properties of 7-DCCA were modulated in the presence of both macrocycles. It was assigned that 7-DCCA forms a 1:2 complex with (2-hydroxypropyl)-γ-cyclodextrin and cucurbit[7]uril. The large modulation of the emission properties of 7-DCCA in the presence of the macrocycles indicates the formation of supramolecular complexes. A significant shift in the bond vibration frequencies in the FTIR studies showed encapsulation of the dyes in the hydrophobic cavity of the macrocycles. This is further substantiated by the (1)H NMR studies, in which the upfield and downfield shifts of the protons were observed in both the aliphatic and aromatic region in the presence of macrocycles. The time-resolved anisotropy measurements further reinforce the conception of host-guest supramolecular complex formation because, in both cases, the rotational relaxation time increases significantly compared to that in water. A deeper understanding between the differences in interaction of an anionic molecule with cucurbit[7]uril and (2-hydroxypropyl)-γ-cyclodextrin will be achieved through this work. From the ITC measurement, we have formulated the forces due to complex formation.

Interaction of the nonsteroidal anti-inflammatory drug indomethacin with micelles and its release.

In this study, we have reported the binding interaction and photophysics of a nonsteroidal anti-inflammatory drug (NSAID) indomethacin (IMC) in the presence of different micelles. We have used several spectroscopic techniques such as UV-vis absorption, steady state fluorescence and time-resolved fluorescence emission spectroscopy. The spectral properties of IMC were modulated in the presence of micelles compared to that in neat water. The weak emitting drug molecule (IMC) becomes highly fluorescent after binding with the micelles. The fluorescence quantum yield and fluorescence lifetime increase in the presence of micelles compared to those in neat water. The isothermal titration calorimetry (ITC) method was used to study the binding interaction of IMC with different micelles. The thermodynamic parameters and the nature of binding between IMC and different micelles have been estimated. Moreover, addition of KCl salt in the respective micelles releases IMC molecule from the micelles to the aqueous medium. This study will help elicidate the binding behavior of IMC in the presence of different micelles for possible use as potential drug delivery systems.

Photophysics of a coumarin in different solvents: use of different solvatochromic models.

This study reported the photophysics of 7‐(diethylamino)coumarin‐3‐carboxylic acid N‐succinimidyl ester (7‐DCCAE) in different neat solvents of varying polarity using steady‐state absorption, fluorescence emission and picosecond time‐resolved spectroscopy. In nonpolar solvents, the dye molecule predominantly exists in nonpolar structure and exhibits very low value of nonradiative decay rate constant (knr), demonstrating the emission takes place from S1‐LE to S0 ground state. The fluorescence quantum yields, lifetime values of 7‐DCCAE in different solvents are rationalized on the basis of intramolecular charge transfer (ICT) followed by twisted intramolecular charge transfer state formation (TICT) as well as specific solute–solvent interactions. Several solvatochromic models (such as Lippert, Dimroth, Kamlet–Taft, Catalán 3P and Catalán 4P models) were used to analyze the solvatochromic shift of 7‐DCCAE in different solvents. The different empirical models show that the observed results are better correlate for nonchlorinated solvents and provide statistically significant best‐fit result. A comparison was done between comparatively new solvatochromic model (Catalán 3P and Catalán 4P model) with Kamlet–Taft model. The ground state structure of the said molecule was optimized by using Density Functional Theory (DFT).

Torsional Dynamics of Thioflavin T in Room-Temperature Ionic Liquids: An Effect of Heterogeneity of the Medium

The ultrafast excited-state dynamics of a fibril binding dye, thioflavin T (ThT), has been studied in two room-temperature ionic liquids (RTILs): 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and methyltrioctylammonium bis(trifluoromethylsulfonyl)imide. Previously, in most studies, it was observed that the excited-state dynamics of the ThT dye were dependent on the viscosity of the medium. In our study, by using RTILs, we have demonstrated that the excited-state dynamics of ThT are not only viscosity dependent, but also dependent on the heterogeneous nature of the medium. The effect of structural heterogeneity present in neat RTILs on the excited-state dynamics of ThT was observed. For both RTILs, excitation wavelength dependency on the emission properties of ThT was observed.

