Synthesis and characterization of polyaniline doped with organic acids

Spectroscopic [UV–visible and Fourier transform IR (FTIR)] and thermal properties of chemically synthesized polyanilines are found to be affected by varying the protonation media (acetic, citric, oxalic, and tartaric acid). The optical spectra show the presence of a greater fraction of fully oxidized insulating pernigraniline phase in polyaniline doped with acetic acid. In contrast, the selectivity in the formation of the conducting phase is higher in oxalic acid as a protonic acid media. The FTIR spectra of these polymers reveal a higher ratio of the relative intensities of the quinoid to benzenoid ring modes in acetic acid doped polyaniline. Scanning electron micrographs revealed a sponge‐like structure derived from the aggregation of the small granules in acetic acid and oxalic acid doped polyaniline. A three‐step decomposition pattern is observed in all the polymers, regardless of the protonic acid used for the doping. The second step loss related to the loss of dopant is found to be higher in the oxalic acid doped polymer. In accordance with these results the conductivity is also found to be higher in oxalic acid doped material. The temperature dependent conductivity measurements show the thermal activated behavior in all the polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2043–2049, 2004     

EPR studies of a molybdenyl complex in single crystals of NH4Cl

Electron paramagnetic resonance of [MoOCl₅]^2? has been studied in single crystals of NH₄Cl. At room temperature the interaction of the unpaired electron with both the even and odd isotopes of molybdenum has been observed. The existence of metal-halogen π bonding is established by the observation of the ligand superhyperfine interaction at liquid nitrogen temperatures. Various possible models corresponding to the different spatial configurations of the molybdenyl complex in the lattice are considered to explain the experimentally observed features. The spectra are analysed using the usual spin-hamiltonian corresponding to tetragonal symmetry. The spin-hamiltonian parameters obtained are: g_∥ = 1.964, g_? = 1.945, A_∥ = 75.53 × 10^?4 cm^?1, A_⊥ = 38.42 × 10^?4 cm^?1.     

Energy transfer from a platinum—nickel excited state to platinum clusters in quasi-one-dimensional Ba(Pt,Ni)(CN)4·nH2O crystals

Laser-induced luminescence in quasi-one-dimensional Ba(Pt, Ni)(CN)₄·nH₂O crystals has been measured from 5 to 300 K. A well-defined luminescence peak is observed, corresponding to an excited electronic state of platinum and nickel. Energy transfer from this Pt—Ni excited state to Pt(CN)₄^2? clusters is found to be very much dependent on the temperature.     

Ruthenium(II)/(III) complexes of bidentate acetyl hydrazide Schiff bases

A series of octahedral Ru^II/Ru^III complexes of the type [Ru(Y)(CO)(BAX)(PPh₃)₂] and [RuCl₂(BAX)(PPh₃)₂] (Y = H or Cl; BAX = benzaldehydeacetylhydrazone anion; X = H, Me, OMe, OH, Cl or NO₂) have been prepared and characterised by spectral, magnetic and cyclic voltammetric studies. The Ru^II complexes are low spin diamagnetic (S = 0) whereas the Ru^III complexes are low spin and paramagnetic (S = 1/2). These Ru^II and Ru^III complexes absorb in the visible region respectively at ca. 16,000 and 28,000 cm^–1 which bands are assigned to the MLCT. The correlation of the _max values of the Ru^III complexes with the ⁺ Hammett parameter, is linear, indicating the profound effect of substituents on the electron density of the central metal. I.r. spectral data reveals that the hydrazone is chelated to ruthenium through the hydrazinic nitrogen and the deprotonated enolic oxygen. The rhombic nature of the e.s.r. spectra of the Ru^III complexes indicates an asymmetry in the electronic environment around the Ru atom. Ru^II complexes in CH₂Cl₂ show an irreversible Ru^II/III redox couple at ca. 0.9–0.5 V, while the Ru^III complexes show two reversible redox couples in the –0.1–0.1 and 0.8–0.6 V range, indicating that the higher oxidation state of ruthenium is stabilised by hydrazones.     

