The effect of water, brine and ethanol flotation on the quality and shelf life of macadamia kernels 2. Kernel pieces

Raw macadamia kernel pieces were immersed in water (specific gravity 1.00 g/cm(3)), brine (SG 1.02 g/cm(3)) or ethanol solution (SG 0.97 g/cm(3)) for 30 or 60 s, then re-dried to below 1.5% moisture (wet basis) and stored under vacuum for 0, 4 and 12 months. Flotation in water had no effect on the quality or shelf life of the kernel pieces over 12 months storage, as measured by sensory evaluation of the kernels and chemical analysis of the kernel oil. Immersion in a salt solution caused unacceptable changes in quality during storage, increasing as storage time increased. Flotation in dilute ethanol also caused unacceptable quality changes during storage. Therefore, only flotation of macadamia kernel pieces in water can be recommended for commercial operations. Microbiological concerns with such a process still need to be addressed.

Evaluation of various pre-treatments for the dehydration of banana and selection of suitable drying models

The thin-layer drying behaviour of bananas in a beat pump dehumidifier dryer was examined. Four pre-treatments (blanching, chilling, freezing and combined blanching and freezing) were applied to the bananas, which were dried at 50 degreesC with an air velocity of 3.1 m s(-1) and with the relative humidity of the inlet air of 10-35%. Three drying models, the simple model, the two-term exponential model and the Page model were examined. All models were evaluated using three statistical measures, correlation coefficient, root means square error, and mean absolute percent error. Moisture diffusivity was calculated based on the diffusion equation for an infinite cylindrical shape using the slope method. The rate of drying was higher for the pre-treatments involving freezing. The sample which was blanched only did not show any improvement in drying rate. In fact, a longer drying time resulted due to water absorption during blanching. There was no change in the rate for the chilled sample compared with the control. While all models closely fitted the drying data, the simple model showed greatest deviation from the experimental results. The two-term exponential model was found to be the best model for describing the drying curves of bananas because its parameters represent better the physical characteristics of the drying process. Moisture diffusivities of bananas were in the range 4.3-13.2 x 10(-10) m(2)s(-1). (C) 2002 Published by Elsevier Science Ltd.

Back to (non)-Basics: Recent developments in neutral and charge-balanced glycosidase inhibitors

Certain glycosidase inhibitors possess potent antiviral, antitumour and antidiabetic properties. Glyconic acid lactones, the earliest glycosidase inhibitors identified, have planar anomeric carbons that mimic the transition state of glycoside hydrolysis. Other classes include lactams, glycals, epoxides, halides and sulfonium ions, the latter based on the natural product salacinol from an antidiabetic herb.

Characterisation of grafted supports used for solid-phase synthesis

A series of 'pellicular' type supports were fabricated by direct gamma-radiation-mediated graft polymerisation of styrene onto polypropylene, followed by aminomethylation. Raman spectroscopy was used for measuring the level of penetration of polystyrene graft into polypropylene, and other structural features such as density of graft and depth of functionalisation. The kinetics of the coupling of fluorenylmethylcarbamate (Fmoc)-labelled amino acids, to the aminomethylated polystyrene grafts have been measured by UV absorption followed cleavage of the Fmoc chromophore. The Raman spectroscopy results showed that for this series of experiments the calculated rate coefficient for coupling of Fmoc-labelled amino acids was primarily dependent on graft thickness, but was also influenced by the proportion of polystyrene graft to polypropylene. In general, it was also shown that with increasing loading capacity of support the calculated rate coefficient for amino-acid coupling decreased correspondingly. In addition, a support that had both a high rate coefficient and a high loading capacity was prepared from polypropylene base material with a co-continuous porous structure (high surface area). (C) 2003 Society of Chemical Industry.

Synthesis and characterization of mono- and bis-ligand zinc(II) and cadmium(II) complexes of the di-2-pyridylketone Schiff base of S-benzyl dithiocarbazate (Hdpksbz) and the X-ray crystal structures of the [Zn(dpksbz)2] and [Cd(dpksbz)NCS]2 complexes