Host-guest interaction of 3-hydroxyflavone and 7-hydroxyflavone with cucurbit [7]uril: A spectroscopic and calorimetric approach

The modulation of photophysical behaviour of small organic molecules in the presence of macrocycles is one of the most interesting areas of research. In this work we reported the interaction of two biologically active molecules 3-hydroxyflavone and 7-hydroxyflavone with macrocyclic host cucurbit [7]uril in aqueous medium. To investigate the change of photophysical properties of these two flavones, we have used steady state absorption, fluorescence, time resolved fluorescence emission spectroscopy and isothermal titration calorimetric technique. It is observed that on complexation with cucurbit [7]uril, the excited state proton transfer processes in both flavones have been facilitated. Isothermal titration calorimetric method was used in order to investigate the involvement of thermodynamic parameters in complexation between flavone with cucurbit [7]uril. The changes in thermodynamic properties due to the complexation of the flavones molecules with cucurbit [7]urils help to understand about the governing parameters involved in this complexation. The inclusion of flavone molecules inside the cavity of cucurbit [7]uril molecules was studied theoretically to decipher the molecular orientation of flavones in the presence of cucurbit [7]uril. The structure of HOMO and LUMO of the complexes between cucurbit [7]uril with flavones was reported. This study will be helpful to get the knowledge about the modulation of photophysical properties of the flavones molecules on addition of macrocyclic host cucurbit [7]uril. This study will be helpful for the use of cucurbit [7]uril as a potential drug delivery system.

Supramolecular interaction of a cancer cell photosensitizer in the nanocavity of cucurbit[7]uril: A spectroscopic and calorimetric study.

The interaction of small biologically active molecules in the nanocavity of supramolecular host is very interesting and thriving research area. In the presence of supramolecular host the absorption and emission properties of small biologically active molecules were modulated several folds compared to bulk solution. In this study we have investigated the supramolecular interaction of a cancer cell photosensitizer molecule harmane in the presence of cucurbit[7]uril (CB7) as host in aqueous buffer solution (pH∼7.2). We have used steady state absorption, emission and time resolved fluorescence spectroscopy techniques. The thermodynamics of the binding between harmane in the nanochannel of CB7 were studied by using isothermal titration calorimetry (ITC) method. The emission properties of harmane are modulated several fold in the presence of CB7. ITC study indicates that the complexation between harmane and CB7 are enthalpically favourable.

Surfactants induced release of a red emitting dye from the nanocavity of a molecular container: A spectroscopic and calorimetric study.

Supramolecular interaction of a red emitting dye Nile blue A (NBA) with Cucurbit[7]uril (CB7) in aqueous solution was studied and the release of the dye from the hydrophobic cavity of CB7 was reported. To investigate the supramolecular host-guest complex formation and release of dye, we have used the steady state absorption, fluorescence and time resolved fluorescence emission spectroscopy, (1)H NMR spectroscopy and isothermal titration calorimetry (ITC). The spectral properties of NBA were changed in the presence of CB7. The change in spectral features of NBA in presence of CB7 indicates the formation of supramolecular host-guest complexes. By using the SED equation the diameter of the complex was estimated. The complex formation further affirmed by the (1)H NMR study. Upfield and downfield shifts of the protons of NBA was observed in both the aliphatic and aromatic region. From the ITC measurement, we have drawn up the forces involved for the complexation of NBA with CB7. We have studied the release of NBA from the hydrophobic cavity of CB7 by using ionic, neutral surfactants and ionic liquid with the help of spectroscopic and calorimetric techniques. It is observed that on addition of SDS and ionic liquid (<cmc) ion-pair formation takes place between NBA and surfactant monomer whereas, it was not observed for neutral and cationic surfactant. Above cmc of the surfactants, complex is formed between NBA and micelle.

