Catalytic effects during cellulose liquefaction

Cellulose can be totally liquefied by heating to 350 °C in the presence of an aqueous phenolic solvent containing a catalyst. The main products are light aromatic hydrocarbons, benzofurans, heavier aromatic hydrocarbons such as substituted indanes and tetralin, and xanthenes. The variation of product distribution with catalyst was examined and it was found that in aqueous phenol, xanthene formation was enhanced by acidity. By substituting guaiacol for phenol, it was determined that most benzofuran formation involved the phenol solvent molecules, although a small proportion did not. This benzofuran may have arises from phenol generated from cellulose, the incorporation of phenol in the products being enhanced through a cage effect.     

Magnesium alkyl reduced titanium (IV) chloride based polymerization catalysts: materials rich in magnesium chloride

Reduction of TiCl₄ with organomagnesiums either in the presence of preformed MgCl₂, or concurrently with the formation of MgCl₂ from chlorocarbons, yields materials which are active catalysts for the polymerization of propene and ethene. Transformation of these materials to a violet allotrope by heating with TiCl₄ gives materials much more active for propene polymerization, albeit stereoregulation is still not good. interestingly, these transformed materials show little advantage for ethene polymerization except at high temperatures. Use of a Lewis base does not give high stereoregulation with propene; although some advantage is gained activity is greatly diminished by this.     

Location of Aluminum in Substituted Calcium Silicate Hydrate (C-S-H) Gels as Determined by 29Si and 27Al NMR and EELS

Solid-state ²⁷Al and ²⁹Si magic angle spinning NMR spectroscopy has been combined with electron energy loss spectroscopy carried out in the transmission electron microscope to determine the location of Al substituting in a semicrystalline C-S-H gel present in a hydrated synthetic slag glass. The gel is found to contain mainly pentameric silicate chains in which the central silicon is substituted by aluminum.     

The Instabilisation of Dye-Fibre Bonds by Peroxide Treatments

The results are presented of an investigation into the instability induced in dye-fibre bonds by peroxide treatments. The nature of the reactions involved are discussed.     

Presence of long-chain dialkyl ethers in cuticular wax of the Australian chrysomelid beetleMonolepta australis

Investigation of the lipid extract of the Australian chrysomelid beetle,Monolepta australis, has revealed a novel homologous series of long-chain, unsaturated-saturated dialkyl ethers in the cuticular wax. Gas chromatography-mass spectrometry, proton magnetic resonance, infrared spectroscopy, and chemical degradation have shown that ethers of formula CH₃(CH₂)₉CH=CH(CH₂)₆O(CH₂)_12–16CH₃ predominate.     

A comparison of the electro-osmotic properties of charged polymer membranes and those predicted from binary electrolyte solution models Part I. Univalent forms of sulphonate membranes and chloride electrolyte models

By changing from the usual solvent-fixed frame of reference for flows to one based upon a fixed anion, electro-osmotic transference numbers are defined for any electrolyte, for which transport numbers are known. For sulphonate membranes, chloride electrolyte analogues were chosen. Agreement between observed transference numbers and those of the model electrolytes are shown to be excellent for both polystyrene based and perfluoro-sulphonic acid membranes.From irreversible thermodynamics it is shown that the transference number for any membrane will have a maximum value equal to the molar ratio of water to fixed charge in the membrane and independent of ionic form. The observed value is in addition, proportional to the fraction of the total water friction, which is due to water interaction with counterion. It is the latter which is estimated successfully from model electrolytes. The ionic forms used were Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and H⁺ at 25°C in membranes in which electrolyte exclusion was almost complete.     

Synthesis of trideuteratedO-alkyl platelet activating factor and lyso derivatives

Racemic heavy isotope analogs of 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) and 1-O-alkyl-2-O-acetyl-sn-glycero-3-phosphocholine (PAF) were prepared for use as internal standards to facilitate quantitative studies based on mass spectrometry. Starting from pentadencane-1,15-diol andrac-glycerol-1,2-acetonide, a convergent synthesis of 1-O-[16′-²H₃]hexadecyl and 1-O-[18′-²H₃]octadecylrac-glycero-3-phosphocholine and their acetyl derivatives is described. Three deuterium atoms were introduced at the terminal position of the 1-O-alkyl group by displacement of thep-toluensulfonyl group from 1-O-alkyl-15′-p-toluensulfonate and 1-O-alkyl-17′-p-toluensulfonate with [²H₃]-methylmagnesium iodide. The 1-O-alkyl-17′-p-toluensulfonate was obtained by reaction of the 1-O-alkyl-15′-p-toluensulfonate with allylmagnesium bromide, followed by reductive ozonolysis and treatment withp-toluenesulfonyl chloride. The hydroxyl group at C-2 was protected by a benzyl group and removed at a late stage in the synthesis. This provided the corresponding lysoderivatives or allowed preparation of racemic PAF by subsequent acetylation of the free hydroxy group. The phosphocholine moiety was introduced at glycerol C-3 by reaction with bromoethyldichlorophosphate and trimethylamine. The synthetic compounds were analyzed by FAB/MS and GC/NICIMS. They were shown to contain less than 0.6% protium impurity.     