New mono- and bis-chelated zinc(II) and cadmium(II) complexes of formula, [M(dpksbz)NCS] (dpksbz = anionic form of the di-2-pyridylketone Schiff base of S-benzyldithiocarbazate) and [M(dpksbz)(2)] (M = Zn-II, Cd-II) have been prepared and characterized. The structure of the bis-ligand complex, [Zn(dpksbZ)(2)] has been determined by X-ray diffraction. The complex has a distorted octahedral geometry in which the ligands are coordinated to the zinc(II) ion as uninegatively charged tridentate chelates via the thiolate sulfur atoms, the azomethine nitrogen atoms and the pyridine nitrogen atoms. The distortion from a regular octahedral geometry is attributed to the restricted bite angles of the Schiff base ligands. X-ray structural analysis shows that the [Cd(dpksbz)NCS](2) complex is a centrosymmetric dimer in which each of the cadmium(II) ions adopts a five-coordinate, approximately square-pyramidal configuration with the Schiff base acting as a tetradentate chelating agent coordinating a cadmium(II) ion via one of the pyridine nitrogen atoms, the azomethine nitrogen atom and the thiolate sulfur atom; the second pyridine nitrogen atom is coordinated to the other cadmium(II) ion of the dimer. The fifth coordination position around each cadmium(II) is occupied by an N-bonded thiocyanate ligand. (C) 2003 Elsevier Science Ltd. All rights reserved.

Structure of the HERG K+ channel S5P extracellular linker - Role of an amphipathic alpha-helix in C-type inactivation

The HERG K+ channel has very unusual kinetic behavior that includes slow activation but rapid inactivation. These features are critical for normal cardiac repolarization as well as in preventing lethal ventricular arrhythmias. Mutagenesis studies have shown that the extracellular peptide linker joining the fifth transmembrane domain to the pore helix is critical for rapid inactivation of the HERG K+ channel. This peptide linker is also considerably longer in HERG K+ channels, 40 amino acids, than in most other voltage-gated K+ channels. In this study we show that a synthetic 42-residue peptide corresponding to this linker region of the HERG K+ channel does not have defined structural elements in aqueous solution; however, it displays two well defined helical regions when in the presence of SDS micelles. The helices correspond to Trp(585)-Ile(593) and Gly(604)-Tyr(611) of the channel. The Trp(585)-Ile(593) helix has distinct hydrophilic and hydrophobic surfaces. The Gly(604)-Tyr(611) helix corresponds to an N-terminal extension of the pore helix. Electrophysiological studies of HERG currents following application of exogenous S5P peptides show that the amphipathic helix in the S5P linker interacts with the pore region of the channel in a voltage-dependent manner.

Compositional changes of Australia-grown Western Schley pecans [Carya illinoinensis (Wangenh.) K. Koch] during maturation

Changes in composition during the maturation of Western Schley pecans [Carya illinoinensis (Wangenh.) K. Koch] grown in Australia were investigated. Pecans of different maturity levels were collected at monthly intervals between March and June in. 1999 and 2000 and analyzed for the concentrations of moisture, total lipid, sucrose, raffinose, protein, and the minerals aluminum, boron, calcium, copper, iron, potassium, magnesium, manganese, sodium, phosphorus, sulfur, and zinc. Moisture, total lipid, and calcium contents changed significantly (p < 0.05) with harvest time and maturity, whereas the other components did not. Western Schley pecans grown in Australia should be harvested after the shuck has opened and it is either green or brown in color to maximize total lipid content and quality. This occurred after May 11 in 1999 and after May 17 in 2000.

Synthesis of optically complex core-shell colloidal suspensions: Pathways to multiplexed biological screening

The ability to generate enormous random libraries of DNA probes via split-and-mix synthesis on solid supports is an important biotechnological application of colloids that has not been fully utilized to date. To discriminate between colloid-based DNA probes each colloidal particle must be 'encoded' so it is distinguishable from all other particles. To this end, we have used novel particle synthesis strategies to produce large numbers of optically encoded particle suitable for DNA library synthesis. Multifluorescent particles with unique and reproducible optical signatures (i.e., fluorescence and light-scattering attributes) suitable for high-throughput flow cytometry have been produced. In the spectroscopic study presented here, we investigated the optical characteristics of multi-fluorescent particles that were synthesized by coating silica 'core' particles with up to six different fluorescent dye shells alternated with non-fluorescent silica 'spacer' shells. It was observed that the diameter of the particles increased by up to 20% as a result of the addition of twelve concentric shells and that there was a significant reduction in fluorescence emission intensities from inner shells as an increasing number of shells were deposited.

New structure formation on gamma-irradiation of poly(chlorotrifluoroethylene)

The radiation chemistry of PCTFE at different temperatures has been studied. The polymer was irradiated under vacuum to absorbed doses of up to 1500 kGy. Three irradiation temperatures were chosen. These included ambient temperature, a temperature well above the T, and a temperature above the crystalline melting temperature. These were 298, 423 and 493 K, respectively. The formation of new structures was identified by solid-state FTIR and F-19 NMR. No branching was observed below the melting temperature, but branches were observed above the melting temperature. G-values for chain-end formation were 1.5 and 2.4 at room temperature and 423 K, respectively and the G-value for the formation of double bonds was found to be < 0.1. For the irradiations at 493 K, the G-values for the formation of chain ends, double bonds and branching points were 3.6, 0.2 and 0.5, respectively. The presence of long-chain branches within the polymer structure could not be proven for radiolysis at 493 K, but scission predominates and network formation does not occur upon irradiation. DSC studies of the polymers irradiated at ambient temperature were consistent with chain scission leading to an increase in the percentage crystallinity, as observed for other fluoropolymers. (C) 2003 Elsevier Science Ltd. All rights reserved.

