Towards the total synthesis of colletofragarones: constructing the macrocyclic lactone by high pressure-mediated intramolecular Diels-Alder reaction

We report herein an intramolecular Diels-Alder approach towards the construction of the macrocyclic lactone ring and the perhydrobenzofuran system of the colletofragarones, novel metabolites produced by fungi of the genus Colletotrichum that are responsible for inhibition of germination of the conidia in these species. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

Exploring Multi-Component Superconducting Compounds by a High-Pressure Method and Ceramic Combinatorial Chemistry

In this short review, we provide some new insights into the material synthesis and characterization of modern multi-component superconducting oxides. Two different approaches such as the high-pressure, high-temperature method and ceramic combinatorial chemistry will be reported with application to several typical examples. First, we highlight the key role of the extreme conditions in the growth of Fe-based superconductors, where a careful control of the composition-structure relation is vital for understanding the microscopic physics. The availability of high-quality LnFeAsO (Ln = lanthanide) single crystals with substitution of O by F, Sm by Th, Fe by Co, and As by P allowed us to measure intrinsic and anisotropic superconducting properties such as Hc2, Jc. Furthermore, we demonstrate that combinatorial ceramic chemistry is an efficient way to search for new superconducting compounds. A single-sample synthesis concept based on multi-element ceramic mixtures can produce a variety of local products. Such a system needs local probe analyses and separation techniques to identify compounds of interest. We present the results obtained from random mixtures of Ca, Sr, Ba, La, Zr, Pb, Tl, Y, Bi, and Cu oxides reacted at different conditions. By adding Zr but removing Tl, Y, and Bi, the bulk state superconductivity got enhanced up to about 122 K.

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Effects Of High Pressure Homogenization On The Activity, Stability, Kinetics And Three-dimensional Conformation Of A Glucose Oxidase Produced By Aspergillus Niger.

High pressure homogenization (HPH) is a non-thermal method, which has been employed to change the activity and stability of biotechnologically relevant enzymes. This work investigated how HPH affects the structural and functional characteristics of a glucose oxidase (GO) from Aspergillus niger. The enzyme was homogenized at 75 and 150 MPa and the effects were evaluated with respect to the enzyme activity, stability, kinetic parameters and molecular structure. The enzyme showed a pH-dependent response to the HPH treatment, with reduction or maintenance of activity at pH 4.5-6.0 and a remarkable activity increase (30-300%) at pH 6.5 in all tested temperatures (15, 50 and 75°C). The enzyme thermal tolerance was reduced due to HPH treatment and the storage for 24 h at high temperatures (50 and 75°C) also caused a reduction of activity. Interestingly, at lower temperatures (15°C) the activity levels were slightly higher than that observed for native enzyme or at least maintained. These effects of HPH treatment on function and stability of GO were further investigated by spectroscopic methods. Both fluorescence and circular dichroism revealed conformational changes in the molecular structure of the enzyme that might be associated with the distinct functional and stability behavior of GO.

Numerical modeling of ductile crack extension in high pressure pipelines with longitudinal flaws

This study examines the applicability of a micromechanics approach based upon the computational cell methodology incorporating the Gurson-Tvergaard (GT) model and the CTOA criterion to describe ductile crack extension of longitudinal crack-like defects in high pressure pipeline steels. A central focus is to gain additional insight into the effectiveness and limitations of both approaches to describe crack growth response and to predict the burst pressure for the tested cracked pipes. A verification study conducted on burst testing of large-diameter, precracked pipe specimens with varying crack depth to thickness ratio (a/t) shows the potential predictive capability of the cell approach even though both the CT model and the CTOA criterion appear to depend on defect geometry. Overall, the results presented here lend additional support for further developments in the cell methodology as a valid engineering tool for integrity assessments of pipelines with axial defects. (C) 2011 Elsevier Ltd. All rights reserved,

On the mechanism of microbial cell disruption in high-pressure homogenisation

The tensions produced in the wall of a rigid, thin-walled, liquid-filled sphere as it moves with an axisymmetric straining flow are examined. This problem has not been previously addressed. A generalised correlation for the maximum wall tension, expressed in dimensionless form as a Weber number (We), is developed in terms of the acceleration number (Ac) and Reynolds number (Re) of the straining flow. At low Reynolds number We is dominated by viscous forces, while inertial forces due to internal pressure gradients caused by sphere acceleration dominate at higher Re. The generalised correlation has been used to examine the case of a typical yeast cell (a thin-walled, liquid-filled sphere) passing through a typical high-pressure homogeniser (a straining-flow device). At 56 MPa homogenising pressure, a 6 mu m yeast cell experiences tensions in the inertially dominated regime (Re = 100). The correlation gives We = 0.206, corresponding to a maximum wall tension of 8 Nm(-1). This is equivalent to an applied compressive force of 150 mu N and compares favourably with the force required to break yeast cells under compressive micromanipulation (40-90 mu N). Inertial forces may therefore be an important and previously unrecognised. mechanism of microbial cell disruption during high-pressure homogenisation. Further work is required to examine the likelihood of cell deformation in the high-strain-rate short-residence-time environment of the homogeniser, and the effect that such deformation may have on the contribution of inertial forces to disruption. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

