Solution‐Processed High‐Performance Tetrathienothiophene‐Based Small Molecular Blends for Ambipolar Charge Transport

Four soluble dialkylated tetrathienoacene ( TTAR) ‐based small molecular semiconductors featuring the combination of a TTAR central core, π‐conjugated spacers comprising bithiophene ( bT ) or thiophene ( T ), and with/without cyanoacrylate ( CA ) end‐capping moieties are synthesized and characterized. The molecule DbT‐TTAR exhibits a promising hole mobility up to 0.36 cm² V^?1 s^?1 due to the enhanced crystallinity of the microribbon‐like films. Binary blends of the p‐type DbT‐TTAR and the n‐type dicyanomethylene substituted dithienothiophene‐quinoid ( DTTQ‐11 ) are investigated in terms of film morphology, microstructure, and organic field‐effect transistor (OFET) performance. The data indicate that as the DbT‐TTAR content in the blend film increases, the charge transport characteristics vary from unipolar (electron‐only) to ambipolar and then back to unipolar (hole‐only). With a 1:1 weight ratio of DbT‐TTAR DTTQ‐11 in the blend, well‐defined pathways for both charge carriers are achieved and resulted in ambipolar transport with high hole and electron mobilities of 0.83 and 0.37 cm² V^?1 s^?1, respectively. This study provides a viable way for tuning microstructure and charge carrier transport in small molecules and their blends to achieve high‐performance solution‐processable OFETs.     

Synthesis of unsymmetrical substituted 1,4-dihydropyridines through thermal and microwave assisted [4+2] cycloadditions of 1-azadienes and allenic esters

Thermal and microwave assisted [4+2] cycloadditions of 1,4-diaryl-1-aza-1,3-butadienes with allenic esters lead to cycloadducts, which after a 1,3-H shift afford variedly substituted unsymmetrical 2-alkyl-1,4-diaryl-3-ethoxycarbonyl-1,4-dihydropyridines in high yields. Reactions carried out under microwave irradiation are cleaner and give higher yields with much shortened reaction times. Density functional theory (DFT) at the B3LYP/6-31G* level has been used to calculate geometric features of the reactants, barrier for s-trans to s-cis and reverse isomerization of azadienes (5a-d, 10a-e), dihedral angles between N(1), C(2), C(3), and C(4) atoms of azadienes along with various indices such as chemical hardness (eta), chemical potential (micro), global electrophilicity (omega), and the difference in global electrophilicity (Deltaomega) between the reacting pairs and Fukui functions (f (+) and f(-)). The results revealed that s-trans is the predominant conformation of azadienes at ambient temperature and the barrier for conversion of the s-trans rotamer of 1-azadienes to s-cis may be the major factor influencing the chemoselectivity, i.e., [4+2] verses [2+2] cycloaddition. The regiochemistry of the observed cycloadditions is collated with the obtained local electrophilicity indices (Fukui functions). Transition states for the formation of both [4+2] and [2+2] cycloadducts as located at the PM3 level indicate that the transition state for the formation of [4+2] cycloadducts has lower energy, again supporting the earlier conclusion that preferred formation of [4+2] cycloaaducts at higher temperature may be a consequence of barrier for s-trans to s-cis transformation of 1-azadienes.     

Comparison of radiometric and non-radiometric methods for uranium determination in groundwater of Punjab,India

Uranium in groundwater samples collected from Punjab state, India was determined using radiometric methods (extractive liquid scintillation and Cerenkov counting). Experimental conditions were optimized by studying the effect of sample pH, quenching and amount of extracting agent added to the scintillation cocktail on recovery of uranium. To ensure the accuracy of results, both radiometric methods were compared with non radiometric method such as adsorptive stripping voltammetry and found to be very good agreement. The distinct advantage of proposed radiometric methods is almost 100 % effective especially extractive liquid scintillation for simultaneous measurement of alpha and beta emitting radionuclides with fast and simple sample preparation.     

Utilization of Cheese Whey Using Synergistic Immobilization of β-Galactosidase and <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> Cells in Dual Matrices

Whey is a byproduct of the dairy industry, which has prospects of using as a source for production of various valuable compounds. The lactose present in whey is considered as an environmental pollutant and its utilization for enzyme and fuel production, may be effective for whey bioremediation. The dairy yeast Kluyveromyces marxianus have the ability to utilize lactose sharply as the major carbon source for the production of the enzyme. Five strains were tested for the production of the β-galactosidase using whey. The maximum β-galactosidase activity of 1.74 IU/mg dry weight was achieved in whey using K. marxianus MTCC 1389. The biocatalyst was further immobilized on chitosan macroparticles and exhibited excellent functional activity at 35 °C. Almost 89 % lactose hydrolysis was attained for concentrated whey (100 g/L) and retained 89 % catalytic activity after 15 cycles of reuse. Finally, β-galactosidase was immobilized on chitosan and Saccharomyces cerevisiae on calcium alginate, and both were used together for the production of ethanol from concentrated whey. Maximal ethanol titer of 28.9 g/L was achieved during fermentation at 35 °C. The conclusions generated by employing two different matrices will be beneficial for the future modeling using engineered S. cerevisiae in scale-up studies.     

