R.K. Sankaranarayanan

Dual Fluorescence of Fast Blue RR and Fast Violet B: Effects of Solvents and Cyclodextrin Complexation

Absorption and steady-state and time-resolved fluorescence spectra of fast blue RR (FBRR) and fast violet B (FVB) were studied in solvents with different polarities and in the presence of α- and β-cyclodextrins (CDs). Dual emission observed in nonpolar solvents suggested that the energy of the intramolecular charge transfer (ICT) state is lower than that of the locally excited state. The normal Stokes-shifted band originated from the locally excited state, and the large Stokes-shifted band was due to the emission from a planar intramolecular charge transfer (PICT) state. The ratio of the PICT emission to the normal emission increased with β-CD concentration, whereas it was constant upon addition of α-CD. This behavior is in accordance with CD-dependent decay times of PICT and normal emissions, indicating the formation of different 1:1 FBRR/CD inclusion complexes. The rise time for the PICT emission increased with β-CD concentration, whereas no rise time was observed in the case of the α-CD complex. The size of the dimethoxyaniline ring suggested that the orientation of FBRR in the β-CD complex was different from that in the α-CD complex. The benzamido moiety of FBRR is deeply encapsulated in the CD cavity, whereas the aniline ring is exposed to the hydrophilic part. Semiempirical quantum-mechanical (ΔE, ΔG, ΔH, ΔS, and HOMO-LUMO) calculations were also carried out to assign the encapsulation of FBRR and FVB.

Intramolecular Proton Transfer Effects on 2,6-diaminopyridine

The photophysical behaviour of 2,6-diaminopyridine (DAP) has been studied in solvents of different polarity, pH, β-cyclodextrin (β-CD) and compared with 2-amino pyridine (2AP). The inclusion complex of both molecules with β-CD are analysed by UV-visible, fluorimetry, FT-IR, 1H NMR, SEM and AM1 methods. The solvent studies shows i) DAP gives more red shifted absorption and emission maxima than 2AP molecule and ii) addition of amino group in 2AP effectively increase the resonance interaction in the pyridine ring. A regular red shift observed in acidic pH solutions suggests intramolecular proton transfer (IPT) present in both molecules. β-CD studies indicates i) in pH  ~ 7, a regular red shifted absorption and emission maxima observed in AP molecules suggests pyridine ring encapsulated in to the β-CD cavity (1:1 inclusion complex formed) and ii) in pH ~ 1, a blue shifted absorption maxima noticed in 2AP, is due to protonated amino group deeply encapsulated in to the hydrophobic part of the β-CD cavity.

Unusual spectral shifts on fast violet-B and benzanilide: Effect of solvents, pH and β-cyclodextin

The absorption and fluorescence spectra of fast violet-B (FVB) and benzanilide (BA) have been analysed in different solvents, pH and beta-cyclodextrin. The inclusion complex of FVB with beta-CD is investigated by UV-visible, fluorimetry, AM 1, FTIR and SEM. The absorption maximum of FVB (anilino substitution) is red shifted than that of BA, but the benzoyl substitution hardly changed the ground state structure of BA. Compared to BA, the emission maxima of FVB largely blue shifted in cyclohexane and aprotic solvents, but red shifted in protic solvents and the longer wavelength maxima in FVB is due to the intramolecular charge transfer (TICT). In BA, the normal emission originates from a locally excited state and the longer wavelength band due to intramolecular proton transfer in non-polar/aprotic solvents and in protic solvents it is due to TICT state. beta-CD studies reveal that, FVB forms 1:2 complex from 1:1 complex and BA forms 1:2 complex with beta-CD.

Absorption and fluorescence spectral characteristics of norepinephrine, epinephrine, isoprenaline, methyl dopa, terbutaline and orciprenaline drugs

The absorption and fluorescence spectral characteristics of norepinephrine, epinephrine, isoprenaline, methyl dopa, orciprenaline and terbutaline have been investigated for levels of different pH and β-cyclodextrin (β-CD). The inclusion processes are discussed based on absorption, emission and semiempirical quantum mechanical calculations (CAChe – DFT). The pH study reveals that, deprotonation takes place in the CHOH group and the longer wavelength emission at 450 nm is due to intramolecular proton transfer. The β-CD study shows that the above-mentioned drugs form 1:1 inclusion complexes. Single-emission maximum in water (∼316 nm) and dual emission (316 nm, 450 nm) in β-CD is noticed for drugs. In the β-CD solutions, the shorter wavelength fluorescence intensity is regularly decreased and longer wavelength fluorescence intensity is increased. The alkyl chain and the hydroxyl group are present in the interior and hydrophilic parts of the β-CD cavity, respectively.

Spectral characteristics of 2-amino-3-benzyloxy pyridine: Effects of solvents, pH, and β-cyclodextrin

Spectral characteristics of 2-amino-3-benzyloxypyridine (2ABP) has been studied in solvents of different polarity, pH, and β-cyclodextrin (β-CD) and compared with 2-amino pyridine (2AP). The inclusion complex of both amino pyridine (AP) molecules with β-CD are analysed by UV-visible, fluorimetry, FTIR, 1H NMR, SEM and AM1 methods. The solvent studies shows no significant shift observed in absorption maxima between both AP molecules, but in the excited state a slight red shift is noticed in 2ABP than in 2AP which indicates that the addition of benzyloxy group in 2AP does not effectively increase the resonance interaction in 2ABP. The regular red shift observed in acidic pH solutions suggests intramolecular proton transfer (IPT) interaction in both molecules. β-CD studies shows that in pH ∼7, 2ABP forms 1: 2 inclusion complex from 1: 1 inclusion complex and 1: 1 inclusion complex is formed in pH ∼ 1. In pH ∼ 7, a red shift observed in 2ABP with lower β-CD concentration suggests aromatic ring encapsulated in the β-CD cavity and blue shift noticed at higher β-CD concentrations indicates pyridine ring encapsulated in the β-CD cavity.

