Synthesis of Pyrazolopyridine Annulated Heterocycles and Study the Effect of Substituents on Photophysical Properties

Pyrazolo[3,4-b]pyridines having 4-chloro-5-chloroethyl side chain are synthesized by the reaction of 5-aminopyrazole and cyclic β-formylester gave aminopyrazolodihydrofuranone intermediate, which on cyclization in phosphorous oxychloride exclusively converted in to 4-chloro-5-chloroethyl pyrazolo[3,4-b]pyridines 4(a-b) in major amount. The side chain with acetic acid, thiourea and aromatic amines are used to form angular ring leads to formation of tricyclic Furo[2,3-d]pyrazolo[2,3-b]pyridines 5(a-b), pyrazolo[3,4-b]thieno[2,3-d]pyridines 6(a-b) and pyrazolo[3,4-b]pyrrolo[2,3-d]pyridines 7(a-n) respectively. The substituents effect at C₄ position on fluorescence properties of pyrazolopyridines has been studied. Moreover the effect of electron donor and halogen substituents on fluorescence properties of pyrazolopyrrolopyridines 7(a-n) has been investigated along with their fluorescent quantum yield.     

A study of the motion in rotating containers using a boundary fitted co-ordinate system

Numerical solutions are often inaccurate because conventional co-ordinate systems do not represent the complex physical boundaries accurately. In the present work, the numerical solution of linear shallow water wave equations has been obtained by transforming the physical domain into a rectangular computational domain using elliptic differential operators. This work is part of a programme to develop three-dimensional body-fit grid systems for environmental flows. Solutions have been obtained for a cylindrical container and also a parabolic container. The initial conditions chosen are the ones for which analytical solutions exist. The numerical solutions compare well with analytical solutions.     

Radon and thoron progeny levels in air samples at Udagamandalam region of Nilgiris in India

Measurement of concentration of radon and thoron daughter products in various indoor environment covering four seasons of a year in Udagamandalam Taluk of Nilgiris biosphere has been carried out using a high volume air sampler to asses the inhalation dose to the population which delivers higher dose than the radon and thoron gas alone. The potential alpha-energy concentrations of the radon and thoron progeny ranged from 0.97 to 12.72 mWL and from 1.63 to 15.83 mWL with a geometric mean of 6.02 and 7.89 mWL, respectively, taking all seasons into account. These measurements have yielded a wealth of data on the variation among the indoor radon and thoron progeny in various places during different seasons. The radon and thoron progeny levels are higher in winter seasons and are less in summer season with autumn and spring data lie in between winter and summer. Using the dose conversion factor for indoor exposures given in UNSCEAR 93 report the internal equivalent dose to the inhalation of radon progeny is evaluated to be 1357 mSv^.y^–1 and the corresponding annual effective dose equivalent value has been found to be 2.13 mSv^.y^–1. It can be observed that the mean value of radon is higher than the Indian average. Also it is found the radon and thoron progeny levels are higher in the case of houses built with rock and granite and in tiled type houses of nearly 100 years old. The levels are less in the case of houses built with brick and cement. The observed results for different types of houses and seasons are discussed in this paper.     

Natural radiation distribution of soils at Kotagiri Taluk of the Nilgiris biosphere in India

The systematic study of background radiation and the distribution of radionuclides in the environment of Nilgiris biosphere in South India, have been carried out with an objective of establishing reliable baseline data on the background radiation level of the region. Soil samples have been collected at various places of Kotagiri taluk in Nilgiris biosphere and are analyzed for radioactivity measurements of primordial radionuclides by 3"×3" NaI(TI) gamma-ray spectrometer. It is observed that the average activity of ²³²Th series, ²³⁸U series and ⁴⁰K in soil samples is found to be 102 Bq^.kg^–1, 41 Bq^.kg^–1 and 229 Bq^.kg^–1, respectively which contributes to a total gamma-dose of 86 nGy^.h^–1. Results of this systematic investigation establish the existence of wide range of variation in ²³²Th series, ²³⁸U series and ⁴⁰K activities, which may be attributable to the existence of wide variety of lithological compounds in the zone under study. The ambient gamma-radiation dose measured is found to vary from 91 to 193 nGy^.h^–1 with a mean of 142.8 nGy^.h^–1. The measured ambient gamma-dose is more than 50% of the dose calculated from soil activities, which is due to the higher cosmic ray contribution to the total dose in the environment. The data is compared with different places around the world and the results are discussed in this paper     

