Ion Association and Hydration in Aqueous Solutions of Nickel(II) and Cobalt(II) Sulfate

Aqueous solutions of nickel(II) and cobalt(II) sulfate have been investigated at 25 ^∘C by dielectric relaxation spectroscopy (DRS) over a wide range of frequencies (0.2 ≤ ν (GHz) ≤ 89) and salt concentrations (0.025 ≤ c(mol-L⁻¹) ≤ 1.4). The spectra indicate, as for MgSO₄(aq) studied previously, the simultaneous presence of double solvent-separated, solvent-shared and contact ion pairs in both NiSO₄(aq) and CoSO₄(aq). The stepwise formation constants for each ion-pair type and the overall association constant, obtained from the data are in good agreement with ultrasonic relaxation and other estimates. The DR spectra at higher concentrations (c ≥ 0.5 mol-L⁻¹) suggest the existence of a nonlinear triple ion M₂SO₄²⁺(aq). Consistent with the very strong hydration of the salts, which have ‘effective’ hydration numbers approaching 27 at infinite dilution, there are no significant differences in any of the relaxation or thermodynamic parameters for NiSO₄(aq) and CoSO₄(aq), except that the triple ion appears to be somewhat more stable for the latter.     

PHOTOSENSITIZATION BY PORPHYRINS DELIVERED TO L CELL FIBROBLASTS BY HUMAN SERUM LOW DENSITY LIPOPROTEINS. A MICROSPECTROFLUOROMETRIC STUDY

Human serum LDL were used as vehicles to deliver protoporphyrin and hematoporphyrin dimer to L cell mouse fibroblasts. Topographic analysis by microspectrofluorometry on single living cells shows that after digestion of LDL, protoporphyrin is localized in cytoplasmic areas. Protoporphyrin and hematoporphyrin dimer are readily bleached by 420 ± 60 nm radiations at the high fluence rate used. Complex bleaching kinetics are observed. Spectral studies using the same technique demonstrate that an intense fluorescent emission (λ_max= 450 nm) is produced immediately after the onset of irradiation with 365 ± 2 nm or 420 ± 60 nm radiations using LDL loaded with protoporphyrin or Photofrin II. These fluorescent products have been previously identified as lipofuscin-like pigments formed by reaction of lipid photoperoxides with amino groups. The permeation of lysosomal membranes is also induced after delivery of the porphyrins by LDL. This permeation can be strongly inhibited not only by the lysosomal inhibitors chloroquine and monensin but also by a-tocopherol. On the other hand, neither α-tocopherol nor chloroquine or monensin inhibit the lipofuscin-like pigment formation.     

New constructions for De Bruijn tori

A De Bruijn torus is a periodicd-dimensionalk-ary array such that eachn ₁ × ... ×n _d k-ary array appears exactly once with the same period. We describe two new methods of constructing such arrays. The first is a type of product that constructs ak ₁ k ₂ -ary torus from ak ₁ -ary torus and ak ₂ -ary torus. The second uses a decomposition of ad-dimensional torus to produce ad+1 dimensional torus. Both constructions will produce two dimensionalk-ary tori for which the period is not a power ofk. In particular, for and for all natural numbers (n ₁ , n ₂ ), we construct 2-dimensionalk-ary De Bruijn tori with order n ₁ , n ₂ and period where .Dedicated to the memory of Tony BrewsterPartially supported by NSF grant DMS-9201467Partially supported by a grant from the Reidler Foundation     

Modulated potential electrogenerated chemiluminescence of luminol and Ru(bpy) 3 2+

Chemiluminescence emission intensity is modulated by modulating the potential of a working electrode which is used to generate a key species in the electrogenerated Chemiluminescence (ECL) reaction. The emission is monitored synchronously using a lock-in amplifier. The reactions used in the characterization are luminol with hydrogen peroxide and tris(2,2-bipyridyl)ruthenium (II) (or Ru(bpy) ₃ ²⁺ ) with oxalate. Modulation widths of ± 50 mV yield maximum signals for luminol when centered at 0.45 V (vs Ag/AgCl) and for Ru(bpy) ₃ ²⁺ when centered at 1.05 V. The resulting signal decreases with increasing modulation frequency and shows that luminol/H₂O₂ is a faster ECL system than Ru(bpy) ₃ ²⁺ /oxalate. Working curves for luminol and for oxalate have essentially the same linear range and slope with the modulated potential approach as with a DC electrode potential. This approach provides capability for differentiating the analytical signal from constant background emission or stray light.     

A global Newton method II: Analytic centers

This paper modifies the convergence conditions of a back-tracking global Newton method announced in Goldstein (1991), making them sharper and easier to apply. A new version of the Kantorovich inequalities is presented that is simple to state and prove. An application is made to the centering problem for polytopes. Based on an idea of Ye (1989), an algorithm is given for the feasibility problem of linear inequalities.This paper is dedicated to Phil Wolfe on the occasion of his 65th birthday.     

Electrochemical oxidation of 6-hydroxy-1,2,3,4-tetrahydro-β-carboline in aqueous solution

The electrochemical oxidation of 6-hydroxy-1,2,3,4-tetrahydro-β-carboline (1), an alkaloid which occurs naturally in the mammalian brain, has been studied in aqueous solution particularly at physiological pH. The first voltammetric oxidation peak of 1 observed at the pyrolytic graphite electrode generates a radical intermediate which dimerizes to give 5,5′-bi-(6-hydroxy-1,2,3,4-tetrahydro-β-carboline) (3). However, the putative radical intermediate can also be further oxidized (1e) to give a C(5)-centered carbocation which can either dimerize in an ion-substrate reaction to give 3 or be attacked by water to give 5,6-dihydroxy-1,2,3,4-tetrahydro-β-carboline (8) which is rapidly oxidized further to 1,2,3,4-tetrahydro-β-carboline-5,6-dione (9). In the presence of glutathione dione 9 forms the 8-S-glutathionyl conjugate of 8 which is easily oxidized to the 8-S-glutathionyl conjugate of 9. It is suggested that 1 might be an alkaloid which is elevated in the brain as a result of chronic alcoholism, and the roles of the oxidative transformations of this compound in some of the addictive and neurophathological consequences of ethanol consumption are discussed.     

1,3-Oxazolidin-4-ones. Synthesis and configuration of cis and trans isomers

Mixtures of cis and trans 1,3-oxazolidin-4-ones were obtained by cyclodehydration, in the presence of p-toluenesulfonic acid or boron trifluoride etherate, of lactamide and N-methyl-lactamide with aromatic and aliphatic aldehydes. The products were separated by column (silica) chromatography and their configurations were determined.     

Zdanovskii’s Rule and Isopiestic Measurements Applied to Synthetic Bayer Liquors

Isopiestic measurements of mixed electrolyte solutions involving sodium hydroxide and other components of Bayer liquors were performed at 50?°C and 100?°C. Most of the systems studied obey Zdanovskii’s rule exactly or very closely. However, those with sodium chloride as one of their components show deviations from Zdanovskii’s rule, which are well predicted by our thermodynamic modelling software based on Pitzer’s equations.