Structural characterization of vanchrobactin, a new catechol siderophore produced by the fish pathogen Vibrio anguillarum serotype O2

Vanchrobactin, a new catecol-type siderophore produced by cells of the fish pathogen Vibrio anguillarum serotype O2, has been isolated from the supernatants of iron-deficient cultures. Its structure was characterized from spectral data and established as N-[N′-(2,3-dihydroxybenzoyl)-arginyl]-serine.     

Kiliani reactions on ketoses: branched carbohydrate building blocks from D-tagatose and D-psicose

D-Tagatose and D-psicose on treatment with sodium cyanide gave mixtures of branched sugar lactones; extraction of the crude products by acetone in the presence of acid permits direct access to branched carbohydrate diacetonides, likely to be of value as new chirons. In both cases, the major lactone products—diacetonides with a 2,3-cis-diol relationship—can be crystallised in around 40-50% yield from the ketohexose. A practical procedure for the conversion of 30 g of D-tagatose to give 24 g of 2,3:5,6-di-O-isopropylidene-2-C-hydroxymethyl-D-talono-1,4-lactone is reported.     

Analytical and multivariate study of roman age architectural terracotta from northeast of Spain

Roman culture employed architectural terracotta made from baked clay as original material to manufacture ceramic pieces. It was often used as a basis for construction of functional and/or decorative elements in roofs, such as plane and curve tiles as well as antefixes with their corresponding “imbrexes”. Some of them are conserved nowadays. They were collected in Roman quarries discovered in old cities and villages sited in the Hispania Citerior (northeast of Spain in Roman age). A study of the origin and manufacturing process (moulding, baking, touching up and painting) of these terracotta pieces has been made on the basis of the data obtained from a physicochemical characterization of samples. The used techniques were mainly flame absorption and emission spectrometry for the elemental analysis (major and minor elements), dilatometry for the study of thermal behaviour, scanning electron microscopy (SEM) for observation of thin layers and X-ray diffraction spectrometry (XRD) for mineralogical composition. In addition, a supervised pattern recognition programme was applied to the results for a selected group of 85 samples and five variables (chromium, copper, lead, nickel and zinc contents). Dilatometry and SEM results showed baking temperatures of these materials below 900 °C and the existence of zones with very different porosity in the same ceramic piece. Results obtained from multielemental analysis and multivariate statistical study by linear discriminant analysis lead us to the following conclusions: (i) the high content of lead found in a large number of antefixes demonstrates the use of lead oxide as an additive in the lime grout treatment, (ii) different contents of Cu, Zn, Cr, and Ni were indicative of the use of varied clay types in the manufacture process (even in the same production centre) as well as of the existence of a pigmentation process, although this last affirmation is not corroborated by the presence of remains of evident painting in the ceramic pieces, (iii) samples can be classified according to the places where these pieces came from and (iv) more variety in their composition was found in Roman age terracotta production centres.     

An operational supramolecular nanovalve

A functioning nanomachine in the form of a supramolecular nanovalve that opens and closes the orifices to molecular-sized pores and releases a small number of molecules on demand is reported. The nanovalve, which is used to open and close the nanocontainer, is a pseudorotaxane composed of two components-a long thread containing a 1,5-dioxnaphthalene donor unit, which is attached to the solid support, and the moving part, the tetracationic cyclophane acceptor/receptor, cyclobis(paraquat-p-phenylene), which controls access to the interior of the nanopore. The nanocontainer is made out of mesoporous silica by using a dip-coating method. Operating the nanovalve involves three steps: (i) filling the container, (ii) closing the valve, and (iii) opening the valve to release the contents of the container on demand. The tubular pores, which are approximately 2 nm wide, are filled with stable luminescent Ir(ppy)3 molecules by allowing them to diffuse into the open pores. The orifices are then closed by pseudorotaxane formation. An external reducing reagent (NaCNBH3) is used to effect dethreading of the pseudorotaxane so as to unlock the tubes and allow the guest molecules to be released. This nanovalve is a supramolecular machine consisting of a solid framework with moving parts capable of doing useful work.     

Highly porous solid-phase microextraction fiber coating based on poly(ethylene glycol)-modified ormosils synthesized by sol-gel technology

The preparation and characteristics of solid-phase microextraction (SPME) fibers coated with Carbowax 20M ormosil (organically modified silica) are described here. Raw fused silica fibers were coated with Carbowax 20M-modified silica using sol-gel process. Scanning electron micrographs of fibers revealed a highly porous, sponge-like coating with an average thickness of (8 +/- 1) microm. The sol-gel Carbowax fibers were compared to commercial fibers coated with 100 microm polydimethylsiloxane (PDMS) and 65 microm Carbowax-divinylbenzene (DVB). Shorter equilibrium times were possible with the sol-gel Carbowax fiber: for headspace extraction of the test analytes, they ranged from less than 3 min for benzene to 15 min for o-xylene. Extraction efficiencies of the sol-gel Carbowax fiber were superior to those of conventional fibers: for o-xylene, the extracted masses were 230 and 540% of that obtained with 100 microm PDMS and 65 microm Carbowax-DVB fibers, respectively.     

