Asymmetric,Three‐Component,One‐Pot Synthesis of Spiropyrazolones and 2,5‐Chromenediones from Aldol Condensation/NHC‐Catalyzed Annulation Reactions

A novel one‐pot, three‐component diastereo‐ and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β‐unsaturated pyrazolones, which react with a second equivalent of enal through an N‐heterocyclic carbene (NHC)‐catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3‐diketones, 2,5‐chromenediones are available through [2+4] annulation.     

Glass transition and crystallization kinetics analysis of Sb–Se–Ge chalcogenide glasses

Differential thermal analysis (DTA) has been employed to investigate the effect of Ge addition on the glass transition behavior and crystallization kinetics of Sb₁₀Se_90?xGe_x (x = 0, 19, 21, 23, 25, 27) alloys. The three characteristic temperatures viz. glass transition (T _g), crystallization (T _c), and melting (T _m) have been determined and found to vary with the heating rates and Ge content. Thermal stability and glass forming tendency have been evaluated in terms of ΔT (= T _c ? T _g) and reduced glass transition temperature. The activation energies for glass transition and crystallization have been used to analyze the nucleation and growth process. The activation energy analysis also determines the suitability of alloys to be used in switching applications. Results have been interpreted in terms of bond energies and structural transformations in the investigated alloys.     

Square Planar Platinum(II) Complexes with N,S-Donor Ligands: Synthesis,Characterisation, DNA Interaction and Cytotoxic Activity

The platinum(II) complexes with N,S-donor ligand have been synthesised and characterised by physiological techniques like elemental, electronic, Fourier transform infrared, hydrogen-1 nuclear magnetic resonance (¹H NMR) and liquid chromatography–mass spectrometry spectra. The synthesised complexes have been checked for their DNA binding ability by absorption titration and viscosity measurement, and the results show that the complexes binds to herring sperm DNA (HS DNA) via covalent mode of binding. The DNA cleavage activity of synthesised complexes has been carried out by gel electrophoresis experiment using supercoiled form of pUC19 DNA, showing the unwinding of the negatively charged supercoiled DNA. Brine shrimp (Artemia cysts) lethality bioassay technique has been applied for the determination of toxic property of synthesised complexes in terms of micromolars.     

First principles calculations of armchair graphene nanoribbons interacting with Cu atoms

We have investigated the electronic properties of bare, H-terminated, Cu-terminated and Cu-doped armchair graphene nanoribbons (AGNRs) using ab-initio approach. We found that H-termination enhances the stability and band gap whereas H extraction introduces dangling bands and lowers the band gap making bare ribbons indirect band gap semiconductors. The calculations revealed that strong hybridization between Cu atoms and AGNRs, lessen the band gap for Cu-terminated ribbons and gives rise to metallicity in Cu-doped AGNRs irrespective of their widths. Formation energy of considered ribbons yield that H-terminated AGNRs with lowest formation energy are most energetically favored, next are one edge Cu-terminated ribbons followed by bare ones whereas both edges Cu-doped ribbons are least energetically plausible. We predict that presence of Cu atoms in GNRs, significantly alter the band gap and can be used in band gap engineering of nanoribbons.     

Selective Interactions of O-Methylated Flavonoid Natural Products with Human Monoamine Oxidase-A and -B

A set of structurally related O-methylated flavonoid natural products isolated from Senecio roseiflorus (1), Polygonum senegalense (2 and 3), Bhaphia macrocalyx (4), Gardenia ternifolia (5), and Psiadia punctulata (6) plant species were characterized for their interaction with human monoamine oxidases (MAO-A and -B) in vitro. Compounds 1, 2, and 5 showed selective inhibition of MAO-A, while 4 and 6 showed selective inhibition of MAO-B. Compound 3 showed ~2-fold selectivity towards inhibition of MAO-A. Binding of compounds 1–3 and 5 with MAO-A, and compounds 3 and 6 with MAO-B was reversible and not time-independent. The analysis of enzyme-inhibition kinetics suggested a reversible-competitive mechanism for inhibition of MAO-A by 1 and 3, while a partially-reversible mixed-type inhibition by 5. Similarly, enzyme inhibition-kinetics analysis with compounds 3, 4, and 6, suggested a competitive reversible inhibition of MAO-B. The molecular docking study suggested that 1 selectively interacts with the active-site of human MAO-A near N5 of FAD. The calculated binding free energies of the O-methylated flavonoids (1 and 4–6) and chalcones (2 and 3) to MAO-A matched closely with the trend in the experimental IC_50′s. Analysis of the binding free-energies suggested better interaction of 4 and 6 with MAO-B than with MAO-A. The natural O-methylated flavonoid (1) with highly potent inhibition (IC₅₀ 33 nM; Ki 37.9 nM) and >292 fold selectivity against human MAO-A (vs. MAO-B) provides a new drug lead for the treatment of neurological disorders.     

Synthesis and characterization of LaB6 thin films on tungsten, rhenium, silicon and other substrates and their investigations as?field emitters

The paper deals with the comparative study of nanocrystalline Lanthanum hexaboride (LaB₆) thin films grown on various substrates by Pulsed laser deposition and Arc plasma method. Field emission studies were carried out on LaB₆ films deposited on various substrates show metallic behavior of the emitters. The high value of field enhancement factors, indicating that the electron emission from LaB₆ nanoscale protrusions deposited on emitter surface. The post field emission surface morphology of the emitters showed no significant erosion of the films during continuous operation. The observed behavior indicates that it is linked with the growth of LaB₆ films on substrate crystal structure. The LaB₆ nanocrystallites/nanowires films were synthesized using arc plasma method shows good emission current stability. The LaB₆ micro/nanocrystallites were also obtained by picosecond laser irradiation which gives high enhancement β factor, and good emission current stability along with high current density. The results reveal that nanocrystalline LaB₆ films, exhibit high resistance to ion bombardment and excellent structural stability and are more promising emitters for practical applications in field emission based new generation devices.     

An efficient and scalable process to produce morpholine-d8

Incorporation of isotopes has long been used as a research tool to label carbons and elucidate biochemical pathways. More recently, H→D exchange has led to analogs of therapeutic agents with improved metabolic stability and properties. Such compounds also have the potential for an improved drug/drug interaction profile and may even avoid the formation of toxic metabolites. Hence, a clear need for an efficient access to deuterated intermediates on large scale has emerged. In the context of an ongoing drug discovery program, we required large quantities of morpholine-d₈. We herein report the successful optimization of a one-pot process allowing a near complete exchange of all methylene hydrogens in morpholine to deuterium atoms using D₂O as the sole source of deuterium and Raney Nickel as catalyst. This facile and safe protocol will be used to scale up the synthesis of morpholine-d₈ in due course.