Two‐Color Valence‐to‐Core X‐ray Emission Spectroscopy Tracks Cofactor Protonation State in a Class I Ribonucleotide Reductase

Proton transfer reactions are of central importance to a wide variety of biochemical processes, though determining proton location and monitoring proton transfers in biological systems is often extremely challenging. Herein, we use two‐color valence‐to‐core X‐ray emission spectroscopy (VtC XES) to identify protonation events across three oxidation states of the O₂‐activating, radical‐initiating manganese–iron heterodinuclear cofactor in a class I‐c ribonucleotide reductase. This is the first application of VtC XES to an enzyme intermediate and the first simultaneous measurement of two‐color VtC spectra. In contrast to more conventional methods of assessing protonation state, VtC XES is a more direct probe applicable to a wide range of metalloenzyme systems. These data, coupled to insight provided by DFT calculations, allow the inorganic cores of the Mn^IVFe^IV and Mn^IVFe^III states of the enzyme to be assigned as Mn^IV(μ‐O)₂Fe^IV and Mn^IV(μ‐O)(μ‐OH)Fe^III, respectively.     

Separation of iodine species by adsorption chromatography

Based on the different properties of iodide and iodate species in somesorption materials a new chromatographic method was developed to study thespeciation of iodine in a mangrove system. Two sorption materials, aluminaand silica, were investigated and several distribution coefficients for iodideand iodate were determined at different concentrations of NaOH, NaNO₃ and NaHCO₃ solutions. The best separation results wereobtained percolating sea water samples, containing iodine species, througha glass column filled with alumina. The iodide passed through the column afterwashing the column with 0.1M sodium nitrate solution, and the iodate was elutedwith a 0.5M sodium bicarbonate solution.     

Solubility of phenobarbital in aqueous cosolvent mixtures revisited: IKBI preferential solvation analysis

The preferential solvation parameters of phenobarbital in aqueous binary mixtures of 1,4-dioxane, t-butanol, n-propanol, ethanol, propylene glycol and glycerol were derived from solution thermodynamic properties by using the IKBI method. This drug is sensitive to preferential solvation effects in all these mixtures. The preferential solvation parameter by the cosolvent (δx_1,3) is negative in almost all the water-rich mixtures but positive in mixtures with similar proportions of solvents and cosolvent-rich mixtures, except in 1-propanol + water mixtures, where negative values are also found in mixtures with x₁ ≥ 0.70. Hydrophobic hydration around the non-polar ethyl and phenyl groups of this drug in water-rich mixtures could play a relevant role in drug solvation. Otherwise, in mixtures of similar solvent compositions and in cosolvent-rich mixtures the preferential solvation by cosolvent could be due to the acidic behaviour of the drug.     

Benz[c]octalen

An expedient new synthesis of benzo[c]octalene starting from the Diels-Alder adduct of benzocyclobutadiene to 7,8-dimethylenecycloocta-1,3,5-triene is described. This octalene derivative, in solution, exists as an equilibrating mixture of the double bond isomers (2) and (3) whereas in its crystalline state only the isomer (2) is present.     

THE QUANTUM EFFICIENCY OF DYE-INDUCED PHOTOELECTRIC EFFECTS IN BILAYER MEMBRANES

Abstract— Voltage transients are generated across lipid bilayer membranes by light flashes as a result of photophysical processes in sorbed dyes which displace electrical charges. A theory is presented which indicates that: (i) the fraction of sorbed dye which displaces charge from one flash can be determined by the fractional reduction in the photovoltage amplitude resulting from a second and identical flash, providing the second flash occurs before dye excited by the first flash returns to its equilibrium condition. (ii) The photoeffect quantum efficiency can be determined from the fraction of dye displacing charge, the light intensity and the dyes' optical absorption cross section. Apparatus constraints required different experimental procedures for dyes with different excited state life times, which are discussed. Experimental results are presented for an azo dye, 3,3'-bis(α-(trimethyiammonium)methyl)azobenzenebromide (Bis-Q), three carbocyanine dyes in the series 3,3'-dimethyl-2,2'-oxacarbocyanine-iodide (diO-C₁-3), an amino-pyridinium dye, 4-( p -(dimethyl-amino)styryl)-1-rnethyl-pyridinium-iodide (di-1-ASP), and a xanthene dye, 2',4',5',7'-tetraiodofluorescein (erythrosin), the sodium salt of which is known as F, D and C red number 3. The dyes' optical absorption cross section values are uncertain owing to solvent and orientational effects in membranes. Photoeffect quantum efficiency values obtained by calculating optical absorption cross sections from the dyes' molar extinction coefficients in aqueous solutions are: Bis-Q (0.08), diO-C₁-3 (0.31), diO-C₂-3 (0.22), diO-C₅-3 (0.08), di-l-ASP (0.3) and erythrosin (0.39).     

The alternate-block-factorization procedure for systems of partial differential equations

The alternate-block-factorization (ABF) method is a procedure for partially decoupling systems of elliptic partial differential equations by means of a carefully chosen change of variables. By decoupling we mean that the ABF strategy attempts to reduce intra-equation coupling in the system rather than intra-grid coupling for a single elliptic equation in the system. This has the effect of speeding convergence of commonly used iteration schemes, which use the solution of a sequence of linear elliptic PDEs as their main computational step. Algebraically, the change of variables is equivalent to a postconditioning of the original system. The results of using ABF postconditioning on some problems arising from semiconductor device simulation are discussed.The work of R. E. Bank was supported in part by the Office of Naval Research under contract N00014-82K-0197. The work of T. F. Chan was supported in part by the National Science Foundation under grant NSF-DMS87-14612 and by the Army Research Office under contract DAAL03-88-K-0085.