Synthesis and cation binding properties of new arylazo- and heteroarylazotetrathiacalix[4]arenes

New macrocyclic tetrathiacalix[4]arenes have been synthesized by incorporating arylazo-, thiazoleazo- and β-naphthylazo- units in the tetrathiacalix[4]arene molecular architecture through diazotization and coupling reactions. The new compounds have been characterized by ¹H NMR, ¹³C NMR and FAB-MS spectroscopic analysis. X-ray crystallography for one of the new dyes (4a) reveals that the compound is present in the cone conformation. The synthesized macrocycles have been examined for their binding with alkali (Li⁺, Na⁺, K⁺, Cs⁺ and Rb⁺), alkaline earth (Ca²⁺, Mg²⁺ and Ba²⁺) and transition metal cations (Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Hg⁺, Hg²⁺, Pd²⁺ and Pt²⁺) by UV-visible spectroscopy to reveal selective bathochromic shifts for heavier alkali metal ions (cesium and rubidium) and palladium in a 1:1 and 2:1 stoichiometry respectively. The study has a significant bearing on the development of useful ionic filters and sensor materials.     

Synthesis and characterization of novel fluorophosphazene-derived cobaltacyclopentadienyl metallacycles: reagents for assembly of aryl-bridged fluorophosphazenes

Reaction of (beta-phenylethynyl)pentafluorocyclotriphosphazene, F5P3N3C identical with CPh, with in situ generated eta5-(MeOC(O)C5H4)Co(PPh3)2 resulted in the formation of two isomers of cobaltacyclopentadienylmetallacycles, (eta(5)-carbomethoxycyclopentadienyl)(triphenylphosphine)-2,5-bis(pentafluorocyclotriphosphazenyl)-3,4-diphenyl cobaltacyclopentadiene (1) and (eta5-carbomethoxycyclopentadienyl)(triphenylphosphine)-2,4-bis(pentafluorocyclotriphosphazenyl)-3,5-diphenyl cobaltacyclopentadiene (2), along with the sandwich compound [eta5-carbomethoxycyclopentadienyl]-[eta4-1,3-bis(pentafluorocyclotriphosphazenyl)-2,4-diphenylcyclobutadiene]cobalt (3). Formation of cobaltacyclopentadienylmetallacycles or cyclobutadienylmetallocene having two fluorophosphazene units on vicinal carbon atoms of the rings was not observed in this reaction. Reaction of 1 with diphenylacetylene resulted in the formation of a novel aryl-bridged fluorophosphazene, 1,4-bis(pentafluorocyclotriphosphazenyl)-2,3,5,6-tetraphenyl benzene (4), and the conversion of cobaltametallacycle to the sandwich compound, [eta5-(MeOC(O)C5H4]Co(eta4-C4Ph4) (5). Reaction of 1 with phenylacetylene resulted in the formation of aryl-bridged fluorophosphazene, 1,4-bis(pentafluorophosphazenyl)-2,3,5,-triphenyl benzene (6). New compounds 1-4 were structurally characterized. In compound 1, the two fluorophosphazene units were oriented in gauche form with respect to each other. However, in compounds 2 and 3, they were eclipsed to each other, and in compound 4, they were oriented anti to each other.     

Spectroscopy of the Kondo problem in a box

Motivated by experiments on double quantum dots, we study the problem of a single magnetic impurity confined in a finite metallic host. We prove an exact theorem for the ground state spin, and use analytic and numerical arguments to map out the spin structure of the excitation spectrum of the many-body Kondo-correlated state, throughout the weak to strong coupling crossover. These excitations can be probed in a simple tunneling-spectroscopy transport experiment; for that situation we solve rate equations for the conductance.     

Measuring the elongation viscosity of lyocell using a semi-hyperbolic die

The lyocell process involves dry jet—wet spinning of a solution of cellulose in N-methyl morpholine oxide monohydrate. Measurement of the elongation viscosity of lyocell is important for the design and optimization of the lyocell process. We present a useful method for the determination of the elongation viscosity of lyocell by using a combination of experimental measurements on a semi-hyperbolic die and viscoelastic simulations.     

