Demetallation of α,β,γ,δ-tetrakis(p-sulfophenyl) porphiniron(III) in mineral acid–alcohol–water media

Demetallation rates of α,β,γ,δ-tetrakis(p-sulfophenyl)porphiniron(III) in hydrochloric acid–ethanol–water, perchloric acid–ethanol–water, and sulfuric acid–alcohol–water media were determined. For a given acidity value H₀ the order of the rates for the three acids was HCl > H₂SO₄ > HClO₄. This is also the order for complex formation between acid anion and iron(III). Consequently ligands as well as protons are involved in the breaking of bonds between the metal and the porphyrin leading to the formation of the activated complex. The log k values for HCl and HClO₄ media were not linearly related to the Hammett acidity function as they were for sulfuric acid–ethanol–water media. The average ΔH? and ΔS?values for the HCl media were 18.4 ± 1.4 kcal/mol and ? 19 ± 3 cal K mol, respectively, in very close agreement with those for H₂SO₄ media despite the difference in H ₀ dependence. For H₂SO₄–alcohol–water media the order of the rates was butanol > propanol > ethanol with little difference between isomeric alcohols.     

A novel conversion of chromone-3-carboxaldehyde to 5-nitro-2,3-benzofurandione-(Z)-2-oxime

The conversion of chromone-3-carboxaldehyde to 5-nitro-2,3-benzofurandione-($\text{Z}$)-2-oxime under nitrating conditions is reported.     

Effect of temperature on carbon-black agglomeration in hydrocarbon liquid with adsorbed dispersant

Suspensions of carbon black in oil, stabilized with adsorbed polyisobutylene succinimide (PIBSI) dispersant, are commonly used as model systems for investigating the soot-handling characteristics of motor oils. The structure of the carbon-black agglomerates changes dramatically with temperature; this results in a concomitant change in the suspension rheology. Linear and nonlinear rheological experiments indicate a large increase of the interparticle attractions as the temperature is raised. To elucidate the origin of this behavior, we investigate the effect of temperature on the stabilizing effect of the dispersant. Measurements of adsorption isotherms of the dispersant on carbon black indicate that there is little variation of the binding energy with temperature. Intrinsic viscosity measurements of PIBSI dispersants in solution clearly exhibit an inverse dependence of the dispersant chain dimension with temperature. These results suggest that the temperature-dependent changes in the chain conformation of the PIBSI dispersant are primarily responsible for the changes in the dispersion rheology, and we propose a simple model to account for these data.     

Theoretical analysis of the 13C NMR of iodoalkynes upon complexation with Lewis bases

Recent experiments have demonstrated that the (13)C NMR spectra of iodoalkynes exhibit a strong solvent effect because of complexation with Lewis-basic solvents. This paper describes DFT NMR calculations (B3LYP-GIAO with LanL2DZ or Sadlej pVTZ basis set) of iodoalkynes and their Lewis acid-base complexes, interpreted by using Natural Chemical Shift (NCS) analysis within the framework of the Ramsey formalism for chemical shift. In particular, the paper presents calculations on diiodoethyne and its complexes with one and two ammonia molecules. Examination of the orbital changes upon forming the mono- and bisammonia complexes indicates that mixing of the nitrogen lone pair with the C-I antibonding orbital increases the paramagnetic deshielding at C1. Further increases can be attributed to increased polarization of the iodine lone-pair orbitals onto C1. The haloiodoalkyne series XCCI (X = F, Cl, Br, I) offers additional support for this model of the solvent effect.     

Effect of age on detection of gaps in speech and nonspeech markers varying in duration and spectral symmetry

Gap detection thresholds for speech and analogous nonspeech stimuli were determined in younger and older adults with clinically normal hearing in the speech range. Gap detection thresholds were larger for older than for younger listeners in all conditions, with the size of the age difference increasing with stimulus complexity. For both ages, gap detection thresholds were far smaller when the markers before and after the gap were the same (spectrally symmetrical) compared to when they were different (spectrally asymmetrical) for both speech and nonspeech stimuli. Moreover, gap detection thresholds were smaller for nonspeech than for speech stimuli when the markers were spectrally symmetrical but the opposite was observed when the markers were spectrally asymmetrical. This pattern of results may reflect the benefit of activating well-learned gap-dependent phonemic contrasts. The stimulus-dependent age effects were interpreted as reflecting the differential effects of age-dependent losses in temporal processing ability on within- and between-channel gap detection.     

Electrophilic aromatic substituted luciferins as bioluminescent probes for glutathione S-transferase assays

New highly sensitive latent bioluminescent luciferin substrates were designed and synthesized for monitoring mammalian glutathione S-transferase (GST) and Schistosoma japonicum enzyme activities.