Rh(III)-Catalyzed One-Step Synthesis of ortho-Alkynylated Perylene Imide Dyes: Optical and Electrochemical Properties of New Derivatives

A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization.     

Expression ofAscaris suum malic enzyme in a mutantEscherichia coli allows production of succinic acid from glucose

Applied Biochemistry and Biotechnology - The malic enzyme gene ofAscaris suum was cloned into the vector pTRC99a in two forms encoding alternative arnino-termini. The resulting plasmids, pMEAl and...     

Capillary electrophoresis in aqueous-organic media. Ionic strength effects and limitations of the Hubbard-Onsager dielectric friction model

The mobilities of three aromatic sulfonates, ranging in charge from -1 to -3, were investigated by capillary electrophoresis using buffers containing 0 to 75% ethanol or 2-propanol. Absolute mobilities were determined by extrapolation of the effective mobilities to zero ionic strength according to the Pitts' equation. For all buffers studied, ions of higher charge experienced larger ionic strength effects. The resulting ionic strength-induced selectivity alterations were more dramatic when organic solvents were present in the media. Furthermore, for different organic modifier types and contents, the magnitude of the ionic strength effect was governed to a large extent by the 1/(eta epsilon 1/2) dependence in the electrophoretic effect of the Pitts' equation. Addition of ethanol or 2-propanol to the electrophoretic media resulted in changes in the absolute mobilities of the ions. These solvent-induced mobility changes are attributed to dielectric friction. As predicted by the Hubbard-Onsager model, dielectric friction increased with increasing organic content and with increasing analyte charge. As a result, dramatic changes in the relative absolute mobilities were observed, such as a reversal in migration order between sulfonates of -1 and -3 charge in 75% 2-propanol. Within the alcohols, the Hubbard-Onsager model was successful at predicting the relative mobility trends upon changing solvent. However, the relative trends observed between acetonitrile-water and alcohol-water media were not consistent with the model. This may be explained by the continuum nature of the model, whereby the different ion-solvent interactions characteristic to each solvent class are not taken into account.     

Structural basis for discriminative regulation of gene expression by adenine- and guanine-sensing mRNAs

Metabolite-sensing mRNAs, or "riboswitches," specifically interact with small ligands and direct expression of the genes involved in their metabolism. Riboswitches contain sensing "aptamer" modules, capable of ligand-induced structural changes, and downstream regions, harboring expression-controlling elements. We report the crystal structures of the add A-riboswitch and xpt G-riboswitch aptamer modules that distinguish between bound adenine and guanine with exquisite specificity and modulate expression of two different sets of genes. The riboswitches form tuning fork-like architectures, in which the prongs are held in parallel through hairpin loop interactions, and the internal bubble zippers up to form the purine binding pocket. The bound purines are held by hydrogen bonding interactions involving conserved nucleotides along their entire periphery. Recognition specificity is associated with Watson-Crick pairing of the encapsulated adenine and guanine ligands with uridine and cytosine, respectively.     

Ruthenium bipyridyl compounds with two terminal alkynyl ligands

Compounds of the form Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)2(X2bipy = 4,4'-X(2)-2,2'-bipyridine, X = Me 3a, Br 3b, I 3c) have been synthesised from the mono-alkynyl precursors Ru(X2bipy)(PPh3)2(-C triple bond CC6H4NO2-p)Cl (X = Me 2a, Br 2b, I 2c); the former are the first ruthenium bis-alkynyl compounds that also contain a bipyridyl ligand. Spectroelectrochemical investigation of 3a shows that the metal is readily oxidised to form the ruthenium(III) compound 3a+, and will also undergo a single-electron reduction at each nitro group to form 3a2-. ESR and UV/visible spectra of these redox congeners are presented. We also report the synthesis of [Ru(Me2bipy)(PPh3)2(-C triple bond CBut)(N triple bond N)][PF6] during the attempted synthesis of Ru(Me2bipy)(PPh3)2(-C triple bond CBut)2, and report its X-ray crystal structure and IR spectrum. X-Ray crystal structures of 3b and 3c(as two different solvates) are presented, and the nature of the intermolecular interactions seen therein is discussed. Z-Scan measurements on Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, But, Ph, C6H4Me) are also reported, and show that Ru(Me2bipy)(PPh3)2(-C triple bond CR)Cl (R = C6H4NO2-p2a, Ph) exhibit moderate third-order non-linearities.     

