Microwave assisted synthesis of thiazolo[3,2‐b][1,2,4]‐triazoles containing 1,8‐naphthyridine moiety

A simple and efficient protocol for the synthesis of 5‐aryl‐2‐(2‐substituted‐1,8‐naphthyridin‐3‐yl)‐thiazolo[3,2‐b][1,2,4]triazoles ( 4 ) is achieved by cyclocondensation of 3‐(2‐substituted‐1,8‐naphthyridin‐3‐yl)‐1,2,4‐triazoles ( 3 ) with α‐halogenoketones in anhyd. methanol under microwave irradiation. The products are obtained in good yields and in a state of high purity.     

Surface State‐Induced Anomalous Negative Thermal Quenching of Multiferroic BiFeO3 Nanowires

Wide‐bandgap semiconductor nanowires with surface defect emission centers have the potential to be used as sensitive thermometers and optical probes. Here, we show that the green luminescence of multiferroic BiFeO₃ (BFO) nanowires shows an anomalous negative thermal quenching (NTQ) with increasing temperatures. The release of trapped carriers from localized surface defect states is suggested as the possible mechanism for the increased green luminescence which was experimentally observed at elevated temperatures. A reasonable interpretation of the photoluminescence (PL) processes in BFO nanowires is achieved, and the activation energies of the PL quenching and thermal hopping are deduced. Negative thermal quenching of BFO nanowires provides a new strategy for optical thermometry at higher temperatures.     

Surface enhanced strong visible photoluminescence from one-dimensional multiferroic BiFeO3 nanostructures

The surface defect dominated visible emission from one-dimensional multiferroic BiFeO₃ (BFO) nanowires (NWs) is characterized by photoluminescence (PL) spectroscopy. The PL spectra of BFO NWs exhibit a weak near band emission (NBE) along with a strong defect-level emission (DLE). It is suggested that excess surface defects exist in BFO NWs which are responsible for strong visible green emission. Passivation of BFO NW surface with H₂ significantly improves the NBE emission while suppressing surface recombination. Such a surface enhanced emission promises many potential applications of BFO NWs not only in photonic devices such as LEDs but also in fluorescence-based chemical sensing.     

Local piezoelectric response of ZnO nanoparticles embedded in a photosensitive polymer

Local piezoelectric properties of ZnO nanoparticles (NPs) embedded in a photo‐epoxy polymer are investigated by piezoresponse force microscopy (PFM). Integrating ZnO NPs into a photosensitive SU‐8 polymer matrix not only retains the highly desired piezoelectric properties of the ZnO, but also preserves photosensitivity and optical transparency of the SU‐8 polymer. These results have strong implications for simple photolithography based low‐cost fabrication of piezoelectric microelectromechanicalsystems (MEMS) and nanoelectromechanicalsystems (NEMS) in both sensing and energy harvesting applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis, potentiometric and antimicrobial studies on metal complexes of isoxazole Schiff bases

The metal complexes of Cu(II), Ni(II) and Co(II) with Schiff bases of 3-(2-hydroxy-3-ethoxybenzylideneamino)-5-methyl isoxazole [HEBMI] and 3-(2-hydroxy-5-nitrobenzylidene amino)-5-methyl isoxazole [HNBMI] which were obtained by the condensation of 3-amino-5-methyl isoxazole with substituted salicylaldehydes have been synthesized. Schiff bases and their complexes have been characterized on the basis of elemental analysis, magnetic moments, molar conductivity, thermal analysis and spectral (IR, UV, NMR and Mass) studies. The spectral data show that these ligands act in a monovalent bidentate fashion, co-ordinating through phenolic oxygen and azomethine nitrogen atoms. Chelates of Co(II), Ni(II) appear to be octahedral and Cu(II) appears to be distorted octahedral. To investigate the relationship between formation constants of binary complexes and antimicrobial activity, the dissociation constants of Schiff bases and stability constants of their binary metal complexes have been determined potentiometrically in aqueous solution at 30+/-1 degrees C and at 0.1 M KNO3 ionic strength and discussed. Antimicrobial activities of the Schiff bases and their complexes were screened. The structure-activity correlation in Schiff bases and their metal(II) complexes are discussed, based on the effect of their stability constants. It is observed that the activity enhances upon complexation and the order of activity is in accordance with stability order of metal ions.     