One-pot synthesis of 2-substituted quinoxalines using K10-montmorillonite as heterogeneous catalyst

An efficient one-pot synthesis of 2-substituted quinoxalines from 1,2-diamines and phenacyl bromides is developed using K10-montmorillonite (K10 clay) as a catalyst at 50 °C in acetonitrile medium. This method offers an easy route for the synthesis of substituted quinoxalines in high yields. A plausible mechanism is proposed in which quinoxalines are formed via dehydration–dehydrohalogenation–cyclization sequence. Further, the K10 clay catalyst is recovered by simple filtration and reused six times without any loss in its catalytic activity.     

Synthesis and in vitro antimicrobial studies of thiodihydropyrimidine derivatives

In the present study, a series of thiodihydropyrimidine derivatives were synthesized from different substituted aromatic aldehydes, ethyl acetoacetate, and urea/thiourea using a bimetallic TUD-1 catalyst. The structures of all the synthesized compounds were characterized by melting point determination, thin layer chromatography (TLC), infrared (IR), ¹HNMR, and ¹³C-NMR values. All the synthesized compounds were screened for their antimicrobial activities against two gram positive bacteria, two-gram negative bacteria, and two fungal strains.     

Synthesis of Peptide Cysteine Dimedone Using Fmoc-Cys(Dmd)-OH: Glutathione Cysteine Dimedone as a Probe in Investigating the Sulfenic Acid Mediated Oxidation of Glutathione

Dimedone is the most widely used chemical probe for detection of cysteine sulfenic acid in peptides and proteins. The reaction of dimedone with cysteine sulfenic acid results in the formation of unique cysteine dimedone motif containing thioether bridge. Based on the structure of cysteine dimedone residue in polypeptide, a new building block of Fmoc-Cys(Dmd)-OH was developed for solid phase synthesis of peptide cysteine dimedone. Mass spectrometric sequencing of synthetic peptides have confirmed successful incorporation of cysteine dimedone in peptide chain using HBTU/HOBt as a coupling agent. The new method permits synthesis of peptides containing both cysteine thiol and cysteine dimedone in the same sequence which was difficult to achieve by conventional methods. The synthetic peptide of glutathione cysteine dimedone was used as a standard in probing the air-mediated oxidation of thiol to disulfide form of glutathione. The co-elution of standard peptide and reaction mixture of oxidation of glutathione in presence of dimedone using RP-HPLC have confirmed the formation of glutathione cysteine sulfenic as an intermediate in the air-mediated oxidation of glutathione. The synthetic peptides of cysteine dimedone may find application in the field of redox proteomics and generation of antibodies against modified cysteine residue.     

A green route for the synthesis of 2-substituted benzoxazole derivatives catalyzed by Al-exchanged K10 clay

A new, simple, and efficient protocol is developed for the synthesis of 2-substituted benzoxazole derivatives through N–C–O bond formation using Al³⁺-exchanged K10 clay (Al³⁺-K10) as catalyst. A wide range of benzoxazole derivatives are synthesized in high yields without affecting many functional groups. Hot filtration experiments showed the absence of metal leaching and catalyst can be reused for five times with only a slight decrease in yield.     

Competitive adsorption of polymers on metal nanoparticles

We investigate the effect of system properties and adsorption sequence on competitive adsorption of poly(methyl methacrylate) (PMMA) and polystyrene (PS) on narrowly polydispersed cobalt (Co) nanoparticles (D ∼ 27 nm). The adsorbed layer composition is studied using thermo-gravimetric analysis (TGA). We find that adsorbed layers of PS are completely displaced by PMMA when the solvent is a common good solvent. An adsorbed layer of only PMMA is also obtained through competitive adsorption from a common good solvent. However, in a selective solvent that is poor for PS, sequential adsorption leads to the formation of mixed layers.