Determination of zwitterionic and cationic surfactants by high-performance liquid chromatography with chemiluminescenscent nitrogen detection

The use of chemiluminescent nitrogen specific detection (CLND) combined with an HPLC separation allows for the identification and quantification of cationic and zwitterionic surfactants. The CLND provides equimolar responses, based on the amount of nitrogen within any compound. This allows for the detection of any nitrogen containing surfactant. Reversed-phase separation methods using cyano columns are developed for cationic and zwitterionic (sulfobetaine) surfactant mixtures. The limits of detection for these surfactants are in the single micromolar range (1 ng N). A linear response was obtained (R2=0.9981) between 50 microM and 5 mM. The methodology was then applied to the determination of an industrial zwitterionic surfactant, Rewoteric AM CAS U [coco(amidopropyl)hydroxyldimethylsulfobetaine].     

Design and development of a common synthetic strategy for a variety of 1-N-iminosugars

[formula: see text] A new synthetic strategy has been developed for a general approach toward the synthesis of a variety of 1-N-iminosugar-type glycosidase inhibitors utilizing precursors developed by the PET-mediated cyclization of alpha-trimethylsilylmethylamine radical cation to a tethered pi-functionality.     

SSZ-53 and SSZ-59: two novel extra-large pore zeolites

The syntheses, structure solutions, and physicochemical and catalytic characterizations of the novel zeolites SSZ-53 and SSZ-59 are described. SSZ-53 and SSZ-59 were synthesized under hydrothermal conditions with the [1-(4-fluorophenyl)cyclopentylmethyl]trimethyl ammonium cation and 1-[1-(4-chlorophenyl)cyclopentylmethyl]-1-methyl azocanium cation, respectively, as structure-directing agents. The framework topology of SSZ-53 was solved with the FOCUS method, and the structure of SSZ-59 was determined by model building. Rietveld refinement of synchrotron X-ray powder diffraction data confirms each proposed model. SSZ-53 and SSZ-59 each possess a one-dimensional channel system delimited by 14-membered rings. Results from transmission electron microscopy, electron diffraction, catalytic experiments (spaciousness index and constraint index tests), and argon and hydrocarbon adsorption experiments are consistent with the proposed structures.     

Radiation synthesis of superabsorbent poly(acrylic acid)–carrageenan hydrogels

A series of superabsorbent hydrogels were prepared from carrageenan and partially neutralized acrylic acid by gamma irradiation at room temperature. The gel fraction, swelling kinetics and the equilibrium degree of swelling (EDS) of the hydrogels were studied. It was found that the incorporation of even 1% carrageenan (sodium salt) increases the EDS of the hydrogels from 320 to 800 g/g. Thermal analysis were carried out to determine the amount of free water and bound water in the hydrogels. Under optimum conditions, poly(acrylic acid)–carrageenan hydrogels with high gel fraction (80%) and very high EDS (800 g/g) were prepared gamma radiolytically from aqueous solution containing 15% partially neutralized acrylic acid and 1–5% carrageenan. The hydrogels were also found to be sensitive to the pH and the ionic strength of the medium.     

A new access to polyhydroxy piperidines of the azasugar class: synthesis and glycosidase inhibition studies

A new synthetic strategy has been devised to access a variety of polyhydroxylated piperidines belonging to the azasugar class of glycosidase inhibitors. The key precursor (3aR, 7aR)-5-benzyl-2,2-dimethyl-7-methylenehexahydro[1,3]dioxo[4,5-c]pyridine is obtained by photoinduced electron transfer (PET) cyclization of the corresponding alpha-trimethylsilylmethylamine radical cation to the tethered acetylene functionality. The new molecules have been evaluated for inhibitory properties for certain beta-glycosidases and have been found to be moderate to weak inhibitors of the enzymes under study.