Directed C−H Halogenation Reactions Catalysed by PdII Supported on Polymers under Batch and Continuous Flow Conditions

A new generation of N-heterocyclic carbene palladium(II) complexes containing vinyl groups in different positions in the backbone of the N-heterocycle have been developed. The fully characterised monomers were copolymerised with divinylbenzene to fabricate robust polymer supported NHC-Pd^II complexes and these polymers were applied as heterogeneous catalysts in directed C−H halogenation of arenes with a pyridine-type directing group. The catalysts demonstrated medium-high catalytic activity with up to 90 % conversion and 100 % selectivity in chlorination. They are heterogeneous and recyclable (at least six times) with no significant leaching of palladium in batch mode catalysis. The best catalyst was also applied under continuous flow conditions where it disclosed an exceptional activity (90 % conversion) and 100 % selectivity for the mono-halogenated product for at least six days, with no leaching of palladium, no loss of activity and an ability to maintain the original oxidation state of Pd^II.     

Characterization on conduction properties of carboxymethyl cellulose/kappa carrageenan blend-based polymer electrolyte system

The present work deals with the development of carboxymethyl cellulose (CMC) blended with kappa carrageenan (KC) as a host-based polymer electrolyte (PE) system. The CMC/KC films were successfully prepared using solution casting method and were characterized through electrical impedance spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) methods, respectively. The FTIR spectrum revealed that the significant region of interaction transpires at wave number 1,057, 1,326, 1,584, and 3,387?cm^?1 which correspond to the bending of C–O–C, bending of –OH, asymmetric of –COO^? as well as the stretching of –OH, respectively. It has also been demonstrated that the complexation process occurred between CMC and KC. The CMC/KC blend PE system with a ratio of 80:20 achieved an optimum conductivity of 3.91?×?10^?7?S?cm^?1 and had the lowest crystallinity percentage as suggested by the XRD analysis.     

Quantum spin Hall and quantum valley Hall effects in trilayer graphene and their topological structures

The present study pertains to the trilayer graphene in the presence of spin orbit coupling to probe the quantum spin/valley Hall effect. The spin Chern-number C_s for energy-bands of trilayer graphene having the essence of intrinsic spin–orbit coupling is analytically calculated. We find that for each valley and spin, C_s is three times larger in trilayer graphene as compared to single layer graphene. Since the spin Chern-number corresponds to the number of edge states,consequently the trilayer graphene has edge states, three times more in comparison to single layer graphene. We also study the trilayer graphene in the presence of both electric-field and intrinsic spin–orbit coupling and investigate that the trilayer graphene goes through a phase transition from a quantum spin Hall state to a quantum valley Hall state when the strength of the electric field exceeds the intrinsic spin coupling strength. The robustness of the associated topological bulk-state of the trilayer graphene is evaluated by adding various perturbations such as Rashba spin–orbit(RSO) interaction αR, and exchange-magnetization M. In addition, we consider a theoretical model, where only one of the outer layers in trilayer graphene has the essence of intrinsic spin–orbit coupling, while the other two layers have zero intrinsic spin–orbit coupling.Although the first Chern number is non-zero for individual valleys of trilayer graphene in this model, however, we find that the system cannot be regarded as a topological insulator because the system as a whole is not gaped.     

Low content Ni and Cr co-doped LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> with enhanced capacity retention

Nanoparticles of the pure and Ni–Cr co-doped lithium manganese oxides Li[Ni_xCr_yMn_2-x-y]O₄ (x = y = 0.01–0.05) have been synthesized by sol–gel method using citric acid as a chelating agent. The effect of low-content doping was noted reflecting the faster ionic movement in the cathode material. The phase structure and morphology of the materials are characterized by XRD, FTIR, SEM and TEM. Electrochemical and impedance measurements established that low-content Ni–Cr substitution substantially improves the structural stability and high rate cycling performance of LiMn₂O₄. Among all the investigated compositions, LiNi_0.01Cr_0.01Mn_1.98O₄ demonstrated the best electrochemical performance. At a substantially high current rate of 5 C, 82% of the initial discharge capacity at 0.1 C is retained. Remarkably, after deep cycling at high rates, a discharge capacity of 104 mAhg^?1 is resumed upon reducing the current rate to 0.1 C which is 91% of the specific capacity in the first cycle.     

Electrochemical Sensing of Ascorbic Acid,Hydrogen Peroxide and Glucose by Bimetallic (Fe,Ni)−CNTs Composite Modified Electrode

In this research, bimetallic supported CNT modified electrode ( Fe,Ni/CNTs/GCE) has been developed for sensitive, stable and highly elctroactive sensing of glucose, ascorbic acid and hydrogen peroxide. Transition metals such as Iron (Fe) and Nickel (Ni) offer high electrical and thermal conductance, high active surface‐to‐volume ratio and presence of d‐band electrons gives enhanced electrocatalytic behavior. While, CNTs provide high surface area, stability and excellent conductivity. Synthesized material is characterized by SEM, EDS, XRD and FTIR to access morphology, elemental composition and structure. This unique combination is employed for the electrochemical sensing of ascorbic acid, glucose and hydrogen peroxide and different experimental parameters are optimized. Fe,Ni/CNTs/GCE shows good sensing efficiency at pH 7.4 which is ideally suitable for variety of analytes. The modified electrode also show good reproducibility and sensitivity under optimized conditions and can be reused upto 30 cycles without compromising the efficiency. With good linearity, reproducibility and limit of detection, this material possess significant potential as non‐enzymatic biosensor for variety of analytes.     

