Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride.

Investigation and optimization of parameters affecting the multiply charged ion yield in AP-MALDI MS

Liquid matrix-assisted laser desorption/ionization (MALDI) allows the generation of predominantly multiply charged ions in atmospheric pressure (AP) MALDI ion sources for mass spectrometry (MS) analysis. The charge state distribution of the generated ions and the efficiency of the ion source in generating such ions crucially depend on the desolvation regime of the MALDI plume after desorption in the AP-tovacuum inlet. Both high temperature and a flow regime with increased residence time of the desorbed plume in the desolvation region promote the generation of multiply charged ions. Without such measures the application of an electric ion extraction field significantly increases the ion signal intensity of singly charged species while the detection of multiply charged species is less dependent on the extraction field. In general, optimization of high temperature application facilitates the predominant formation and detection of multiply charged compared to singly charged ion species. In this study an experimental setup and optimization strategy is described for liquid AP-MALDI MS which improves the ionization effi- ciency of selected ion species up to 14 times. In combination with ion mobility separation, the method allows the detection of multiply charged peptide and protein ions for analyte solution concentrations as low as 2 fmol/lL (0.5 lL, i.e. 1 fmol, deposited on the target) with very low sample consumption in the low nL-range.

Comparison of properties of native and extruded amaranth (Amaranthus cruentus L. - BRS Alegria) flour

The aim of this study was to compare some of the properties of native and extruded amaranth flour obtained under mild and severe extrusion conditions. The chemical composition of the flours was similar. Flours obtained by both extrusion processes presented high solubility in water, low values of L* (luminosity) and an absence of endothermic peak on the DSC method. Water absorption, retrogradation tendency, final viscosity and the viscous behavior by rheology analysis were also studied. The results indicate that extruded flours have a good potential as an ingredient for food exposed to heat treatment at a high temperature and mechanical shear, for use in instant meal products. On the other hand, original flour properties are comparable to those of amaranth starch, which exhibits similarly high quality paste stability, low solubility in water, and elastic behavior, and could be used as a substitute for raw flour in a range of food formulas. (C) 2011 Elsevier Ltd. All rights reserved.

Relationship between the somatic cell count in raw milk and the casein fractions of UHT milk

The relationship between somatic cell count (SCC) in raw milk and casein fractions of 15 batches of the corresponding ultra-high-temperature (UHT) milk was examined. Raw milk was collected, pasteurised and submitted to UHT treatment. Samples of the UHT milk were taken on days 8, 30, 60, 90 and 120 of storage at room temperature and their casein fractions analysed by high performance liquid chromatography. SCC ranged from 197,000 to 800,000 cells/mL. No correlation (p>0.05) was found between SCC and K-casein concentrations in raw or UHT milks. The alpha(s2) and P-casein concentrations in raw milk were negatively correlated with SCC (p<0.05). In UHT milk, negative correlations were observed for a,1-casein (p<0.05) and beta-casein (p<0.05) on the 8th day, and for alpha S-2-casein (p<0.01) on the 60th day of storage. Results indicate that higher SSC in raw milk is associated with substantial degradation of beta-casein and alpha(s)-casein, which may lead to quality defects in UHT milk during storage. Aust. J. Dairy Technol. 63, 45-49

Response surface analysis of extract yield and flavour intensity of Brazilian cherry (Eugenia uniflora L.) obtained by supercritical carbon dioxide extraction

This work evaluated the effect of pressure and temperature on yield and characteristic flavour intensity of Brazilian cherry (Eugenia uniflora L) extracts obtained by supercritical CO(2) using response surface analysis, which is a simple and efficient method for first inquiries. A complete central composite 2(2) factorial experimental design was applied using temperature (ranging from 40 to 60 degrees C) and pressure (from 150 to 250 bar) as independent variables. A second order model proved to be predictive (p <= 0.05) for the extract yield as affected by pressure and temperature, with better results being achieved at the central point (200 bar and 50 degrees C). For the flavour intensity, a first order model proved to be predictive (p <= 0.05) showing the influence of temperature. Greater characteristic flavour intensity in extracts was obtained for relatively high temperature (> 50 degrees C), Therefore, as far as Brazilian cherry is concerned, optimum conditions for achieving higher extract yield do not necessarily coincide to those for obtaining richer flavour intensity. Industrial relevance: Supercritical fluid extraction (SFE) is an emerging clean technology through which one may obtain extracts free from organic solvents. Extract yields from natural products for applications in food, pharmaceutical and cosmetic industries have been widely disseminated in the literature. Accordingly, two lines of research have industrial relevance, namely, (i) operational optimization studies for high SFE yields and (ii) investigation on important properties extracts are expected to present (so as to define their prospective industrial application). Specifically, this work studied the optimization of SFE process to obtain extracts from a tropical fruit showing high intensity of its characteristic flavour, aiming at promoting its application in natural aroma enrichment of processed foods. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of somatic cell counts on lipolysis, proteolysis and apparent viscosity of UHT milk during storage

