Excimer emission of caffeine with α- and β-cyclodextrins: spectral and molecular modelling studies

Excimer emission of caffeine with α-CD and β-CD were studied by UV-visible, fluorescence, time-resolved fluorescence, FTIR, ¹H NMR and molecular modelling techniques. Changes in the absorbance and fluorescence and lifetime of the caffeine with cyclodextrin (CD) solutions indicate (i) caffeine shows dual emission in the CD solutions, (ii) normal emission originates from a monomer and the longer wavelength emission is due to excimer and (iii) in both CDs caffeine forms 1:2 inclusion complex. Carbonyl stretching frequency moved to higher wave numbers and broadening of the N–H stretching band indicated the formation of inclusion complex. The resonance of the methyl protons of caffeine show remarkable upfield or downfield shift in the ¹H NMR, which indicates imidazole ring of the caffeine entrapped in the CD cavities. Investigations of energetic, thermodynamic and electronic properties of PM3 computational calculations confirmed the stability of the inclusion complex.     

Encapsulation of ciprofloxacin,sparfloxacin, and ofloxacin drugs with α- and β-cyclodextrins: spectral and molecular modelling studies

Inclusion complexation of ciprofloxacin (CIP), sparfloxacin (SPA), and ofloxacin (OFL) drugs with α-CD and β-CD was studied by UV-visible, fluorescence, time-resolved fluorescence, Fourier transform infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (¹HNMR), scanning electron microscopy (SEM), and molecular modelling techniques. Changes in the absorbance and fluorescence intensities and fluorescence lifetime of the drugs in the cyclodextrin (CD) solutions suggest the formation of inclusion complexes. Carbonyl stretching frequency moved to higher wave numbers and broadening of the N–H stretching band indicated the formation of inclusion complex. Cyclohexane ring protons of the drugs show remarkable upfield or downfield shift in the ¹HNMR spectrum, indicating that the cyclohexane part of the guest molecule is entrapped inside CD cavities. SEM images of CIP/CD, SPA/CD, and OFL/CD complexes have a crystal structure with different morphology from the isolated CIP, SPA, OFL, and CDs. Investigations of the energetic, thermodynamic, and electronic properties of parametric model number 3 computational calculations confirmed the stability of the inclusion complex.     

Ruthenium(ii)-catalyzed regioselective direct C4- and C5-diamidation of indoles and mechanistic studies

A ruthenium(ii)-catalyzed regioselective direct diamidation of 3-carbonylindoles at the C4- and C5-positions using various dioxazolones is described. This novel protocol allows for the effective installation of two amide groups on the benzene ring in indole. A remarkably broad substrate scope, excellent functional group tolerance, and mild reaction conditions are notable features of this protocol. Further explorations reveal that benzo[b]thiophene-3-carboxaldehyde is a viable substrate and affords its corresponding diamidation products. The diamido indoles are further converted into various functionalized products and used as sensors for metal ion detection. Density functional theory studies are also conducted to propose a reaction mechanism and provide a detailed understanding of the regioselectivity observed in the reaction.

Ruthenium(ii)-catalyzed regioselective C4-/C5-diamidation of 3-carbonylindoles is described and a DFT study is conducted to understand the observed regioselectivity and the mechanism.     

Excimer Emission in Norepinephrine and Epinephrine Drugs with α- and β-Cyclodextrins: Spectral and Molecular Modeling Studies

The inclusion complexation behavior of norepinephrine (NORE) and epinephrine (EPIN) with native cyclodextrins (α-CD and β-CD) were investigated by UV-visible, fluorimetry, time-resolved fluorescence, SEM, TEM, FT-IR, ¹H NMR, DSC, powder XRD and PM3 methods. Single emission was observed in aqueous solution where as dual emission (excimer) noticed in the CD solutions. Both drugs form 1:1 drug-CD complexes in lower CD concentrations and 1:2 CD-drug₂ complexes in the higher CD concentrations. Time-resolved fluorescence studies indicated that both drugs showed single exponential decay in water and biexponential decay in CD. Nano-sized self-aggregated particles of drug-CD were found by TEM studies. Molecular modeling studies indicated that aliphatic chain part of the drug was entrapped in the CD cavity. Thermodynamic parameters and binding affinity of complex formation of the CD were determined according to PM3 method. The PM3 results were in good agreement with the experimental results.     

Structural,electrical, thermal and optical properties of the nonlinear optical crystal L‐Arginine Fluoride

Single crystals of L‐Arginine Fluoride (LAF) have been grown by the slow evaporation technique, and the crystalline perfection was studied by HRXRD. Optical absorption studies reveal the lower cut off wavelength (280 nm) and the band gap (5.1 eV). The dielectric constant and dielectric loss have been measured as a function of frequency (42 Hz–5 MHz) and temperature (307‐368K) and the activation energy is 77 μeV. The thermal transport properties such as thermal conductivity (0.88 ± 0.02 W/mK) and specific heat capacity (482±24 J/kg/K) have been estimated by the photopyroelectric technique. The nonlinear refractive index n₂, is found to be of the order of 10⁻¹³ cm²/W by the Z‐scan technique.     

Gas sensing property of lithium tetraborate clad modified fiber optic sensor

The micro structured plate-like lithium tetraborate, Li₂B₄O₇ (1 μm in diameter) has been prepared by sol–gel method and characterized structurally by X-ray diffraction and morphologically by scanning electron microscopy. UV–Vis spectrum shows about 60% transparency in the visible region and the optical energy band gap is found to be 3.5 eV which is also confirmed by strong near band edge emission from luminescence spectrum. The spectral characteristics of the cladding modified fiber optic sensor coated with microcrystalline Li₂B₄O₇ are studied for various concentrations of ethanol, methanol and ammonia (50–500 ppm). At 298 K, the sensitivity for ethanol is ?10 counts/ppm which is relatively higher than ammonia (?4 counts/ppm) and methanol (?3 counts/ppm). The time response of the sensor is presented for pure Li₂B₄O₇ with ethanol gas.     

Third-order NLO properties of solution grown methyl-p-hydroxy benzoate single crystals

The third-order nonlinear optical properties of solution-grown methyl-p-hydroxy benzoate (MHB) single crystals were studied by Z-scan technique using a He-Ne (632.8 nm, 30 mW) laser. From the closed aperture Z-scan data, the valley followed by peak on the normalized transmittance indicates the sign of the nonlinear refractive index is positive and shows a self focusing nature. From the open aperture Z-scan curve, it is found that the nonlinear absorption is due to saturation. The order of magnitude of third order susceptibility was estimated to be 10^?6 esu. UV-Vis-NIR spectrum of MHB single crystal reveals a very low cutoff wavelength (310 nm) and transparency in the entire visible region. Also the material has direct allowed transition and it possesses a band gap of 3.7 eV. The dissipation factor is low and SHG efficiency is high. The higher magnitudes of second and third order NLO parameters make the material suitable for photonic applications like frequency conversion and eye/sensor protection.