Nanostructures formed by cyclodextrin covered aminobenzophenones through supramolecular self assembly.

Cyclodextrin (α and β) based nanostructures formed with 2-aminobenzophenone, 3-aminobenzophenone through the supramolecular self assembly are studied by absorption, fluorescence, time-resolved fluorescence, SEM, TEM, FT-IR, DSC, PXRD and (1)H NMR. The unequal layer by layer nanosheets and nanoribbons are formed through self assembly of 3ABP/CD inclusion complexes. 2ABP/α-CD complex nanostructures show the self assembly hierarchical thread structure and β-CD complexes displays a nanobrick structure. The formation of nanostructures are prearranged to HO⋯H, NH2⋯O and H2N⋯H intermolecular hydrogen bond between individual complexes. The absorption and fluorescence spectral changes explicit formation of 1:1 inclusion complexes and solvent study demonstrate the ESIPT and TICT present in both molecules. The thermodynamic parameters (ΔH, ΔG and ΔS) of 2ABP and 3ABP molecule and the inclusion complexes were determined from semiempirical PM3 calculations.

Nanostructures formed by cyclodextrin covered procainamide through supramolecular self assembly--spectral and molecular modeling study.

Inclusion complexation behavior of procainamide (PCA) with two cyclodextrins (α-CD and β-CD) were analyzed by absorption, fluorescence, scanning electron microscope (SEM), transmission electron microscope (TEM), Raman image, FT-IR, differential scanning colorimeter (DSC), Powder X ray diffraction (XRD) and (1)H NMR. Blue shift was observed in β-CD whereas no significant spectral shift observed in α-CD. The inclusion complex formation results suggest that water molecules also present in the inside of the CD cavity. The present study revealed that the phenyl ring of the PCA drug is entrapped in the CD cavity. Cyclodextrin studies show that PCA forms 1:2 inclusion complex with α-CD and β-CD. PCA:α-CD complex form nano-sized particles (46 nm) and PCA:β-CD complex form self-assembled to micro-sized tubular structures. The shape-shifting of 2D nanosheets into 1D microtubes by simple rolling mechanism were analysed by micro-Raman and TEM images. Thermodynamic parameters (ΔH, ΔG and ΔS) of inclusion process were determined from semiempirical PM3 calculations.

Nanochain and vesicles formed by inclusion complexation of 4,4′-diaminobenzanilide with cyclodextrins

The nanochain-like agglomerates and spherical nanovesicles were formed from supramolecular self-assembly of 4,4′-diaminonenzanilide (DABA) with α- and β-cyclodextrins. The DABA with α-CD and β-CD inclusion complex nanomaterials were prepared and characterised by transmission electron microscopy, scanning electron microscopy, FTIR, differential scanning calorimetry, 1H NMR and powder X-ray diffraction. 1H NMR analysis indicated that the benzamido ring of DABA was encapsulated into the cyclodextrin (CD) cavity. Absorption and fluorescence spectral studies suggested that DABA forms different types of nanomaterials in α-CD and β-CD solutions. Higher occupied molecular orbital, lower unoccupied molecular orbital, and thermodynamic parameter values confirmed DABA dye entrapped in the CD cavities.

Nanorod formation of cyclodextrin-covered sudan dyes through supramolecular self-assembly

Cyclodextrin-covered sudan III (SDIII) and sudan IV (SDIV) dyes produced various nanostructures such as pseudorotaxanes through supramolecular self-assembly, studied by absorption, fluorescence, time-resolved fluorescence, SEM, TEM, FT-IR, DSC, PXRD and 1H NMR. Solvent study shows that azo–hydrazo tautomer is present in sudan dyes. Absorption and fluorescence spectroscopy data gave evidence for the formation of 1:2 inclusion complexes. Big nanorod (∼36 nm) surrounded by small nanorod (∼3 nm) was identified in SDIV/α-CD complexes. This confirms that the rigid molecular nanorod aggregates of α-CD and β-CD complexes are formed through the initial formation of smaller nanorods. An unequal morphology noticed in SDIII/CD suggests that the 1:2 inclusion complexes were self-assembled into irregular arrangement. The thermodynamic parameters (ΔH, ΔG and ΔS) of inclusion processes were determined from semi-empirical PM3 calculations.

Dual fluorescence of omeprazole: effect of solvents and pH

Absorption, steady state fluorescence and time-resolved fluorescence spectra of omeprazole (OMP) have been studied in solvents of different polarity and pH. With an increase in the polarity of the solvents, blue shift is observed in the longer wavelength whereas red shift is noticed in the shorter wavelength band. The dual emission observed in non-polar solvents suggests that the energy of the twisted intramolecular charge transfer (TICT) state is lower than that of the locally excited (LE) state. The normal Stokes-shifted band originates from the LE state, and the large Stokes-shifted band is due to the emission from a TICT state. The Stokes shift of OMP is correlated with various solvent polarity scales like ET(30) and f (D,n).