A mathematical model for Escherichia coli debris size reduction during high pressure homogenisation based on grinding theory

Experimental data for E. coli debris size reduction during high-pressure homogenisation at 55 MPa are presented. A mathematical model based on grinding theory is developed to describe the data. The model is based on first-order breakage and compensation conditions. It does not require any assumption of a specified distribution for debris size and can be used given information on the initial size distribution of whole cells and the disruption efficiency during homogenisation. The number of homogeniser passes is incorporated into the model and used to describe the size reduction of non-induced stationary and induced E. coil cells during homogenisation. Regressing the results to the model equations gave an excellent fit to experimental data ( > 98.7% of variance explained for both fermentations), confirming the model's potential for predicting size reduction during high-pressure homogenisation. This study provides a means to optimise both homogenisation and disc-stack centrifugation conditions for recombinant product recovery. (C) 1997 Elsevier Science Ltd.

High-pressure phase diagram of the drug mitotane in compressed and/or supercritical CO(2)

This work provides experimental phase diagram of mitotane, a drug used in the chemotherapy treatment of adrenocortical carcinoma, in compressed and/or supercritical CO(2). The synthetic-static method in a high-pressure variable-volume view cell coupled with a transmitted-light intensity probe was used to measure the solid-fluid (SF) equilibrium data. The phase equilibrium experiments were determined in temperature ranging from (298.2 to 333.1) K and pressure up to 22 MPa. Peng-Robinson equation of state (PR-EoS) with classical mixing rule was used to correlate the experimental data. Excellent agreement was found between experimental and calculated values. (C) 2009 Elsevier Ltd. All rights reserved.

Electron beam current loss at the high-vacuum-high-pressure boundary in the environmental scanning electron microscope

A significant loss in electron probe current can occur before the electron beam enters the specimen chamber of an environmental scanning electron microscope (ESEM). This loss results from electron scattering in a gaseous jet formed inside and downstream (above) the pressure-limiting aperture (PLA), which separates the high-pressure and high-vacuum regions of the microscope. The electron beam loss above the PLA has been calculated for three different ESEMs, each with a different PLA geometry: an ElectroScan E3, a Philips XL30 ESEM, and a prototype instrument. The mass thickness of gas above the PLA in each case has been determined by Monte Carlo simulation of the gas density variation in the gas jet. It has been found that the PLA configurations used in the commercial instruments produce considerable loss in the electron probe current that dramatically degrades their performance at high chamber pressure and low accelerating voltage. These detrimental effects are minimized in the prototype instrument, which has an optimized thin-foil PLA design.

The agroindustrial residue valorisation with high pressure CO2 within biorefinery concept

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Development of a "green process" for the isolation of natural functional extracts with anti-cancer activity - Application of high-pressure technology

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Effect of high pressure processing on the microbiology of skin-vacuum packaged sliced meat products: cooked pork ham, dry cured pork ham and marinated beef loin

High hydrostatic pressure is being increasingly investigated in food processing. It causes microbial inactivation and therefore extends the shelf life and enhances the safety of food products. Yeasts, molds, and vegetative cells of bacteria can be inactivated by pressures in the range of 200 to 700 MPa. Microorganisms are more or less sensitive to pressure depending on several factors such as type, strain and the phase or state of the cells. In general, Gram-positive organisms are usually more resistant than Gram-negative. High pressure processing modifies the permeability of the cell membrane, the ion exchange and causes changes in morphology and biochemical reactions, protein denaturations and inhibition of genetic mechanisms. High pressure has been used successfully to extend the shelf life of high-acid foods such as refrigerated fruit juices, jellies and jams. There is now an increasing interest in the use of this technology to extend the shelf life of low-acid foods such as different types of meat products.

Bioequivalence of meat products treated with high pressure processing

The effects of high pressure on the composition of food products have not been evaluated extensively. Since, it is necessary to take in consideration the possible effects in basis to the changes induced in the bio molecules by the application of high pressures. The main effect on protein is the denaturation, because the covalent bonds are not affected; however hydrogen bonding, hydrophobic and intermolecular interactions are modified or destroyed. 1 High pressure can modify the activity of some enzymes. If this is done the proteolysis and lipolysis could be more or less intense and the content of free amino acids and fatty acids will be different. This could be related to the bioavailability of these compounds. Low pressures (100 MPa) have been shown to activate some enzymes (monomeric enzymes). Higher pressures induce loss of the enzyme activity. However some enzymes are very stable (ex. Lipase ~ 600 - 1000 MPa). Lipoxygenase is less stable, and there is little information about the effects on antioxidant enzymes. Other important issue is the influence of high pressure on oxidation susceptibility. This could modify the composition of lipids if the degree of the oxidation would have been higher or lower than in the traditional product. Pressure produces the damage of cell membranes favouring the contact between substrates and enzymes, exposure to oxidation of membrane fatty acids and loos of the efficiency of vitamin E. These effects can also affect to protein oxidation. In this study different compounds were analysed to establish the differences between non-treated and high-pressure treated products.