Growth, microstructure and electrical properties of sputter-deposited hafnium oxide (HfO2) thin films grown using a HfO2 ceramic target

Hafnium oxide (HfO₂) thin films have been made by radio-frequency (rf) magnetron-sputtering onto Si(1 0 0) substrates under varying growth temperature (T_s). HfO₂ ceramic target has been employed for sputtering while varying the T_s from room temperature to 500 °C during deposition. The effect of T_s on the growth and microstructure of deposited HfO₂ films has been studied using grazing incidence X-ray diffraction (GIXRD), and high-resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive X-ray spectrometry (EDS). The results indicate that the effect of T_s is significant on the growth, surface and interface structure, morphology and chemical composition of the HfO₂ films. Structural characterization indicates that the HfO₂ films grown at T_s < 200 °C are amorphous while films grown at T_s > 200 °C are nanocrystalline. An amorphous-to-crystalline transition occurs at T_s = 200 °C. Nanocrystalline HfO₂ films crystallized in a monoclinic structure with a (−1 1 1) orientation. An interface layer (IL) formation occurs due to reaction at the HfO₂-Si interface for HfO₂ films deposited at T_s > 200 °C. The thickness of IL increases with increasing T_s. EDS at the HfO₂-Si cross-section indicate that the IL is a (Hf, Si)-O compound. The electrical characterization using capacitance-voltage measurements indicate that the dielectric constant decreases from 25 to 16 with increasing T_s. The current-voltage characteristics indicate that the leakage current increases significantly with increasing T_s due to increased ILs.     

Synthesis of 3,5-diarylisoxazoles under solvent-free conditions using iodobenzene diacetate

A simple and efficient method has been developed for conversion of chalcone oximes to 3,5-diaryl isoxazoles in excellent yields under solvent-free conditions. The synthesized compounds were characterized by infrared spectroscopy, ^1H NMR, ^13C NMR and HRMS.     

Polyaniline nanostructures expedient as working electrode materials in supercapacitors

Granular type polyaniline (PANi), PANi nanofibers (NFs), and PANi nanotubes (NTs) expedient as working electrode materials for supercapacitors are synthesized. The synthesis procedure used in this work facilitates not only the synthesis of solid powders of the PANi nanostructures, but also thin films constituted by the same PANi nanostructures in the same experiment. PANi NFs are found to exhibit faster electrode kinetics and better capacitance when compared to PANi NTs and granular PANi. Specific capacitance and energy storage per unit mass of PANi NFs are 239.47 Fg^?1 (at 0.5 Ag^?1) and 43.2 Wh?kg^?1, respectively. Electrical conductivity of PANi NFs is also better when compared to the other two nanostructures. Properties of the three PANi nanostructures are explicated in correlation with crystallinity, intrinsic oxidation state, doping degree, BET surface area, and ordered mesoporosity pertaining to the nanostructures.     

Substrate inhibition: Oxidation of D-sorbitol and D-mannitol by potassium periodate in alkaline medium

In the oxidation of D-sorbitol and D-mannitol by potassium periodate in alkaline media, substrate inhibition was observed with both substrates, i.e., a decrease in the rate of the reaction was observed with an increase in the concentration of substrate. The substrate inhibition was attributed to the formation of stable complex between the substrate and periodate. The reactions were found to be first order in case of periodate and a positive fractional order with hydroxide ions. Arrhenius parameters were calculated for the oxidation of sorbitol and mannitol by potassium periodate in alkali media.     

Total synthesis of mangiferaelactone

Herein we document the first total synthesis of mangiferaelactone and thus establish its absolute configuration. The central nonenolide ring was constructed using ring closing metathesis and Yamaguchi esterification. The key alcohol fragment was synthesized by the Bernet–Vasella fragmentation of C-ribofuranoside.     

Structural Stability and Unfolding Properties of Cutinases from Thermobifida fusca

A comparative analysis of the structural and functional aspects along with equilibrium unfolding of two homologous cutinases, Cut1 and Cut2, from Thermobifida fusca was carried out. The CD and fluorescence profile at different pH in the range of 6 to 9 showed no structural variations for both cutinases, indicating their stability to a wide range of pH. Tryptophan quenching studies suggested that all the four Trp residues in the protein are in inaccessible hydrophobic pockets. Further, near-UV CD analysis of tertiary structure revealed a dissimilar distribution of aromatic amino acid on the surface of these two enzymes. Denaturation profiles obtained in aqueous solutions of the guanidine hydrochloride revealed different tolerance levels for unfolding of the two cutinases, with Cut2 showing higher resistivity to unfolding in comparison to Cut1. Both cutinases retained all the structural parameters even in the presence of 8 M urea, indicating the protein to be highly resistant to urea-induced unfolding. Structural study by homology modeling revealed a high resemblance of secondary structure between the two cutinases; however, their tertiary structure, hydrophobicity, and surface electrostatic properties were very different, which contributed to the difference in the structural stability of these two cutinases.     