Influence of double confinement on photophysics of 7-(diethylamino)coumarin-3-carboxylic acid in water/AOT/isooctane reverse micelles

The effect of double confinement on the photophysics of 7-(diethylamino)coumarin-3-carboxylic acid (7-DCCA) inside the water pool of water/AOT/isooctane reverse micelles has been reported in this study. At first a supramolecular host–guest complex was formed in water between 2-hydroxypropyl-γ-cyclodextrin (HP-γ-CD) and 7-DCCA. Then the aqueous solution of this complex was used to form reverse micelles at any particular w0 value (w0 = [water]/[surfactant]). We have used sodium dioctyl sulfosuccinate (AOT) as surfactant and isooctane as non-polar solvent to prepare reverse micelles. A comparative study between double confinement system and the single confinement system, where the 7-DCCA molecule was incorporated inside the core of the water/AOT/isooctane reverse micelles, was done. We have used the steady state absorption and fluorescence emission techniques to highlight the significant shift of the spectral behaviour of the 7-DCCA due to the double encapsulation of the dye in the nanopool of the reverse micelles. More affirmation has been achieved by the use of time resolved fluorescence emission spectroscopy. The study of solvation dynamics and rotational relaxation dynamics was used as tools to investigate the effect of double encapsulation on the excited state dynamics of the probe molecule. These excited state dynamics clearly show that even at the highest w0 value studied here, the excited state dynamics of the doubly confined dye are significantly different from those of the single confined dye in the reverse micelle. The higher values of fluorescence emission decay time, rotational relaxation and solvent relaxation times in the doubly confined system compared to those of the single confined system at different w0 values proved the existence of the supramolecular host–guest complex inside the core of the water/AOT/isooctane reverse micelle.

Photophysics of 7-(diethylamino)coumarin-3-carboxylic acid in cationic micelles: effect of chain length and head group of the surfactants and urea

In this work, we have studied the effects of chain length and the head group of different cationic surfactants on the photophysics of an anionic dye, 7-(diethylamino)coumarin-3-carboxylic acid (7-DCCA), using steady state absorption and fluorescence emission spectroscopy, and time resolved emission spectroscopy. We have observed pronounced effects on the photophysics of 7-DCCA, by varying the chain length and the head group of the surfactants. The fluorescence quantum yield, decay time, solvent relaxation time, and rotational relaxation time changes with chain length and the head group of the surfactants. We have studied the effect of urea on the photophysics of 7-DCCA bound to the micellar media and found that urea causes increases in the fluorescence quantum yield, fluorescence decay time, and solvent relaxation time. These aspects clearly demonstrate that the addition of urea does not cause the removal of the dye from the micellar surface.

The photophysics of 7-(diethylamino)coumarin-3-carboxylic acid N-succinimidyl ester in reverse micelle: excitation wavelength dependent dynamics

This paper focuses on the photophysical studies of 7-(diethylamino)coumarin-3-carboxylic acid N-succinimidyl ester (7-DCCAE) in aqueous reverse micelles using steady state absorption, fluorescence emission and picosecond time resolved emission spectroscopy. We used sodium dioctylsulfosuccinate (AOT) as surfactant to prepare reverse micelles. We have observed excitation wavelength dependent photophysics of 7-DCCAE in the reverse micelles. The red edge excitation shift (REES) was found in the reverse micelles, at different w0 values. The REES gradually decreases with increase in size of the water pool. The rotational relaxation time of the dye molecule decreases with increasing the mole ratio of water to surfactant (w0) inside the reverse micelles. The fluorescence anisotropy decays were found biexponential in nature with fast and slow reorientation times, which is explained by two steps and “wobbling-in-cone model”. We have observed the excitation wavelength dependent dynamics of 7-DCCAE in the reverse micelles. We have observed the difference in the photophysics 7-DCCAE with its acid form.