Synthesis and kinetic investigation of the selective acidolysis of para-substituted N-benzyl- or N-phenyl-N-phenylacetyl-α,α-dialkylglycine cyclohexylamides

Several derivatives of N-phenylacetyl-N-benzyl-α,α-dimethylglycine cyclohexylamide and their α,α-dibenzylglycine analogues were synthesised by a Ugi-Passerini reaction. In addition, a few analogues of the former but having an N-phenyl instead of a benzyl group at the nitrogen atom were synthesised. The compounds in each of these three sets differed from each other at position 4 of the N-benzyl (and N-phenyl) group. These adducts were submitted to acidolysis with TFA to obtain the corresponding free acids, the reactions being monitored by HPLC and data collected for kinetic purposes. The kinetic data were submitted to Hammett uni- and biparametric relationships and the results were analysed in terms of structure-reactivity in connection with the sensitivity of the reaction rates to the electronic contributions of the various substituents at position 4 of the aromatic rings. The results allowed comparison with information obtained in previous investigations and rationalise the contribution of the substituent at the nitrogen atom to the lability of the C-terminal amide bond.     

On the mechanism of arene-catalyzed lithiation: the role of arene dianions--naphthalene radical anion versus naphthalene dianion

The use of lithium and a catalytic amount of an arene is a well-established methodology for the preparation of organolithium reagents that manifest greater reactivity than the classical lithium-arene solutions. In order to rationalize this conduct, the participation of a highly reduced species, the dianion, is proposed and its reactivity explored. Studies of kinetics and of distribution of products reveal that the electron-transfer (ET) reactivity profile of dilithium naphthalenide in its reaction with organic chlorides excludes alternative mechanisms of halogen-lithium exchange. The process generates organolithium compounds. The dianion thus emerges along with the radical anion as a suitable candidate for catalytic cycles in certain processes. Endowed with a higher redox potential than its radical anion counterpart, dilithium naphthalene displays a broader spectrum of reactivity and so increases the range of substrates suitable for lithiation. The reaction of dilithium naphthalene with THF is one example of the divergent reactivity of the radical anion and the dianion, which has been the source of apparent misinterpretation of results in the past and has now been appropriately addressed.     

Drude-type conductivity of charged sphere colloidal crystals: density and temperature dependence

We report on extensive measurements in the low-frequency limit of the ac conductivity of colloidal fluids and crystals formed from charged colloidal spheres suspended in de-ionized water. Temperature was varied in a range of 5 degrees C < Theta < 35 degrees C and the particle number density n between 0.2 and 25 microm(-3) for the larger, respectively, 2.75 and 210 microm(-3) for the smaller of two investigated species. At fixed Theta the conductivity increased linearly with increasing n without any significant change at the fluid-solid phase boundary. At fixed n it increased with increasing Theta and the increase was more pronounced for larger n. Lacking a rigorous electrohydrodynamic treatment for counterion-dominated systems we describe our data with a simple model relating to Drude's theory of metal conductivity. The key parameter is an effectively transported particle charge or valence Z(*). All temperature dependencies other than that of Z(*) were taken from literature. Within experimental resolution Z(*) was found to be independent of n irrespective of the suspension structure. Interestingly, Z(*) decreases with temperature in near quantitative agreement with numerical calculations.     

Novel carbonyl bromoallylation/Heck reaction sequence. Stereocontrolled access to bicyclic beta-lactams

[reaction: see text] The reaction of 2,3-dibromopropene with racemic as well as enantiopure 4-oxoazetidine-2-carbaldehydes 1 in aqueous media was promoted by tin in the presence of several additives to afford the corresponding bromohomoallyl alcohols 2 in high diastereoselectivities. However, indium or zinc were unable to promote the bromoallylation reaction of aldehydes 1 under similar Barbier-type conditions. Vinyl bromides 2 bearing an extra alkene tether were used for the preparation of differently sized, fused bicyclic beta-lactams of nonconventional structure via Heck cyclization.     

Primary alkyl fluorides as regioselective alkylating reagents of lithium arene dianions. Easy prediction of regioselectivity by MO calculations on the dianion

Lithium arene dianions derived of polycyclic aromatic hydrocarbons, such as naphthalene, anthracene, phenanthrene, fluoranthene, pyrene, chrysene and binaphtyl react cleanly with n-alkylfluorides to afford regiochemically controlled alkylated dihydroarenes after hydrolysis. These arene dianions can be easily prepared by simple treatment of the arene with lithium in THP. Unlike simple radical coupling, the alkylation of these species with alkyl fluorides apparently goes through a S_N2 transition state, despite the inertness of alkyl fluorides to undergo nucleophilic substitution. It is also atypical for reduced arenes, which tend to give ET reactions with other alkyl halides. Prediction of the regiochemistry was easily conducted by means of MO calculations (PM3) on the dianion, and in all cases were consistent with the experimental.