Crystal engineering of metalloporphyrin assemblies. New supramolecular architectures mediated by bipyridyl ligands

Targeted synthesis of new supramolecular motifs of metalloporphyrins in crystals by a concerted mechanism of molecular recognition in three dimensions, aided by organic ligands, is presented; it involves induced assembly of [tetrakis(4-hydroxyphenyl)porphyrinato]zinc species by a combination of axial coordination through bridging bipyridyls and of lateral hydrogen bonding.     

Dialgebra cohomology as a G-algebra

It is well known that the Hochschild cohomology of an associative algebra admits a G-algebra structure. In this paper we show that the dialgebra cohomology of an associative dialgebra has a similar structure, which is induced from a homotopy G-algebra structure on the dialgebra cochain complex .

     

Synthesis,spectral characterization and redox studies of [1-alkyl-2-(naphthyl-β-azo)imidazole] palladium(II) catecholates

1-Alkyl-2-(naphthyl--azo)imidazoles [-NaiR; R = Me (a), Et (b), CH₂Ph (c)] react with Pd(MeCN)₂Cl₂ to yield Pd(-NaiR)Cl₂ (2), the i.r. spectra of which support the presence of a cis-PdCl₂ configuration. The complexes react with catechols in the presence of Et₃N to yield ternary complexes [Pd(-NaiR)(O,O)] [O,O = pyrocatecholato (cat) (3), 4-t-butylcatecholato (tbcat) (4), 3,5-di-t-butylcatecholato (dtbcat) (5), and tetrachlorocatecholato (tccat) (6)], which were characterized by elemental analysis, i.r. and ¹H-n.m.r. spectral data. Redox studies by cyclic voltammetry suggest the existence of four successive redox couples wherein two responses, positive to s.c.e. are due to catechol to semiquinone and semiquinone to quinone oxidation, respectively; the couples at negative to s.c.e. are referred to azo reductions. The complexes exhibit ligand-ligand charge-transfer transitions in the near-i.r. region. The band position is largely dependent upon the substitutent on the catechol frame and exhibits negative solvatochromic effects. The transition is qualitatively assigned as the HOMO (cat) LUMO (-NaiR) transition. This fact is also supported by theoretical calculations using the PM3 method.     

Erratum to: Solution behavior of aqueous mixtures of low and high molecular weight hydrophobic amphiphiles

Mixtures of a hydrophobic triblock copolymer (L121, PEO₅PPO₆₈PEO₅) and a hydrophobic anionic surfactant (AOT, Sodium bis(2-ethylhexyl)sulfosuccinate), each alone forming turbid vesicular solutions in water, aggregate to produce a thermodynamically stable, transparent and isotropic solution. Mixed AOT/L121 aggregates could be confirmed by fluorescence, surface tension, differential scanning calorimetry (DSC) and isothermal titration calorimetry (ITC). In an isotropic region, where mixed aggregates are formed, there is a synergistic interaction between monomers of AOT and L121 in the mixture. In addition, Small Angle Neutron Scattering (SANS) experiments provided evidence that mixed aggregates have the shape of either spheres (with a certain polydispersity) or very short ellipsoids (axial ratio below 2), confirming a transition from giant multilamellar vesicles to small aggregates upon mixing the two hydrophobic amphiphiles. Upon dilution, the morphology changes to disk-like. From an examination of the results of all the methods the peculiar behavior of the mixed AOT/L121 system is explained.     

Finite frames,P-frames and basically disconnected frames

Let \({\mathcal{P}}\) be an ideal of closed quotients of a completely regular frame L and \({\mathcal{R}_{\mathcal{P}}(L)}\) the collection of all functions in the ring \({\mathcal{R}(L)}\) whose support belong to \({\mathcal{P}}\) . We show that \({\mathcal{R}(L)}\) is a Noetherian ring if and only if \({\mathcal{R}(L)}\) is an Artinian ring if and only if L is a finite frame. Using this result, we next show that if \({\mathcal{P}}\) is the ideal of all compact closed quotients of L and L is \({\mathcal{P}}\) -continuous, then \({\mathcal{R}_{\mathcal{P}}(L)}\) is a Noetherian ring if and only if L is finite. Moreover, we show that L is a P-frame if and only if each ideal of \({\mathcal{R}(L)}\) is of the form \({\mathcal{R}_{\mathcal{P}}(L)}\) for some choice of \({\mathcal{P}}\) . We furnish equivalent conditions for \({\mathcal{R}_{\mathcal{P}}(L)}\) to be a prime ideal, a free ideal, and an essential ideal of \({\mathcal{R}(L)}\) separately in terms of the cozero elements of L. Finally, we show that L is basically disconnected if and only if \({\mathcal{R}(L)}\) is a coherent ring.     

Quantitative Characterization of Bovine Serum Albumin, α-Lactalbumin and β-Lactoglobulin in Commercial Whey Sample by RP-LC

A simple, sensitive and precise reverse phase liquid chromatographic method has been developed and validated for quantification of bovine serum albumin (BSA), α-lactalbumin (α-La) and β–lactoglobulin (β-Lg) that are removed from whey waste by foam fractionation method. The data is reproducible over a wide concentration range. This optimized method allowed analysis of BSA, α-La, β-Lg in a mixture within 5 min and could be applied to the analysis of a variety of commercial and laboratory whey products within a short time.     

Fiber-optic Singlet Oxygen [1O2 (1Δg)] Generator Device Serving as a Point Selective Sterilizer

Traditionally, Type II heterogeneous photo-oxidations produce singlet oxygen via external irradiation of a sensitizer and external supply of ground-state oxygen. A potential improvement is reported here. A hollow-core fiber-optic device was developed with an “internal” supply of light and flowing oxygen, and a porous photosensitizer-end capped configuration. Singlet oxygen was delivered through the fiber tip. The singlet oxygen steady-state concentration in the immediate vicinity of the probe tip was ca 20 f m by N-benzoyl- dl -methionine trapping. The device is portable and the singlet oxygen-generating tip is maneuverable, which opened the door to simple disinfectant studies. Complete Escherichia coli inactivation was observed in 2 h when the singlet oxygen sensitizing probe tip was immersed in 0.1 mL aqueous samples of 0.1–4.4 × 10⁷ cells. Photobleaching of the probe tip occurred after ca 12 h of use, requiring baking and sensitizer reloading steps for reuse.     

Micellar Effect on Chromium(VI) Oxidation of Ethanol and Propan-1-ol in Aqueous Acid Media

Cetylpyridinium chloride (CPC) inhibits the Cr(VI) oxidation of ethanol and propan-1-ol while sodium dodecyl sulfate (SDS) catalyzes the title reactions. At higher values of the [surfactant], the rate attains a limiting value. The micellar effect has been explained by considering the preferential partitioning of the reactants in terms of the suggested mechanism. Applicability of the Menger-Portnoy model and Piszkiewicz model to explain the observed micellar effect has been examined. This revised version was published online in June 2006 with corrections to the Cover Date.     

Bredon cohomology of cyclic geometric realization of G -cyclic sets

We define equivariant cyclic and Hochschild cohomology modules of a cyclic objectX in the category ofG-sets and relate them with the Bredon cohomologies of the cyclic geometric realization |X|^cy.