Total synthesis of marinomycins A-C and of their monomeric counterparts monomarinomycin A and iso-monomarinomycin A

Marinomycins A-C (1-3), and their monomeric analogues monomarinomycin A (m-1) and iso-monomarinomycin A (m-2), were synthesized by a convergent strategy from key building blocks ketophosphonate 5, aldehyde 6, and dienyl bromide carboxylic acid 7. The first attempt to construct marinomycin A [1, convertible to marinomycins B (2) and C (3) by light] by direct Suzuki-type dimerization/cyclization of boronic acid dienyl bromide 4 led to premature ring closure to afford, after global desilylation, monomarinomycin A (m-1) and iso-monomarinomycin A (m-2) in good yield and only small amounts (< or =2%) of the desired product. A subsequent stepwise approach based on Suzuki-type couplings improved considerably the overall yield of marinomycin A (1), and hence of marinomycins B (2) and C (3). Alternative direct dimerization approaches based on the Stille and Heck coupling reactions also led to monomarinomycins A (m-1 and m-2), but failed to deliver useful amounts of marinomycin A (1).     

If You Don't Have a Good Laboratory,Find a Good Volcano: Mount Vesuvius as a Natural Chemical Laboratory in Eighteenth-Century Italy

This essay that examines the role of the volcano as a chemical site in the late eighteenth century, as the “new chemistry” spread throughout the southern Italian Kingdom of Naples, resulting in lively debates. In Naples itself, these scientific debates were not confined to academies, courts, and urban spaces. In the absence of well-equipped chemical laboratories, Neapolitan scholars also carried out research on chemistry on the slopes of Mount Vesuvius, a natural site that furnished them with all the tools and substances necessary for practising chemistry. By examining various Neapolitan publications on Vesuvius and the chemical reactions and products associated with its periodic eruptions, I argue that the volcano's presence contributed to a distinctive, local approach to chemical theory and practice. Several case studies examine the ways in which proximity to Vesuvius was exploited by Neapolitan scholars as they engaged with the new chemistry, including Giuseppe Vairo, Michele Ferrara, Francesco Semmola, and Emanuele Scotti.     

Preparation of enzyme multilayers on colloids for biocatalysis

The construction of enzyme multilayer films on colloidal particles for biocatalysis is described. The enzyme multilayers were assembled on submicrometer‐sized polystyrene spheres via the alternate adsorption of poly(ethyleneimine) and glucose oxidase using a layer‐by‐layer approach. Microelectrophoresis and single particle light scattering measurements revealed regular and step‐wise assembly of the multilayers on the colloids. The high surface area bio‐multilayer coated particles formed were subsequently utilized in enzymatic catalysis.     

Determination of Non-Ionic Surfactants of the Alcohol Polyethoxylate Type by Means of High Temperature Gas Chromatography and Atomic Emission Detection

High temperature gas chromatography (HT-GC) coupled to atomic emission detection (AED) has been applied for the determination of alkyl chain distribution, mole average degree of ethoxylation and weight percent distribution of the corresponding homologues of alcohol ethoxylates without all the actual homologues being available as pure references. Based upon its constant elemental response, the HT-GC-AED system has been evaluated for its applicability to compound independent calibration within the homologous series of the alcohols and alcohol ethoxylates. Discrimination against high molecular weight components by gas chromatography requires conversion to the acetyl or trimethylsilyl derivatives. The latter includes introduction of the hetero atom silicon and thus allows monitoring of the silicon trace. Thus selectivity will be enhanced by excluding detection of compounds which do not react with the derivatization reagent. The method has been validated with the analysis of the technical product Brij 30, consisting of a mixture of alcohol ethoxylates with a vendor-specified mole average degree of ethoxylation of four. The experimental result yields a mole average degree of 4.0 ± 0.1 in the carbon, silicon and oxygen traces.