A. Antony Muthu Prabhu

Excimer formation in inclusion complexes of β-cyclodextrin with salbutamol, sotalol and atenolol: Spectral and molecular modeling studies

The inclusion complexation behavior of salbutamol, sotalol and atenolol drugs with β-cyclodextrin (β-CD) were investigated by UV-visible, fluorometry, time resolved fluorescence, FT-IR, (1)H NMR, SEM and PM3 methods. The above drugs gave a single emission maximum in water where as dual emission in β-CD. In β-CD solutions the shorter wavelength fluorescence intensity was regularly decreased and longer wavelength fluorescence intensity increased. Addition of β-CD to aqueous solutions of drugs resulted into excimer emission. The excimer emission is concluded to be due to a 1:2 inclusion complex between β-CD and drug. Nanosecond time-resolved studies indicated that all drugs exhibited biexponential decay in solvents and triexponential decay in CD. Investigations of thermodynamic and electronic properties confirmed the stability of the inclusion complex.

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.

Azonium-Ammonium Tautomerism and Inclusion Complexation of 1-(2,4-diamino phenylazo) Naphthalene and 4-aminoazobenzene

Spectral characteristics of 1-(2,4-diamino phenylazo) naphthalene (FBRR, fat brown RR) and 4-aminoazobenzene (AAB) have been studied in various solvents, varying hydrogen ion concentrations and in β-cyclodextrin (β-CD). The inclusion complex of FBRR and AAB with β-CD were analysed by UV-visible, fluorometry and CAche-DFT methods. Solvent study reveals that only azo tautomer is present in both compounds and the large red shifted absorption and emission maxima of FBRR indicate naphthalene ring effectively increases the π-π* transition. Unusual red shift is observed in acid solutions suggests azonium-ammonium tautomer is present in both molecules. In β-CD solutions, the large hypsochromic shift is observed in S0 and S1 states indicates ortho amino group of FBRR molecule is entrapped in the β-CD cavity and the large bathochromic shift for AAB in the S1 state indicates 1:1 inclusion complex is formed.

Spectral characteristics of sulphadiazine, sulphisomidine: effect of solvents, pH and β-cyclodextrin

The absorption and fluorescence spectra of sulphadiazine (SDA), sulphisomidine (SFM) and sulphanilamide (SAM) have been analysed in different solvents, pH and β-cyclodextin. The inclusion complexes of the above sulphonamides with β-CD were investigated by UV–Vis, fluorometry, DFT, FT–IR and 1H-NMR. The solvent study shows that the absorption and emission maxima of the SDA and SFM are more red-shifted than SAM molecule. In non-aqueous solvents, a single fluorescence band (340 nm) is observed, whereas in water and β-CD solutions, dual emission (at 340 and 430 nm) is noticed for SDA and SFM molecules. The dual emission is due to twisted intramolecular charge transfer band (TICT). Studies on β-CD solutions reveal that (1) sulphonamides form 1 : 1 inclusion complex with β-CD; and (2) the red-shift and the presence of TICT in the β-CD medium confirm that the heterocyclic ring is encapsulated in the hydrophobic part and aniline ring is present in the hydrophilic part of the β-CD cavity.

Azo-hydrazo Tautomerism and Inclusion Complexation of 1-phenylazo-2-naphthols with Various Solvents and β-cyclodextrin

Spectral characteristics of sudan I (SDI), sudan II (SDII) and mordant violet-5 (MV5) have been studied in various solvents and β-cyclodextrin (β-CD). The inclusion complex of the above molecules with β-CD was analyzed by UV-visible, fluorometry, and DFT methods. The solvent study shows that azo-hydrazo tautomer is present in these molecules. The increase in the fluorescence intensity and a large bathochromic shift in the S1 state indicate these molecules forms 1:1 inclusion complex with β-CD.

Encapsulation of Labetalol, Pseudoephedrine in β-cyclodextrin Cavity: Spectral and Molecular Modeling Studies

The absorption and fluorescence spectra of labetalol and pseudoephedrine have been studied in different polarities of solvents and β-cyclodextrin (β-CD). The inclusion complexation with β-CD is investigated by UV-visible, steady state and time resolved fluorescence spectra and PM3 method. In protic solvents, the normal emission originates from a locally excited state and the longer wavelength emission is due to intramolecular charge transfer (TICT). Labetalol forms a 1:2 complex and pseudoephedrine forms 1:1 complex with β-CD. Nanosecond time-resolved studies indicated that both molecules show triexponential decay. Thermodynamic parameters (ΔG, ΔH, ΔS) and HOMO, LUMO orbital investigations confirm the stability of the inclusion complex. The geometry of the most stable complex shows that the aromatic ring is deeply self included inside the β-CD cavity and intermolecular hydrogen bonds were established between host and guest molecules. This suggests that hydrophobic effect and hydrogen bond play an important role in the inclusion process.

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.

Unusual spectral shifts of imipramine and carbamazepine drugs.

The absorption and fluorescence spectra of imipramine and carbamazepine have been recorded in solvents of different polarity and β-cyclodextrin (β-CD). The inclusion complexes for both drugs are investigated by UV-visible, fluorimetry and DFT. Solvents study shows isotropic polarizability structure is present in imipramine while the amide group inhibits the above structure in carbamazepine. The band width half a maximum of carbamazepine decreased in polar solvents suggest that different species present in non-polar solvents and among that one of this species is affected in protic solvents. Both drugs form two different 1:2 inclusion complexes with β-CD. The structured longer wavelength emission in β-CD solution suggests viscosity plays major roles in the inclusion complex. This study also confirms van der Waals forces and hydrophobic interactions are the driving forces in imipramine and hydrogen bonding interactions play major roles in carbamazepine.

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.