Development of homogeneous polyamine organocatalyst for the synthesis of 2-aryl-substituted benzimidazole and benzoxazole derivatives

A new polyamine was prepared by the ring opening polymerization of epichlorohydrin and properly characterized. The catalytic property of the prepared polymer was assessed by synthesizing 2-aryl-substituted benzimidazole and benzoxazole derivatives by the conjugation of o-phenylenediamine/o-aminophenol with various aromatic aldehydes in the presence of atmospheric oxygen. Significant attributes of the present synthesis include short reaction time, good to excellent yield, high purity, easy reusability, and room temperature reaction. The reaction was carried out in the absence of any metal catalyst and other cooxidants.     

Recording multiple holographic gratings in silver-doped photopolymer using peristrophic multiplexing

Plane-wave transmission gratings were stored in the same location of silverdoped photopolymer film using peristrophic multiplexing techniques. Constant and variable exposure scheduling methods were adopted for storing gratings in the film using He-Ne laser (632.8 nm). The role of recording geometry on the dynamic range of the material was studied by comparing the results obtained from both techniques. Peristrophic multiplexing with rotation of the film in a plane normal to the bisector of the incident beams resulted in better homogenization of diffraction efficiencies and larger M/# value.     

Porous‐Organic‐Framework‐Templated Nitrogen‐Rich Porous Carbon as a More Proficient Electrocatalyst than Pt/C for the Electrochemical Reduction of Oxygen

Porous nitrogen‐rich carbon (POF‐C‐1000) that was synthesized by using a porous organic framework (POF) as a self‐sacrificing host template in a nanocasting process possessed a high degree of graphitization in an ordered structural arrangement with large domains and well‐ordered arrays of carbon sheets. POF‐C‐1000 exhibits favorable electrocatalytic activity for the oxygen‐reduction reaction (ORR) with a clear positive shift of about 40 mV in the onset potential compared to that of a traditional, commercially available Pt/C catalyst. In addition, irrespective of its moderate surface area (785 m² g^?1), POF‐C‐1000 showed a reasonable H₂ adsorption of 1.6 wt % (77 K) and a CO₂ uptake of 3.5 mmol g^?1 (273 K).     

Variations in steady-state and time-resolved background luminescence from surface-enhanced resonance Raman scattering-active single Ag nanoaggregates

We observed a background luminescence emission that was associated with surface-enhanced resonance Raman scattering (SERRS) of rhodamine 6G (R6G) molecules adsorbed on single Ag nanoaggregates and investigated the origin of the background luminescence. Thanks to the observation of single nanoaggregates, we clearly identified nanoaggregate-by-nanoaggregate variations in the steady-state and time-resolved background luminescence spectra of each nanoaggregate. From the variations in the steady-state spectra, two kinds of key properties were revealed. First, the background luminescence spectra were divided into four components: one fluorescence band corresponding to the monomers of R6G and three Lorentzian bands whose maxima were red-shifted from the fluorescence maximum of the monomer by several tens of nanometers. On the basis of the red-shifted luminescence maxima, and experimental and theoretical studies of background luminescence, we attributed the three background luminescences to fluorescence from aggregates (dimer and two kinds of higher-order aggregates) of R6G molecules on an Ag surface. Second, a positive correlation was observed between wavelengths of background luminescence maxima and wavelengths of plasmon resonance maxima. This positive correlation invoked the idea that the dipoles of both the background luminescence and the plasmon radiation are coupled with each other. From the key observations in the steady-state background luminescence spectra, we propose that two factors contribute to the variations in the steady-state background luminescence spectra; one is the aggregation (monomer, dimer, and two kinds of higher-order aggregates) of R6G molecules on an Ag surface, and the other is plasmon resonance maxima of single Ag nanoaggregates. Considering these two factors, we propose that the variations in the time-resolved background luminescence spectra are associated with deaggregation of R6G molecules (higher- to lower-order aggregates) and temporal shifts in the plasmon resonance maxima of single Ag nanoaggregates.     

Anti-inflammatory and anticancer activities of erythrodiol-3-acetate and 2,4-di-tert-butylphenol isolated from Humboldtia unijuga

Abstract

Humboldtia unijuga Bedd., endemic to Agasthyamala in Western Ghats in India, is traditionally used by local Kani tribes for chicken pox, head ache and snake bite. This study reports the isolation of erythrodiol-3-acetate (HU-1) and 2,4-di-tert-butylphenol (HU-2) from H. unijuga roots and their anti-inflammatory and anticancer activities in macrophage, skin and breast cancer cell lines. Effects of HU-1 and HU-2 treatments (50, 100?µg/mL) on gene expression profiles of pro-inflammatory cytokines TNFα, IL-6 and IL-1β, and apoptosis genes p53 and caspase 7 were studied. HU-2 exerted a significantly superior anti-inflammatory effect compared to HU-1 in all three pro-inflammatory genes. HU-2 showed a superior dose dependent anticancer effect through activation of p53 gene over HU-1 in MCF-7 cells. HU-1 exhibited a dose dependent effect on caspase 7 gene in both cell lines while HU-2 was more effective in A431. HU-2 has potential for development as a novel anti-inflammatory and anticancer agent.     

Uncovering the Neglected Similarities of Arynes and Donor–Acceptor Cyclopropanes

Arynes and donor–acceptor (D–A) cyclopropanes are two classes of strained systems having the potential for numerous applications in organic synthesis. The last two decades have witnessed a renaissance of interest in the chemistry of these species primarily because of the mild and robust methods for their generation or activation. Commonly, arynes as easily polarizable systems result in 1,2‐disubstitution, whereas D‐A cyclopropanes as polarized systems lead to 1,3‐bisfunctionalization thereby showing striking similarities. Transformations with 1,2‐ and 1,3‐dipoles afford cyclic structures. With arynes, emerging four‐membered rings as intermediates might react further, whereas the analogous five‐membered rings obtained from D–A cyclopropanes are most often the final products. However, there are a few cases where these intermediates behave surprisingly differently. This Minireview highlights the parallels in reactivity between arynes and D–A cyclopropanes thereby shedding light on the neglected similarities of these two reactive species.     

A Quadrupole mass spectrometer for resolution of low mass isotopes

The qualitative and quantitative identification of low mass isotopes in the mass range 1–6 u poses certain difficulties when attempting to achieve the required resolution with an instrument suitable for deployment within a process environment. Certain adjacent species present in the process sample (HT and D₂) require a resolution greater than 930 to achieve an accurate measurement. We demonstrate here through simulation techniques that this level of performance required is unachievable using commercially available instruments. Using previously reported simulation techniques, this article demonstrates how the required performance for resolving the low mass isotopes can be achieved by a quadrupole mass spectrometer (QMS), which incorporates a quadrupole mass filter (QMF) constructed from hyperbolic electrodes and operated in zone 3 of the Mathieu stability diagram.     

Gold catalysis: non-spirocyclic intermediates in the conversion of furanynes by the formal insertion of an alkyne into an aryl-alkyl cc single bond

It takes al-kynes: The formation of furyl-substituted heterocycles from furanynes with donor groups on the furan-alkyne tether and mechanistic control experiments indicate the involvement of open-chained carbenium ions in the overall insertion of an alkyne into a C?C bond, rather than the usual spirocyclic intermediates.