Kinetics of vinylation of 4′-bromoacetophenone with n-butyl acrylate using palladacycle catalyst

The kinetics of vinylation of 4′-bromoacetophenone (4′-BAP) with n-butyl acrylate (n-BA) has been studied using palladacycle catalyst precursor 1, in the presence of sodium acetate (NaOAc) as a base and tetrabutylammonium bromide (TBAB) as a promoter in N-methyl-2-pyrrolidinone (NMP) solvent. The rate was found to be first order with respect to 4′-BAP, fractional order with the catalyst, and first order tending to zero order with NaOAc concentration. The rates passed through a maximum with variation of TBAB and n-butyl acrylate concentrations. The rate data have been analyzed to propose an empirical model, which is in good agreement with the mechanism already established for Heck reactions using palladacycle catalysts.     

Charge Recombination Dynamics in Organic Photovoltaic Systems with Enhanced Dielectric Constant

Increasing the dielectric constant of organic photovoltaic materials to reduce recombination rates has long been pursued, however, material modification often results in the modification of multiple device characteristics, making system comparison difficult. In this study, a fullerene derivative with an increased blend dielectric constant is examined by the addition of a triethylene glycol appendage to the fullerene (TEG‐PCBM). Density functional theory calculations show a small change to the permanent dipole moment between TEG‐PCBM and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₀BM) resulting in similar solubility, morphology, and device performance. TEG‐PCBM is blended with donors P3HT and PTB7‐Th and a comparable performance to PC₆₀BM is found. This model system shows the rarely reported characteristic of an increase in the dielectric constant while leaving its other properties unaltered. Looking at light intensity effects on open‐circuit voltage (V_oc), short‐circuit current (J_sc), and fill factor (FF) along with exciton dissociation efficiency, it is observed that when switching to the TEG‐ modified fullerene derivative, geminate recombination is not reduced, and Shockley–Read–Hall recombination is increased. While triethlyene glycol appendages may prove to be ineffective in improving recombination through increased dielectric constant, an approach for studying recombination in future high dielectric systems is provided.     

SIR analysis and interference cancellation in uplink OFDMA with large carrier frequency/timing offsets

In uplink orthogonal frequency division multiple access (OFDMA), large timing offsets (TO) and/or carrier frequency offsets (CFO) of other users with respect to a desired user can cause significant multiuser interference (MUI). In this letter, we analytically characterize the degradation in the average output signal-to-interference ratio (SIR) due to the combined effect of both TOs as well as CFOs in uplink OFDMA. Specifically, we derive closed-form expressions for the average SIR at the DFT output in the presence of large CFOs and TOs. The analytical expressions derived for the signal and various interference terms at the DFT output are used to devise an interference cancelling receiver to mitigate the effect of CFO/TOinduced interferences.     

Synthesis of fused pyrimidines from amines and cyclic β-formylesters

A highly efficient method was successfully developed for the synthesis of fused pyrimidines via aminoheterocyclic dihydrofuranone intermediates obtained from 2-aminoheterocycles and cyclic β-formylesters by three different methods.     

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Conversion of biomass to chemicals provides essential products to human society from renewable resources. In this context, achieving atom‐economical and energy‐efficient conversion with high selectivity towards target products remains a key challenge. Recent developments in nanostructured catalysts address this challenge reporting remarkable performances in shape and morphology dependent catalysis by metals on nano scale in energy and environmental applications. In this review, most recent advances in synthesis of heterogeneous nanomaterials, surface characterization and catalytic performances for hydrogenation and oxidation for biorenewables with plausible mechanism have been discussed. The perspectives obtained from this review paper will provide insights into rational design of active, selective and stable catalytic materials for sustainable production of value‐added chemicals from biomass resources.