Mechanisms of Enhanced Catalysis in Enzyme–DNA Nanostructures Revealed through Molecular Simulations and Experimental Analysis

Understanding and controlling the molecular interactions between enzyme substrates and DNA nanostructures has important implications in the advancement of enzyme–DNA technologies as solutions in biocatalysis. Such hybrid nanostructures can be used to create enzyme systems with enhanced catalysis by controlling the local chemical and physical environments and the spatial organization of enzymes. Here we have used molecular simulations with corresponding experiments to describe a mechanism of enhanced catalysis due to locally increased substrate concentrations. With a series of DNA nanostructures conjugated to horseradish peroxidase, we show that binding interactions between substrates and the DNA structures can increase local substrate concentrations. Increased local substrate concentrations in HRP(DNA) nanostructures resulted in 2.9‐ and 2.4‐fold decreases in the apparent Michaelis constants of tetramethylbenzidine and 4‐aminophenol, substrates of HRP with tunable binding interactions to DNA nanostructures with dissociation constants in the micromolar range. Molecular simulations and kinetic analysis also revealed that increased local substrate concentrations enhanced the rates of substrate association. Identification of the mechanism of increased local concentration of substrates in close proximity to enzymes and their active sites adds to our understanding of nanostructured biocatalysis from which we can develop guidelines for enhancing catalysis in rationally designed systems.     

BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for High‐Temperature Capacitor Applications

Solid solutions of (1?x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (0 ≤ x ≤ 0.6) were prepared via a standard mixed‐oxide solid‐state sintering route and investigated for potential use in high‐temperature capacitor applications. Samples with 0.4 ≤ x ≤ 0.6 showed a temperature independent plateau in permittivity (ε_r). Optimum properties were obtained for x = 0.5 which exhibited a broad and stable relative ε_r ~940 ± 15% from ~25°C to 550°C with a loss tangent <0.025 from 74°C to 455°C. The resistivity of samples increased with increasing Bi(Mg_2/3Nb_1/3)O₃ concentration. The activation energies of the bulk were observed to increase from 1.18 to 2.25 eV with an increase in x from 0 to 0.6. These ceramics exhibited excellent temperature stable dielectric properties and are promising candidates for high‐temperature multilayer ceramic capacitors for automotive applications.     

The Role of α1-Adrenoceptor Antagonists in the Treatment of Prostate and Other Cancers

This review evaluates the role of α-adrenoceptor antagonists as a potential treatment of prostate cancer (PCa). Cochrane, Google Scholar and Pubmed were accessed to retrieve sixty-two articles for analysis. In vitro studies demonstrate that doxazosin, prazosin and terazosin (quinazoline α-antagonists) induce apoptosis, decrease cell growth, and proliferation in PC-3, LNCaP and DU-145 cell lines. Similarly, the piperazine based naftopidil induced cell cycle arrest and death in LNCaP-E9 cell lines. In contrast, sulphonamide based tamsulosin did not exhibit these effects. In vivo data was consistent with in vitro findings as the quinazoline based α-antagonists prevented angiogenesis and decreased tumour mass in mice models of PCa. Mechanistically the cytotoxic and antitumor effects of the α-antagonists appear largely independent of α 1-blockade. The proposed targets include: VEGF, EGFR, HER2/Neu, caspase 8/3, topoisomerase 1 and other mitochondrial apoptotic inducing factors. These cytotoxic effects could not be evaluated in human studies as prospective trial data is lacking. However, retrospective studies show a decreased incidence of PCa in males exposed to α-antagonists. As human data evaluating the use of α-antagonists as treatments are lacking; well designed, prospective clinical trials are needed to conclusively demonstrate the anticancer properties of quinazoline based α-antagonists in PCa and other cancers.