Terpyridine Based Heteroleptic Ruthenium Complexes: Influence of Donor and Acceptor Ligands in Photosensitization

We report heteroleptic ruthenium complexes of terpyridine (tpy) ligands with directly linked carboxylic acid anchors. These complexes feature methyl or methoxy-substituted ^4′−Phtpy as donor ligands. We prepared these heteroleptic complexes from the ruthenium (II) precursor via a milder route to preclude the homoleptic complex formation. The donor−acceptor arrangement of tpy ligands in these ruthenium complexes renders visible light absorption giving metal and ligand-to-ligand charge transfer excitations at c.a. 490 nm. We evaluate the effect of the tpy donor substituents on the light-harvesting ability in Dye-Sensitized Solar Cells (DSSCs) and compare their photosensitizing ability with heteroleptic complexes bearing phenyl spacer at the acceptor end. Further, scrutinizing their photovoltaic performance, we studied their electron transfer kinetics in DSSCs using electrochemical impedance spectroscopy. This paper presents the structure-photosensitization relationship of these heteroleptic ruthenium complexes through a combined experimental and computational approach.     

Influence of barium titanate nanofiller on PEO/PVdF-HFP blend-based polymer electrolyte membrane for Li-battery applications

Organic-inorganic hybrid membranes based on poly(ethylene oxide) (PEO) 6.25 wt%/poly(vinylidene fluoride hexa fluoro propylene) [P(VdF-HFP)] 18.75 wt% were prepared by using various concentration of nanosized barium titanate (BaTiO₃) filler. Structural characterizations were made by X-ray diffraction and Fourier transform infrared spectroscopy, which indicate the inclusion of BaTiO₃ in to the polymer matrix. Addition of filler creates an effective route of polymer-filler interface and promotes the ionic conductivity of the membranes. From the ionic conductivity results, 6 wt% of BaTiO₃-incorporated composite polymer electrolyte (CPE) showed the highest ionic conductivity (6 × 10^?3 Scm^?1 at room temperature). It is found that the filler content above 6 wt% rendered the membranes less conducting. Morphological images reveal that the ceramic filler was embedded over the membrane. Thermogravimetric and differential thermal analysis (TG-DTA) of the CPE sample with 6 wt% of the BaTiO₃ shows high thermal stability. Electrochemical performance of the composite polymer electrolyte was studied in LiFePO₄/CPE/Li coin cell. Charge-discharge cycle has been performed for the film exhibiting higher conductivity. These properties of the nanocomposite electrolyte are suitable for Li-batteries.     

qNMR for profiling the production of fungal secondary metabolites

Analysis of complex mixtures is a common challenge in natural products research. Quantitative nuclear magnetic resonance spectroscopy offers analysis of complex mixtures at early stages and with benefits that are orthogonal to more common methods of quantitation, including ultraviolet absorption spectroscopy and mass spectrometry. Several experiments were conducted to construct a methodology for use in analysis of extracts of fungal cultures. A broadly applicable method was sought for analysis of both pure and complex samples through use of an externally calibrated method. This method has the benefit of not contaminating valuable samples with the calibrant, and it passed scrutiny for line fitting and reproducibility. The method was implemented to measure the yield of griseofulvin and dechlorogriseofulvin from three fungal isolates. An isolate of Xylaria cubensis (coded MSX48662) was found to biosynthesize griseofulvin in the greatest yield, 149 ± 8 mg per fermentation, and was selected for further supply experiments. Copyright © 2016 John Wiley & Sons, Ltd.     

Exploring the effect of radiation crosslinking on the physico‐mechanical,dynamic mechanical and dielectric properties of EOC–PDMS blends for cable insulation applications

This work focuses on the effect of electron beam irradiation on the physico‐mechanical, dynamic mechanical and dielectric properties of blends based on ethylene octene copolymer (EOC) and poly dimethyl siloxane (PDMS) rubber. It is found that electron beam irradiation caused considerable improvement in the physico‐mechanical properties; the tensile strength was enhanced by nearly 35% for 70:30 EOC:PDMS blend. Phase morphology of the blends analyzed before irradiation by scanning electron microscopy (SEM) exhibited droplet/matrix morphology with sizes of the PDMS rubber domain varying from 0.55 µm to 0.47 µm as the amount of PDMS rubber decreased from 30 wt% to 10 wt%. This reduction in the PDMS rubber domain has been correlated with the physico‐mechanical properties of the blends. Further, the dynamic mechanical properties and creep behavior of these EOC:PDMS blends before and after irradiation has been studied. It is inferred that the 70:30 blend after radiation crosslinking shows a 17% decrease in the creep compliance, i.e. higher creep resistance compared to neat blends. All the radiation crosslinked blends exhibited lower dielectric constant, lower dielectric loss and higher electrical resistivity as compared to the virgin blends which makes it suitable for cable insulating application. Copyright © 2016 John Wiley & Sons, Ltd.     