Flexible and Rigid Amine‐Functionalized Microporous Frameworks Based on Different Secondary Building Units: Supramolecular Isomerism,Selective CO2 Capture,and Catalysis

We report the synthesis, structural characterization, and porous properties of two isomeric supramolecular complexes of ([Cd(NH₂?bdc)(bphz)_0.5]?DMF?H₂O}_n (NH₂?bdc=2‐aminobenzenedicarboxylic acid, bphz=1,2‐bis(4‐pyridylmethylene)hydrazine) composed of a mixed‐ligand system. The first isomer, with a paddle‐wheel‐type Cd₂(COO)₄ secondary building unit (SBU), is flexible in nature, whereas the other isomer has a rigid framework based on a μ‐oxo‐bridged Cd₂(μ‐OCO)₂ SBU. Both frameworks are two‐fold interpenetrated and the pore surface is decorated with pendant ?NH₂ and ?N?N? functional groups. Both the frameworks are nonporous to N₂, revealed by the type II adsorption profiles. However, at 195 K, the first isomer shows an unusual double‐step hysteretic CO₂ adsorption profile, whereas the second isomer shows a typical type I CO₂ profile. Moreover, at 195 K, both frameworks show excellent selectivity for CO₂ among other gases (N₂, O₂, H₂, and Ar), which has been correlated to the specific interaction of CO₂ with the ?NH₂ and ?N?N? functionalized pore surface. DFT calculations for the oxo‐bridged isomer unveiled that the ?NH₂ group is the primary binding site for CO₂. The high heat of CO₂ adsorption (ΔH_ads=37.7 kJ mol^?1) in the oxo‐bridged isomer is realized by NH₂???CO₂/aromatic π???CO₂ and cooperative CO₂???CO₂ interactions. Further, postsynthetic modification of the ?NH₂ group into ?NHCOCH₃ in the second isomer leads to a reduced CO₂ uptake with lower binding energy, which establishes the critical role of the ?NH₂ group for CO₂ capture. The presence of basic ?NH₂ sites in the oxo‐bridged isomer was further exploited for efficient catalytic activity in a Knoevenagel condensation reaction.     

Supramolecular Gating of Ion Transport in Nanochannels

Several covalent strategies towards surface charge‐reversal in nanochannels have been reported with the purpose of manipulating ion transport. However, covalent routes lack dynamism, modularity and post‐synthetic flexibility, and hence restrict their applicability in different environments. Here, we introduce a facile non‐covalent approach towards charge‐reversal in nanochannels (<10 nm) using strong charge‐transfer interactions between dicationic viologen (acceptor) and trianionic pyranine (donor). The polarity of ion transport was switched from anion selective to ambipolar to cation selective by controlling the extent of viologen bound to the pyranine. We could also regulate the ion transport with respect to pH by selecting a donor with pH‐responsive functional groups. The modularity of this approach further allows facile integration of various functional groups capable of responding to stimuli such as light and temperature to modulate the transport of ions as well as molecules.     

Optical microwell array for large scale studies of single mitochondria metabolic responses

Microsystems based on microwell arrays have been widely used for studies on single living cells. In this work, we focused on the subcellular level in order to monitor biological responses directly on individual organelles. Consequently, we developed microwell arrays for the entrapment and fluorescence microscopy of single isolated organelles, mitochondria herein. Highly dense arrays of 3-μm mean diameter wells were obtained by wet chemical etching of optical fiber bundles. Favorable conditions for the stable entrapment of individual mitochondria within a majority of microwells were found. Owing to NADH auto-fluorescence, the metabolic status of each mitochondrion was analyzed at resting state (Stage 1), then following the addition of a respiratory substrate (Stage 2), ethanol herein, and of a respiratory inhibitor (Stage 3), antimycin A. Mean levels of mitochondrial NADH were increased by 29 % and 35 % under Stages 2 and 3, respectively. We showed that mitochondrial ability to generate higher levels of NADH (i.e., its metabolic performance) is not correlated either to the initial energetic state or to the respective size of each mitochondrion. This study demonstrates that microwell arrays allow metabolic studies on populations of isolated mitochondria with a single organelle resolution.

A carbohydrate-based approach for the total synthesis of aculeatin D and 6-epi-aculeatin D

A concise approach for the total synthesis of aculeatin D and 6-epi-aculeatin D employing differentially protected anti, anti-1,3,5-triol alkyne prepared from alpha-D-glucoheptonic-gamma-lactone derivative is documented. Phenol protecting group manipulation for selective O-debenzylation during the hydrogenation of the diyne intermediate and one-pot phenolic oxidation with concomitant spiroketalization highlight the accomplished total synthesis.