In this work, lipolysis, proteolysis and viscosity of ultra-high temperature (UHT) milk containing different somatic cell counts (SCC) were investigated. UHT milks were analysed on days 8, 30, 60, 90 and 120 of storage. Lipolysis as measured by free fatty acids increase, casein degradation and viscosity of UHT milk were not affected by SCC but increased during storage. A negative relationship was observed between SCC and casein as a percentage of true protein on the 120th day of storage, hence indicating that high SCC increases the proteolysis of UHT milk by the end of its shelf life.

Impacts of climate changes on crop physiology and food quality

Carbon emissions related to human activities have been significantly contributing to the elevation of atmospheric [CO(2)] and temperature. More recently, carbon emissions have greatly accelerated, thus much stronger effects on crops are expected. Here, we revise literature data concerning the physiological effects of CO(2) enrichment and temperature rise on crop species. We discuss the main advantages and limitations of the most used CO(2)-enrichment technologies, the Open-Top Chambers (OTCs) and the Free-Air Carbon Enrichment (FACE). Within the conditions expected for the next few years, the physiological responses of crops suggest that they will grow faster, with slight changes in development, such as flowering and fruiting, depending on the species. There is growing evidence suggesting that C(3) crops are likely to produce more harvestable products and that both C(3) and C(4) crops are likely to use less water with rising atmospheric [CO(2)] in the absence of stressful conditions. However, the beneficial direct impact of elevated [CO(2)] on crop yield can be offset by other effects of climate change, such as elevated temperatures and altered patterns of precipitation. Changes in food quality in a warmer, high-CO(2) world are to be expected, e.g., decreased protein and mineral nutrient concentrations, as well as altered lipid composition. We point out that studies related to changes in crop yield and food quality as a consequence of global climatic changes should be priority areas for further studies, particularly because they will be increasingly associated with food security. (c) 2009 Elsevier Ltd. All rights reserved.

Metastable Phase Diagram of Nanocrystalline ZrO(2)-Sc(2)O(3) Solid Solutions

We have investigated the crystal structures and phase transitions of nanocrystalline ZrO(2)-1 to -13 mol % Sc(2)O(3) by synchrotron X-ray powder diffraction and Raman spectroscopy. ZrO(2)-Sc(2)O(3) nanopowders were synthesized by using a stoichiometric nitrate-lysine get-combustion route. Calcination processes at 650 and at 850 degrees C yielded nanocrystalline materials with average crystallite sizes of (10 +/- 1) and (25 +/- 2) nm, respectively. Only metastable tetragonal forms and the cubic phase were identified, whereas the stable monoclinic and rhombohedral phases were not detected in the compositional range analyzed in this work. Differently from the results of investigations reported in the literature for ZrO(2)-Sc(2)O(3) materials with large crystallite sizes, this study demonstrates that, if the crystallite sizes are small enough (in the nanometric range), the metastable t ``-form of the tetragonal phase is retained. We have also determined the t`-t `` and t ``-cubic compositional boundaries at room temperature and analyzed these transitions at high temperature. Finally, using these results, we built up a metastable phase diagram for nanocrystalline compositionally homogeneous ZrO(2)-Sc(2)O(3) solid solutions that strongly differs from that previously determined from compositionally homogeneous ZrO(2)-Sc(2)O(3), Solid solutions with much larger crystallite sizes.

The long wavelength limit of hard thermal loop effective actions

We derive a closed form expression for the long wavelength limit of the effective action for hard thermal loops in an external gravitational field. It is a function of the metric, independent of time derivatives. It is compared and contrasted with the static limit, and with the corresponding limits in an external Yang-Mills field. (C) 2009 Elsevier B.V. All rights reserved.

Instabilities in thermal gravity with a cosmological constant

It is shown that in quantum gravity at finite temperature, the effective potential evaluated in the tadpole approximation can have a local minimum below a certain critical temperature. However, when the leading higher order thermal loop corrections are included, one finds that no static solution exists at high temperature. (C) 2008 Elsevier B.V. All rights reserved.

