A zwitterionic viologen disulfonate–hydroquinone charge‐transfer crystal: 2,2′‐(4,4′‐bipyridinium‐1,1′‐diyl)di(ethanesulfonate)–hydroquinone (1/2)

The structure of the title compound, C₁₄H₁₆N₂O₆S₂·2C₆H₆O₂, consists of 2,2′‐(4,4′‐bipyridinium‐1,1′‐diyl)di(ethanesulfon­ate) mol­ecules (with crystallographically imposed twofold symmetry) that are hydrogen bonded to each other, as well as to hydro­quinone mol­ecules, in a complex three‐dimensional motif. The orange color of the crystals is indicative of the donor–acceptor interaction between the electron‐rich hydro­quinone π‐donor and the electron‐deficient bipyridinium π‐acceptor. The dihedral angle between the bipyridyl planes is 38.31 (11)°. The distance from the centroid of one of the hydro­quinone mol­ecules to the center of the bipyridinium group is 3.653 (3) Å, which is within the range typically observed for molecular complexes exhibiting charge‐transfer characteristics.     

Electrochemical detection of the oxidation of alcohols byN-hydroxyethylethylenediamminetriacetatoruthenate(IV)

The oxidation of [Ru^III(hedta)(H₂O)]=(1) to its Ru^IV monomeric complex at a glassy carbon electrode is abserved to promote oxidation of alcohols bearing an a-hydrogen (i-PrOH benzyl alcohol,sec-phenethyl alcohol). Tertiary substitution blocks the oxidation (t-BuOH). The oxidation of the alcohols is detected by an enhancement in the current of the Ru^IV/III waves at potentials above 0.96V, caused by scavenging (reduction) of Ru^IV by the alcohols. Binuclear complexes which possess Ru^IV bridged by oxo to either a second Ru^IV or to Ru^III in species of composition [LRuORuL]ⁿ⁻, L=hedta³⁻, fail to oxidize the alcohols. The terminal oxo moiety attached to Ru^IV is postulated to facilitate the oxidation of primary and secondary alcohols in a manner analogous to Meyer's [RuO(trpy)(bpy)]²⁺ catalyst. The dissociation of the (III,IV) binuclear complex into its monomers provides a pathway which increases catalytic activity at the expense of the inactive (III, IV) binuclear complex's concentration. TMC 2531     

Ultraviolet Spectral Energy Differences Affect the Ability of Sunscreen Lotions to Prevent Ultraviolet-Radiation-Induced Immunosuppression*

Acute exposure to UV radiation causes immunosuppression of contact hypersensitivity (CH) responses. Past studies conducted with unfiltered sunlamps emitting nonsolar spectrum UV power (wavelengths below 295 nm) or using excessive UV doses have suggested sunscreens may not prevent UV-induced immunosuppression in mice. This study was thus designed to evaluate critically the effects of different UV energy spectra on the immune protection capacity of sunscreen lotions. Minimum immune suppression doses (MISD), i.e. the lowest UV dose to cause~50% suppression of the CH response to dinitrofluorobenzene in C3H mice, were established for three artificial UV sources. The MISD for each UV source was 0.25 kJ/m² for unfiltered FS20 sunlamps (FS), 0.90 kJ/m² for Kodacel-filtered FS20 sunlamps (KFS), which do not emit UV power at wavelengths <290 nm, and 1.35 kJ/m² for a 1000 W filtered xenon arc lamp solar simulator. Using MISD as baseline, sunscreens with labeled sun protection factors (SPF) of 4, 8, 15 and 30 were tested with each UV source to establish their relative immune protection factors. The immune protection factor of each sunscreen exceeded its labeled SPF in tests conducted with the solar simulator, which has a UV power spectrum (295–400 nm) similar to that of sunlight. Conversely, sunscreen immune protection factors were significantly less than the labeled SPF in tests conducted with FS and KFS. Comparison of the immunosuppression effectiveness spectra showed that relatively small amounts of nonsolar spectrum UV energy, i.e. UVC (200–290 nm) and/or shorter wavelength UVB (between 290 and 295 nm), produced by FS and KFS contributes significantly to the induction of immunosuppression. For example, 36.3% and 3.5% of the total immunosuppressive UV energy from FS and KFS, respectively, lies below 295 nm. Sunscreen absorption spectra showed that transmission of immunosuppressive UV energy below 295 nm for FS was at least eight-fold higher than that for KFS. Compared to the solar simulator UV spectrum the transmission of nonsolar immunosuppressive UV energy through sunscreens was >15-fold higher for FS and ≥1.5-fold higher for KFS. These data demonstrate that relevant evaluations of sunscreen immune protection can only be obtained when tests are conducted with UV sources that produce UV power spectra similar to that of sunlight and UV doses are employed that are based on established MISD.     