Potential of Kalopanax septemlobus Leaf Extract in Synthesis of Silver Nanoparticles for Selective Inhibition of Specific Bacterial Strain in Mixed Culture

Silver nanoparticles (AgNPs) were synthesised using Kalopanax septemlobus plant leaf extracts. UV-visible spectrophotometric, Fourier-transform infrared, electron dispersive X-ray spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses confirmed synthesis of AgNPs. TEM micrographs revealed presence of well-dispersed AgNPs predominantly of small size and different shapes with an average particle size of 30.8 nm. Antimicrobial susceptibility tests of AgNP treatments revealed variability in sensitivity of bacteria Bacillus cereus and Saccharophagus degradans under study. Minimum inhibitory concentration (MIC) values of the AgNPs for B. cereus and S. degradans were found to be 30 and 10 μg/mL, respectively. The mixed culture of B. cereus and S. degradans treated with AgNPs at 10 μg/mL showed increase in growth with time, suggesting survival of bacteria in liquid media. The plating of mixed culture before AgNP treatment showed presence of both bacteria, but 24-h-old mixed culture treated with AgNPs at the concentration of 10 μg/mL showed presence of B. cereus colonies. SEM micrographs revealed damage to S. degradans cells but no effect on B. cereus cells after AgNP treatment. Confocal microscopic observations of AgNP-treated mixed cultures by Nile blue A staining indicated intact polyhydroxyalkanoates producing flourescent cells of B. cereus but damage and deformities in S. degradans cells. This study suggests that AgNPs can selectively inhibit growth of S. degradans and retain B. cereus at MIC of S. degradans. This report is a case study for selective inhibition of one bacteria and growth of the other in a culture using plant-synthesized silver nanoparticles.     

An Efficient Microwave‐Assisted Synthesis and Antimicrobial Activity of Novel 2‐Amino 3‐Cyano Pyridine Derivatives using Two Reusable Solid Acids as Catalysts

Two solid acids, Fe³⁺ K‐10 montmorillonite clay and HY‐zeolite, have been employed efficiently for synthesis of 2‐amino 3‐cyano pyridines 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j , 4k , 4l , 4m , 4n , 4o , 4p , 4q , 4r , 4s , 4t , 4u , 4v , 4w , 4x by multicomponent reaction of 3‐acetyl 4‐hydroxy coumarin 1a , 1b , 1c , 1,3‐diphenyl‐1H‐pyrazole‐4‐carbaldehyde 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h , malononitrile 3 , and ammonium acetate. Both the catalysts are recoverable and recyclable. The main significant of this procedure is short reaction time, high yields, easy workup procedure, and being environmentally friendly. The structures of all the compounds have been well characterized by IR, ¹H NMR, ¹³C NMR, and mass spectral data. All the synthesized compounds were screened for their antimicrobial and antifungal activities.     

Synthesis and evaluation of neutral anion receptors based on acylhydrazide-appended calix[4]arenes

A new class of neutral receptors based upon acylhydrazide-appended calix[4]arenes was synthesised and evaluated for recognition of anions. Detailed NMR and single-crystal X-ray analyses of one of the synthesised compounds reveal that anion recognition in such derivatives is achieved through cooperative hydrogen bond interactions. The presence of three centred NH–O and two OH–O hydrogen bonds at the lower rim of the synthesised calixarene architecture apparently helps the molecular scaffold to retain cone conformation to enable deployment of intermolecular hydrogen bonds for selective recognition of HSO₄ ^? ion in preference to F^?, Cl^?, Br^?, I^?, ClO₄ ^?, AcO^? and PF₆ ^? ions.     

Dielectric critical behaviour at a metal-insulator transition under lattice compression

We study dielectric critical behaviour around a continuous metal-insulator transition in crystalline Cesium Iodide induced by changing the lattice parameter. The ab initio calculations of band structure and various quantities related to the dielectric response are performed in the transition region, within the local density approximation of the density functional theory. These calculations allow us to establish the power-law singularities of various quantities on two sides of the transition. The exponents obtained here are mean-field like due to the approximation in which interactions and disorder are treated. The critical behaviour is discussed by applying the scaling principle to the wavevector and frequency dependent dielectric function. We further investigate the effect of dielectric anomalies on optical properties by calculating the reflectance around transition region taking the ionic contribution to the dielectric function also into account. We find that the reflectance as a function of frequency shows very different kind of behaviour on both sides of the metal-insulator transition.     

Temperature dependence of EPR spectrum of Mn2+ doped in ammonium iodide single crystals

EPR of Mn²⁺ doped in ammonium iodide single crystal has been studied at X-band in the temperature range 573–577 K. The observed temperature dependence of line widths and spin Hamiltonian parameter b₂⁰ below room temperature is related to the structural transformations in the crystal. The coexistence of high temperature phase (NaCl) and low temperature phase (CsCl) is attributed to the large thermal hysteresis in line widths and b₂⁰. The dissociation of ion vacancy pairs occurs near 500 K and is reflected in the reversible change of an anisotropic EPR spectrum in an isotropic sextet near this temperature. The ion vacancy pair models for NaCl and CsCl phases are discussed along with the effects of thermal processing of the samples. Heating the crystals above 500 K leads to expulsion of Mn²⁺ impurity from the crystal.