Reductive Fluorescence Quenching of the Photoexcited Free Base <Emphasis Type="Italic">meso</Emphasis>-Tetrakis (Pentafluorophenyl) Porphyrin by Amines

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H₂F₂₀TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H₂F₂₀TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ _f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H₂F₂₀TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H₂F₂₀TPP. The fluorescence quenching rate constants ranged from 1 × 10⁹ to 4 × 10⁹ s⁻¹, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H₂F₂₀TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G⁰) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.     

Bismuth ferrite clusters induced hydrogel formation in human serum albumin

Amyloid-fibril formation in human serum albumin (HSA) led to hydrogel formation in the presence of clusters of bismuth ferrite (BiFeO(3) or BFO) nanoparticles (NPs). Factors responsible for hydrogel formation were size and phase of NPs.     

Role of hydrogen bonding in the photophysical properties of isomeric tetrapyridylporphyrins in aprotic solvent

Extensive photophysical properties of isomeric tetra-2-pyridylporphyrin (TpyP(2)), tetra-3-pyridylporphyrin (TpyP(3)), and tetra-4-pyridylporphyrin (TpyP(4)) have been studied in the presence of a series of phenols of increasing hydrogen bonding power in dichloromethane solution by employing UV/vis spectroscopy; steady-state, time-resolved fluorescence spectroscopy; and transient absorption spectroscopic techniques. The change of absorption spectra of all three porphyrins as a function of different phenol concentrations established the preference of hydrogen bonded complex formation to the peripheral pyridyl nitrogen rather than the pyrrole nitrogen of the porphyrin macrocycle. The fluorescence behaviors of the porphyrins which were observed upon addition of different phenols point to a marked dependence on the nature of the added phenols. Phenols with an electron withdrawing group do not quench the fluorescence of porphyrins, whereas phenols with an electron donating group quench the singlet porphyrin both in static and dynamic pathways. A remarkable difference in quenching behaviors of singlet excited porphyrin by 4-methylphenol (4-MePhOH) and 4-MeOPhOH/4-EtOPhOH (4-EtOPhOH = 4-ethoxyphenol) are observed. The quenching of singlet excited porphyrins by 4-MePhOH is attributed to be purely static in nature, and the H-bond provides a strong nonradiative channel to singlet excited porphyrins. However, the quenching of singlet excited porphyrins by 4-MeOPhOH/4-EtOPhOH is mostly dynamic, and it is ascribed to be the reductive quenching of single excited porphyrins. Picosecond transient absorption study with TpyP(2) and 4-MeOPhOH provides the evidence of porphyrin radical anion and phenol radical cation of equal lifetime, which indicates the fact that electron transfer occurs from phenol to singlet excited porphyrin. The temperature effect on dynamic quenching by 4-MeOPhOH/4-EtOPhOH and kinetic deuterium isotope effect established the reaction to be a photoinduced concerted proton coupled electron transfer.     

Effect of annealing atmosphere on microstructural and photoluminescence characteristics of multiferroic BiFeO3 thin films prepared by pulsed laser deposition technique

The effect of annealing atmosphere on microstructural and photoluminescence characteristics of multiferroic BiFeO₃ (BFO) thin films deposited by pulsed laser deposition (PLD) technique is reported. The films annealed in oxygen environment showed improved microstructure and photoluminescence (PL) characteristics. The PL spectra of oxygen-annealed BFO thin films at room temperature show a strong emission in the blue region. A plot of (αE)² vs. photon energy (E) (α-absorption coefficient) and the linear extrapolation to (αE)²=0 indicates a direct gap at 2.69±0.02 eV, which is in agreement with the previous reports. The results obtained in this study are accordingly expected to facilitate the understanding and optimization of BFO thin films for photovoltaic applications.