Zinc is an essential cofactor for type I isopentenyl diphosphate:dimethylallyl diphosphate isomerase

Isopentenyl diphosphate (IPP) isomerase catalyzes the interconversion of IPP and dimethylallyl diphosphate (DMAPP). This is an essential reaction in the mevalonate pathway for biosynthesis of isoprenoid compounds. A crystal structure of Escherichia coli type I IPP isomerase shows a his3glu2 octahedral metal binding site (Durbecq, V. et al. EMBO, 2001, 20, 1530-1537). A metal ion analysis of recombinant E. coli type I IPP isomerase purified from metal-free buffer or buffer containing 10 muM ZnCl2 and 10 muM MnCl2 indicated that the protein contained one atom of Zn2+ per molecule. The metal content and the activity of the enzyme did not change when dialyzed for 6 h against metal-free buffer but rapidly decreased upon dialysis against buffer containing o-phenanthroline. Structural and catalytic roles for Zn2+ are discussed.     

Synthesis and structural studies of hydrophilic mesocyclic trithioethers

The functionalized mesocyclic trithioethers, 1,4,7-trithiacyclodecane-9,9-dimethanol (10S3-diMeOH), 9 -methyl-1, 4, 7 - trithiacyclodecane - 9 -carboxylic acid (Me-10S3-acid), 1,4,7-trithiacycloundecane-9,10-diol (dihydroxy-11S3), 1,5,9-trithiacyclododecane-3,3-dimethanol (12S3-diMeOH), 3-methyl-1,5,9-trithiacyclododecane-3-carboxylic acid (Me-12S3-acid), and 1 , 5 , 9 - trit hiacyclo tride cane -11 , 12 - diol ( dihydroxy - 13S3), have been synthesized using the cesium dithiolate technique. The single-crystal X-ray structure has been determined for 3-methyl-1,5,9-trithiacyclododecane-3-carboxylic acid. The compound crystallizes in the monoclinic space group P2₁/n, with a = 9.513(2) Å, b = 5.706(1) Å, c = 25.70(1) Å, β = 96.50(1)°, Z = 4, and R = 0.075. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:123–128, 1998     

A role for fucose alpha(1-2) galactose carbohydrates in neuronal growth

We report a fucose alpha(1-2) galactose-mediated pathway for the modulation of neuronal growth and morphology. Our studies provide strong evidence for the presence of Fucalpha(1-2)Gal glycoproteins and lectin receptors in hippocampal neurons. Additionally, we show that manipulation of Fucalpha(1-2)Gal-associated proteins using small-molecule and lectin probes induces dramatic changes in neuronal morphology. These findings may provide a novel pathway to stimulate neuronal growth and regeneration.     

Solid phase deprotection of 2-nitrobenzenesulfonamides: synthesis of simple 2-(alkylamino)-pyrroles

The 2-nitrobenzenesulfonamide cleavage using a solid-phase thiophenolate reagent gives simple 2-(alkylamino)-pyrroles without the presence of the competing nucleophilic substitution product.     

Optimizing State Patrol Manpower Allocation

One of the most difficult tasks of state highway patrol administrators is allocation of manpower; i.e. determining the most effective level of operational manpower for patrol tasks. Typically, administrators resolve the allocation problem by relying on prior statistical data and by employing subjective analysis. In general, only limited systematic analyses have been applied to the problem. This paper presents an integer goal programming model for allocating highway patrolmen to road segments within a patrol region. The model is demonstrated via a case example of the Nebraska State Patrol. The results of the model are valuable to the patrol administrator for considering departmental goals and priority structure, in addition to available historical data, in the assignment of state patrol manpower.