Aqueous two‐phase systems for the recovery of a recombinant viral coat protein from Escherichia coli

In this study the use of an aqueous two‐phase system (ATPS) following the direct chemical extraction of a recombinant viral coat protein, from the cytoplasm of Escherichia coli, is evaluated. The driving force is the need to establish an economically‐viable process for the manufacture of a vaccine against human papilloma infection. The partition behaviour of recombinant L1 protein, the major structural protein of the virus, and DNA was investigated in a polyethylene glycol (PEG)–phosphate system. An evaluation of system parameters including PEG molecular mass and the concentrations of PEG and phosphate was conducted, to estimate conditions under which the L1 protein and DNA partition to opposite phases. ATPS extraction comprising a volume ratio of 1.00, PEG 1000 (18.0%(w/w)) and phosphate (15.0%(w/w)) provided the conditions for accumulation of DNA into the bottom phase and concentration of L1 protein into the opposite phase (ie partition coefficient of DNA; ln K_DNA < 0.0 and partition coefficient of L1; ln K_L1 > 2.5). The findings reported here demonstrate the potential of ATPS to recover recombinant protein released from E coli by direct chemical extraction. © 2002 Society of Chemical Industry     

Silphinene Sesquiterpenes as Model Insect Antifeedants

Silphinene sesquiterpenes are established chrysomelid antifeedants. In this work, nine silphinene analogs, 11-acetoxy-5-angeloyloxysilphinen-3-one (1), 11-acetoxy-5-tigloyloxysilphinen-3-one (2), 11-acetoxy-5-iso- butyryloxysilphinen-3-one (3), 11-hydroxy-5-angeloyloxysilphinen-3-one (4), 11,5-dihydroxysilphinen-3-one (5), 11,5-diacetoxysilphinen-3-one (6), 5,11-diisobutyryloxysilphinen-3-one (7), silphinen-3,5,11-trione (8), and O-methyl-5-epicantabrenolic acid methyl ester (10), and a presilphiperfolane sesquiterpene (9) were tested against several divergent insect species, including the lepidopteran Spodoptera littoralis, the chrysomelid Leptinotarsa decemlineata, and five aphid species, and their antifeedant effects were compared with those of picrotoxinin, a GABA-antagonist, and thymol, an allosteric modulator for insect GABA receptors. All insects tested responded to at least one silphinene analog and/or GABA antagonist. Compound 3 and thymol were effective antifeedants against all species tested except S. littoralis, with varying potencies according to their feeding ecologies. The toxicity of these compounds was species-dependent and did not correlate with their antifeedant effect.     

Kinetics of Solid-State Reactions in Heterogeneous Catalysis from Time-Resolved X-Ray Absorption Spectroscopy

The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies.     

Screening of Soluble Rhodium Nanoparticles as Precursor for Highly Active Hydrogenation Catalysts: The Effect of the Stabilizing Agents

We report the preparation of rhodium nanoparticles (NPs) stabilized by 1-octadecanethiol (ODT), polyvinyl alcohol (PVA), and tetraoctylammonium bromide (TOAB), and their application for hydrogenation catalysis. The three metal–ligand systems correspond to different mechanism of NPs stabilization via strong covalent linkage, chemisorbed atoms and electrostatic interactions, respectively. We found a strong effect of the interaction between the stabilizer and the surface of the metal nanoparticle on the catalytic activity. The Rh NPs were studied as soluble nanoparticle catalysts and as precursors for the synthesis of supported catalysts. All catalysts were tested in the hydrogenation of cyclohexene under similar conditions as a model reaction. Generally, Rh–ODT NPs were inactive, Rh–PVA NPs exhibited distinct activities in solution (aqueous biphasic catalysis) and as a supported catalyst, and Rh–TOAB NPs exhibited similar activities in solution and after immobilization. This last result opens the opportunity for the preparation of highly active Rh NP catalysts both in solution and as a heterogeneous catalyst. Additionally, the stability of the nanoparticles depends on the choice of ligand and on the functionalization of the support surface before immobilization. By optimizing the catalyst synthesis and reaction conditions, turnover frequencies as high as 700,000 h^?1 where observed for stable and recyclable catalyst.     

Surface Property Modification of Epoxy Coatings by Polydimethylsiloxanes

Surface properties of epoxy coatings are modified by PDMS additives in cationic UV curing of a cycloaliphatic epoxy resin. The cured films show a very high hydrophobicity that does not depend on PDMS concentration, indicating that a threshold is reached even at 0.3 wt% additive. A slight increase of the water contact angle as a function of PDMS molecular weight is observed. The additive selectively modified the air‐side of the film, while the glass‐side retains the surface properties of the pure resin. This segregation phenomenon permits to obtain highly hydrophobic films with still good adhesion properties on polar substrates, which is an important advantage over common surface‐modified resins.