Stability-Indicating High-Performance Thin-Layer Chromatographic Method for the Estimation of Ambroxol Hydrochloride and Doxofylline in a Pharmaceutical Formulation Using Experimental Design in Robustness Study

JPC – Journal of Planar Chromatography – Modern TLC - A sensitive, specific, and accurate stability-indicating high-performance thin-layer chromatographic method for the analysis of...     

Surface Plasmon Resonance (SPR) Based Optimization of Biosynthesis of Silver Nanoparticles from Rhizome Extract of <Emphasis Type="Italic">Curculigo orchioides</Emphasis> Gaertn. and Its Antioxidant Potential

The present study for the first time explores the use of Central composite design (CCD) of RSM to optimize the process parameters of biosynthesis of AgNPs from rhizome extract of Curculigo orchioides based on the absorbance of surface plasmon resonance (SPR) band at 430 nm that corresponds to the synthesis of mono-disperse, spherical AgNPs. A polynomial model was established as a functional relationship between the synthesis of AgNPs and four independent variables such as concentration of AgNO₃, % rhizome extract, pH and temperature. The optimum conditions for maximum AgNPs synthesis were 2 mM concentration of AgNO₃, 20 % rhizome extract, pH 8, and temperature of 60 °C. A significant correlation (R ² = 0.8947) was observed between the experimental data and the predicted values indicating the adequacy of the model. Transmission electron microscopy (TEM) revealed spherical particles with size range of 5–28 nm. Selected area electron diffraction pattern and X-ray diffraction analysis confirmed the face-centered cubic structure of metallic silver. The plausible mechanism for the reduction of AgNO₃ to AgNPs was proposed following the identification of functional groups by FTIR. The antioxidative activity of AgNPs was demonstrated with scavenging of hydrogen peroxide (H₂O₂), 1,1-Diphenyl-2-picrylhydrazyl (DPPH) and superoxide radicals.     

Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction

The first example of a biocatalytic [2,3]‐sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle–Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C?C bond‐forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl‐, benzyl‐, and alkyl‐substituted allylic sulfides) and α‐diazo esters. Moreover, the scope of this myoglobin‐mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active‐site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle–Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon–carbon bonds.     

Swift ion irradiation effect on high-k ZrO2- and Al2O3-based MOS devices

This paper describes the heavy ion-induced effects on the electrical characteristics of reactively sputtered ZrO₂ and Al₂O₃ high-k gate oxides deposited in argon plus nitrogen containing plasma. Radiation-induced degradation of sputtered high-k dielectric ZrO₂/Si and Al₂O₃/Si interface was studied using 45?MeV Li³⁺ ions. The devices were irradiated with Li³⁺ ions at various fluences ranging from 5?×?10⁹ to 5?×?10¹²?ions/cm². Capacitance–voltage and current–voltage characteristics were used for electrical characterization. Shift in flat band voltage towards negative value was observed in devices after exposure to ion radiation. Post-deposition annealing effect on the electrical behavior of high-k/Si interface was also investigated. The annealed devices showed better electrical and reliability characteristics. Different device parameters such as flat band voltage, leakage current, interface defect density and oxide-trapped charge have been extracted.The surface morphology and roughness values for films deposited in nitrogen containing plasma before and after ion radiation are extracted from Atomic Force Microscopy.     

Slave fermion formalism for the tetrahedral spin chain

We use the SU(2) slave fermion approach to study a tetrahedral spin 1/2 chain, which is a one-dimensional generalization of the two dimensional Kitaev honeycomb model. Using the mean field theory, coupled with a gauge fixing procedure to implement the single occupancy constraint, we obtain the phase diagram of the model. We then show that it matches the exact results obtained earlier using the Majorana fermion representation. We also compute the spin-spin correlation in the gapless phase and show that it is a spin liquid. Finally, we map the one-dimensional model in terms of the slave fermions to the model of 1D p-wave superconducting model with complex parameters and show that the parameters of our model fall in the topological trivial regime and hence does not have edge Majorana modes.     

One-step synthesis of oxazoline and dihydrooxazine libraries

The reactions of 1,2- and 1,3-hydroxyalkyl azides and aldehydes in the presence of Lewis acid result in the one-step construction of oxazolines and dihydrooxazines, respectively. The reaction was adapted to parallel synthesis using a polymer-bound phosphine to scavenge excess hydroxyalkyl azide. Thus, a 60-member library of various disubstituted oxazolines and di- and trisubstituted dihydrooxazines was generated.