Population Structure Analysis and Selection of Core Set among Common Bean Genotypes from Jammu and Kashmir,India

Understanding the genetic diversity of a crop is useful for its effective utilization in breeding programmes. For better understanding of the genetic variability in common bean, the first and foremost step is to study its genetic diversity. In the present investigation, 138 genotypes of common bean collected from various regions of Jammu and Kashmir, India, representing major common bean growing areas of this region, were evaluated using 23 SSRs. These SSRs were found highly polymorphic and possess high values for various parameters indicating their high discriminatory power. The average PIC value observed was 0.692, with 0.730 as average gene diversity value, and 0.267 as heterozygosity. Twenty-three SSRs produced a total of 251 alleles. The dendrogram generated with un-weighted neighbour joining cluster analysis grouped genotypes into three main clusters with various degrees of sub-clustering within the clusters. The model-based STRUCTURE analysis using 23 SSR markers identified a population with 3 sub-populations which corresponds to distance-based groupings with average F _ST value and expected heterozygosity of 0.1497 and 0.6696, respectively, within the sub-population, as such high level of genetic diversity was observed within the population. Further, Core Hunter II was used to identify a core set of 96 diverse genotypes. This core set of diverse 96 genotypes is a potential resource for association mapping studies and can be used by breeders as a material to make desirable genetic crosses to generate elite varieties for the fulfilling global market needs. These findings have further implications in common bean breeding as well as conservation programs.     

Irradiation effects of 12 eV oxygen ions on polyimide and fluorinated ethylene propylene

Polyimide (PI) and Fluorinated Ethylene Propylene (FEP) samples (15 mm×15 mm×50 μm ) were exposed to atomic oxygen ions of average energy ～12 eV and flux ～5×10¹³ ions cm ^?2 s ^?1, produced in the Electron Cyclotron Resonance (ECR) plasma. The energy and the flux of the oxygen ions at different positions in the plasma were measured by a retarding field analyzer. The fluence of the oxygen ions was varied from sample to sample in the range of ～5×10¹⁶ to 2×10¹⁷ ions cm ^?2 by changing the irradiation period. The pre- and the post-irradiated samples were characterized by the weight loss, Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), and Fourier Transform Infrared (FTIR) techniques. The weight of the PI and FEP samples decreased with increasing the ion fluence. However, the erosion yield for the PI is found to be higher, by almost a factor five, when compared with that of FEP. On the surface region of irradiated samples, the concentrations of the carbon, fluorine, and oxygen and their corresponding chemical bonds have changed appreciably. Moreover, blisters and nanoglobules were also observed even at a fluence of ～10¹⁷ ions cm ^?2. This oxygen ion fluence is almost two orders of magnitude lower than that of the 5 eV atomic oxygen, which a satellite encounters in the space, at the low Earth orbit, during its mission period of about 7 years.     

Demonstration of a bias tunable quantum dots-in-a-well focal plane array

Infrared detectors based on quantum wells and quantum dots have attracted a lot of attention in the past few years. Our previous research has reported on the development of the first generation of quantum dots-in-a-well (DWELL) focal plane arrays, which are based on InAs quantum dots embedded in an InGaAs well having GaAs barriers. This focal plane array has successfully generated a two-color imagery in the mid-wave infrared (i.e. 3–5 μm) and the long-wave infrared (i.e. 8–12 μm) at a fixed bias voltage. Recently, the DWELL device has been further modified by embedding InAs quantum dots in InGaAs and GaAs double wells with AlGaAs barriers, leading to a less strained InAs/InGaAs/GaAs/AlGaAs heterostructure. This is expected to improve the operating temperature while maintaining a low dark current level. This paper examines 320 × 256 double DWELL based focal plane arrays that have been fabricated and hybridized with an Indigo 9705 read-out integrated circuit using Indium-bump (flip-chip) technology. The spectral tunability is quantified by examining images and determining the transmittance ratio (equivalent to the photocurrent ratio) between mid-wave and long-way infrared filter targets. Calculations were performed for a bias range from 0.3 to 1.0 V. The results demonstrate that the mid-wave transmittance dominates at these low bias voltages, and the transmittance ratio continuously varies over different applied biases. Additionally, radiometric characterization, including array uniformity and measured noise equivalent temperature difference for the double DWELL devices is computed and compared to the same results from the original first generation DWELL. Finally, higher temperature operation is explored. Overall, the double DWELL devices had lower noise equivalent temperature difference and higher uniformity, and worked at higher temperature (70 K and 80 K) than the first generation DWELL device.