Design,synthesis, and antibacterial studies of potent pyrazolinyltriazoles

Research on Chemical Intermediates - A library of pyrazolinyltriazole hybrids (3a–l, 4a–l) was synthesized via azide–alkyne dipolar (Huisgen) cycloaddition of azidoacetyl...     

Multispectroscopic and theoretical studies on rapid,selective and sensitive visual sensing of cyanide ion in aqueous solution by receptors possessing varying HBD property

Research on Chemical Intermediates - Three new benzoquinone–imidazole ensembles possessing varying number (0, 1 and 2) of electron-withdrawing bromo substituents on the quinone ring have been...     

Electrochemical and photocatalytic investigation of nickel oxide for energy storage and wastewater treatment

Nickel oxide (NiO) was synthesized via a one-step facile method. X-ray diffraction analysis confirmed the face-centered cubic structure of NiO. The bonding nature and surface purity were confirmed via Fourier-transform infrared spectroscopy. NiO revealed partial spherical morphology with less particle aggregation. The optical bandgap of NiO was found to be 3.75 eV. Cyclic voltammetry revealed well-defined oxidation and reduction peaks for NiO. The charge–discharge curve exhibited specific capacitance of 184.6 F/g at current density of 0.3 A/g. NiO electrode exhibited longer cyclic stability of 93 % up to 1500 cycles. In addition, NiO + H₂O₂ revealed efficient photocatalytic degradation of methylene blue (organic pollutant) under visible-light irradiation with degradation efficiency of ~88 %. These results confirm that nanosized NiO is more suitable for dual application.

     

Tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers as burning rate catalysts for ammonium perchlorate‐based propellant decomposition

Ferrocene‐based derivatives show potential application as burning rate catalysts (BRCs) for solid composite propellants. However, migration problems of simple ferrocene‐based derivatives limit their application as BRCs in solid composite propellants. To overcome the migration problems of ferrocene‐based BRCs and to enhance the burning rate of ammonium perchlorate (AP)‐based propellants, zero‐ to second‐generation tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers (G0, G1 and G2) were synthesized. The structures of G0, G1 and G2 were confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopies. The electrochemical behavior of G0, G1 and G2 was investigated using cyclic voltammetry. It was found that G0, G1 and G2 showed redox behavior due to the presence of ferrocene and this redox behavior was diffusion controlled over the investigated scan range. The burning rate catalytic effect of G0, G1 and G2 on thermal decomposition of AP was investigated using thermogravimetry and differential thermogravimetry. G0, G1 and G2 showed good catalytic effect on the thermal decomposition of AP. Anti‐migration studies showed that migration of G0, G1 and G2 was much slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene.     

Palladium nanoparticles immobilized on sepiolite–cyclodextrin nanosponge hybrid: Efficient heterogeneous catalyst for ligand‐ and copper‐free C─C coupling reactions

A novel hybrid system composed of sepiolite clay and cyclodextrin nanosponge (CDNS) was prepared via reaction of Cl‐functionalized sepiolite with amine‐functionalized CDNS. CDNS–sepiolite was then applied for immobilization of Pd(0) nanoparticles. The resulting hybrid system, Pd@CDNS‐sepiolite, was characterized using various techniques and successfully used as an efficient and heterogeneous catalyst for ligand‐ and copper‐free Sonogashira and Heck coupling reactions under mild reaction conditions. Recycling experiments confirmed that Pd@CDNS‐sepiolite was recyclable and could be used for several consecutive reaction runs with slight Pd leaching and loss of catalytic activity.     

Mechanism of Evolution of Koneramine Complexes from One‐Pot Reactions: Snapshots of Intermediates Offer Facile Routes to New Dipicolylamines

Koneramines (L^ROR′, R=Ph or Ts; R′=Me, iPr) and their complexes were found to emerge from the system of pyridine‐2‐carboxaldehyde and N‐phenyl/tosylethylenediamine when a primary or secondary alcohol was used as solvent. Imidazolidinylpyridines (L^R, R=Ph or Ts) became major emergents whereas hemi‐aminals (L^ROH, R=Ph or Ts) are minor emergents of the system when tertiary butanol was used as the solvent; the bulky tertiary butyl group prevented the addition of alcohol to the iminium ion that diverted the equilibrium towards imidazolidinylpyridines. By playing with the components of the reaction mixture, crystals of the metastable intermediates bound to copper(II) and/or zinc(II) were obtained and the structures were determined by X‐ray diffraction analysis. The reported results shed light on how to control the emergents of the multicomponent reaction mixture that forms koneramines. Reactivity studies of the intermediates pave the way for a new type of koneramine complexes that are new dipicolylamines where the two pyridine moieties of the resulting koneramine are not the same.