Glassy states in the stochastic Potts model

We have studied by numerical simulations the relaxation of the stochastic seven-state Potts model after a quench from a high temperature down to a temperature below the first-order transition. For quench temperatures just below the transition temperature the phase ordering occurs by simple coarsening under the action of surface tension. For sufficient low temperatures however the straightening of the interface between domains drives the system toward a metastable disordered state, identified as a glassy state. Escaping from this state occurs, if the quench temperature is nonzero, by a thermal activated dynamics that eventually drives the system toward the equilibrium state. (C) 2009 Elsevier B.V. All rights reserved.

Loops, Chains, Sheets, and Networks from Variable Coordination of Cu(hfac)(2) with a Flexibly Hinged Aminoxyl Radical Ligand

One pair of reactants, Cu(hfac)(2) = M and the hinge-flexible radical ligand 5-(3-N-tert-butyl-N-aminoxylphenyl)pyrimidine (3PPN = L), yields a diverse set of five coordination complexes: a cyclic loop M(2)L(1) dimer; a 1:1 cocrystal between an M(2)L(2) loop and an ML(2) fragment; a ID chain of M(2)L(2) loops linked by M; two 2D M(3)L(2) networks of (M-L)(n) chains crosslinked by M with different repeat length pitches; a 3D M(3)L(2) network of M(2)L(2) loops cross-linking (M-L)(n)-type chains with connectivity different from those in the 2D networks. Most of the higher dimensional complexes exhibit reversible, temperature-dependent spin-state conversion of high-temperature paramagnetic states to lower magnetic moment states having antiferromagnetic exchange within Cu-ON bonds upon cooling, with accompanying bond contraction. The 3D complex also exhibited antiferromagnetic exchange between Cu(II) ions linked in chains through pyrimidine rings.

Synthesis, Characterization, Luminescence and Defect Centres in CaYAl(3)O(7):Eu(3+) Red Phosphor

CaYAl(3)O(7):Eu(3+) phosphor was prepared at furnace temperatures as low as 550A degrees C by a solution combustion method. The formation of crystalline CaYAl(3)O(7):Eu(3+) was confirmed by powder X-Ray diffraction pattern. The prepared phosphor was characterized by SEM, FT-IR and photoluminescence techniques. Photoluminescence measurements indicated that emission spectrum is dominated by the red peak located at 618 nm due to the (5)D(0)-(7)F(2) electric dipole transition of Eu(3+) ions. Electron Spin Resonance (ESR) studies were carried out to identify the centres responsible for the thermoluminescence (TL) peaks. Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0126 is identified as an O(-) ion while centre II with an isotropic g-factor 2.0060 is assigned to an F(+) centre (singly ionized oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F(+) centre appears to correlate with the observed high temperature TL peak in CaYAl(3)O(7):Eu(3+) phosphor.

Luminescence and defect centres in Tb(3+) doped LaMgAl(11)O(19) phosphors

Terbium (Tb) doped LaMgAl(11)O(19) phosphors have been prepared by the combustion of corresponding metal nitrates (oxidizer) and urea (fuel) at furnace temperature as low as 500 C Combustion synthesized powder phosphor was characterized by X-ray diffraction and field emission scanning electron microscopy techniques LaMgAl(11)O(19) doped with trivalent terbium ions emit weakly in blue and orange light region and strongly in green light region when excited by the ultraviolet light of 261 nm Electron Spin Resonance (ESR) studies were carried out to study the defect centres Induced in the phosphor by gamma irradiation and also to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of at least two defect centres One of the centres (centre I) with principal g-values g(parallel to) = 2 0417 and g(perpendicular to) = 2 0041 is identified as O(2)(-) ion while centre II with an axially symmetric g-tensor with principal values g(parallel to) = 19698 and g(perpendicular to) = 1 9653 is assigned to an F(+) centre (singly ionized oxygen vacancy) An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons) The F centre and also the F+ centre appear to correlate with the observed high temperature TSL peak in LaMgAl(11)O(19) Tb phosphor (C) 2010 Elsevier Masson SAS All rights reserved

TL, OSL and ESR studies on beryllium oxide

Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermoluminescence (TL) and optically stimulated luminescence (OSL) processes in BeO phosphor. Two defect centres were identified in irradiated BeO phosphor by ESR measurements, which were carried out at room temperature and these were assigned to an O(-) ion and Al(2+) centre. The O(-) ion (hole centre) correlates with the main 190 degrees C TL peak. The Al(2+) centre (electron centre), which acts as a recombination centre, also correlates to the 190 degrees C TL peak. A third centre, observed during thermal annealing studies, is assigned to an O(-) ion and is related to the high temperature TL at 317 degrees C. This centre also appears to be responsible for the observed OSL process in BeO phosphor. (c) 2010 Elsevier B.V. All rights reserved.