     

Light olefins dimerization to high quality gasoline components

New attractive technologies can be designed in the field of light olefins dimerization (C₃–C₅) in order to obtain products useful as gasoline blending components; the technologies are characterized both by low investment costs and by high product quality. Isobutene dimerization is a powerful alternative to MTBE production whenever the use of the latter will be forbidden in gasoline. Also the dimerization of iso-amylenes and propylene, when properly designed, can give products (both the olefins and the corresponding hydrogenated derivatives) characterized by very high octane numbers. More in general all these technologies can help to debottleneck the FCC downstream when enhanced olefins production is achieved by means of new FCC catalysts and processes.     

Sol–Gel Processing and Characterization of Pure and Metal-Doped SnO2 Thin Films

A chloride-based inorganic sol–gel route was used for preparing pure and metal (osmium, nickel, palladium, platinum)-doped SnO₂ sol. SnCl₄ was first reacted with propanol, then the resulting compound was hydrolyzed and subsequently mixed with solutions of the metal dopants. The obtained sols were used for depositing thin films by spin coating or for preparing powders by solvent evaporation at 110°C. FTIR spectroscopy and thermal analysis of the powders revealed that chlorine still bound to tin stabilized the sol against gelation by hindering the condensation reactions. Film characterizations showed that platinum and palladium, unlike nickel and osmium, were likely to form nanoparticles in the SnO₂ lattice. This result was discussed with regard to the different ways that platinum and palladium, on one hand, and nickel and osmium, on the other, modified the growth of SnO₂ grains and the film roughness and morphology. Dopants that formed nanoparticles (platinum, palladium) resulted in the roughest film, while dopants that did not form particles (nickel, osmium) resulted in SnO₂ grain size very close to that of pure SnO₂.     

Development of semitransparent wood‐polymer composites

A new material has been developed consisting of pieces of wood embedded within a matrix of acrylic polymer, resulting in a transparent or semitransparent wood‐based product. This material presents quite appealing aesthetic features, thereby opening new possibilities for decorative applications. Because acrylic and methacrylic monomers are in the liquid state at room temperature, it is possible to introduce wood (in the current case, walnut wood) into a mixture of acrylic (hydroxypropyl acrylate) and/or methacrylic monomers (methyl methacrylate and 2‐hydroxyethyl methacrylate) along with a plasticizer (dioctyl phthalate) in the presence of a chemical initiator (benzoyl peroxide). A transparent polymeric matrix with dispersed wood is then obtained through bulk free‐radical polymerization. Introducing this reaction mixture along with pieces of wood into a mold results in a wood‐polymer composite. A 2^4?1 experimental fractional factorial design was implemented to study the importance of the composition of these materials on several relevant properties. The sheets produced were characterized by tensile testing, dynamic mechanical thermal analysis, thermal gravimetric analysis, and heat deflection temperature. The models obtained for predicting each property pointed to valuable insights regarding the influential constituents. In particular, our results suggested that monomers to be used in future applications of this material should be selected in terms of their cost and the desired flexibility for the final product, not in terms of their polarity. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Microgel/SiO2 hybrid colloids prepared using a water soluble silica precursor

In the present work we demonstrate that functional polymer microgels may act as smart self-catalyzing system inducing controlled formation of silica nanoparticles inside the polymer network and formation of hybrid colloids. We synthesized a water soluble silica precursor PEG-PEOS via post-modification of hyperbranched poly(ethoxysiloxane) (PEOS) with poly(ethylene glycol) monomethyl ether. We used poly(N-vinylcaprolactam)-based microgel functionalized with imidazole and β-diketone groups as a matrix for biomimetic deposition of silica. Composite microgel particles containing silica nanoparticles (up to 20 wt.-%) have been prepared by simultaneous PEG-PEOS conversion and silica deposition in the microgels. TEM studies indicate the infiltration of silica nanoparticles (～10 nm) inside the corona region of the microgels due to the strong acid–base interaction between the acidic silica and basic imidazole groups. The resulting composite particles were found to be colloidally stable and no aggregation was observed even after months of storage. The incorporation of silica nanoparticles increased the rigidity of the microgel particles and reduced their thermal sensitivity.     

Submicron laser-textured vents for self-cleaning injection molds

Clogging of venting slots in injection molds is a common maintenance problem caused by the degradation and the accumulation of gaseous and volatiles by-products of polymer melting. In this work, the effect of laser-induced periodic surface structures on the self-cleaning properties of venting slots is investigated. The degradation of poly(ethylene terephthalate) (PET) over different surfaces is characterized by reproducing the mechanisms that occurs in mold cavities when the air is pushed through the venting channel. An imaging technique is developed for the quantification of the sediment that deposits on sample surfaces due to condensation of by-products of PET melting. The experimental results indicate that the use of a multiscale texture minimizes the deposition of residues on the vent surface reducing it from 17.2 to 3.1%. A linear dependency between contact angle and clogging ratio indicates the efficacy of the model that explains vent self-cleaning properties considering their wetting properties.