Chiral resolution of hexaamine cobalt(III) cages: Substituent effects on chiral discrimination

Chiral resolution of the cobalt cage complexes [Co(diNOsar)](3+) and [Co(diAMsarH(2))](5+) have been achieved by selective crystallization with the anion bis-mu-(R),(R)-tartratodiantimonate(III) ([Sb-2(R,R-tart)(2)](2-)) and also by column chromatography with Na-2[Sb-2(R, R-tart)(2)] as eluent. The X-ray crystal structures of Lambda-[ Co(diNOsar)][Sb-2(R, R-tart)(2)] Cl . 7H(2)O and Delta-[Co(diAMsarH(2))][Sb-2(R, R-tart)(2)](2)Cl . 14H(2)O are reported, which reveal an unexpected reversal of chiral discrimination when the cage substituent is changed from nitro (Lambda-enantiomer) to ammonio (Delta-enantiomer) and shows that the ammonio- substituted cage is capable of forming a three-point hydrogen-bonding interaction with each complex anion, whereas the nitro analogue can only form two hydrogen bonds with each [Sb-2(R, R-tart)(2)](2-) anion. During cation exchange chromatography of the racemic cobalt cage complexes with Na-2[Sb-2(R, R-tart)(2)] as eluent, Lambda-[Co(diNOsar)](3+) elutes first, which implies a tighter ion pairing interaction than for the Delta-enantiomer. On the other hand, Delta-[Co(diAMsarH(2))](5+) elutes first during chromatography under identical conditions, which is also consistent with a preferred outer-sphere complex formed between Delta-[Co(diAMsarH(2))](5+) and [Sb-2(R, R-tart)(2)](2-) relative to Lambda-[Co(diAMsarH(2))](5+) and [Sb-2(R,R-tart)(2)](2-).

High energy radiation grafting of fluoropolymers

Fluoropolymers are known as chemically inert materials with good high temperature resistance, so they are often the materials of choice for harsh chemical environments. These properties arise because the carbon-fluorine bond is the strongest of all bonds between other elements and carbon, and, because of their large size, fluorine atoms can protect the carbon backbone of polymers such as poly(tetrafluoroethylene), PTFE, from chemical attack. However, while the carbon-fluorine bond is much stronger than the carbon hydrogen bond, the G values for radical formation on high energy radiolysis of fluoropolymers are roughly comparable to those of their protonated counterparts. Thus, efficient high energy radiation grafting of fluoropolymers is practical, and this process can be used to modify either the surface or bulk properties of a fluoropolymer. Indeed, radiation grafted fluoropolymers are currently being used as separation membranes for fuel cells, hydrophilic filtration membranes and matrix substrate materials for use in combinatorial chemistry. Herein we present a review of recent studies of the high energy radiation grafting of fluoropolymers and of the analytical methods available to characterize the grafts. (C) 2003 Elsevier Ltd. All rights reserved.

Structural definition of the low-temperature phase transition of tris(ethane-1,2-diamine)zinc(II) dinitrate

The 93 K X-ray crystal structure of tris(ethane-1,2-diamine)zinc(II) dinitrate is reported. As predicted by the spectroscopic studies of other workers, there is a reversible phase transition of the structure at low temperature. We have determined this temperature to be 143 K. The structure at this temperature and below resembles that of the room temperature structure, except the crystallographic D-3 symmetry of the complex cation (296 K) is lowered to C-2 ( below 144 K) by subtle changes in cation-anion hydrogen bonding. No change in the conformation of the cation or its bond lengths and angles was found.

Investigation of the vapor-phase grafting of styrene onto PFA

Poly(tetrafluoroethylene-co-perfluoropropyI vinyl ether), PFA, was grafted with styrene from the vapor phase using a simultaneous radiation grafting method. The graft yields were measured as a function of the dose and dose rate and were found to be initially linearly dependent on the dose and independent of the dose rate up to dose rates of similar to3 kGy/h. However, at a dose rate of 6.2 kGy/h, the slope of the yield-grafting time plot decreased. Raman depth profiles of the grafts showed that the polystyrene concentrations were greatest near the surface of the grafted samples and decreased with depth. The maximum penetration depth of the graft depended on the radiation dose for a fixed dose rate. Fmoc-Rink loading tests showed that the grafts displayed superior loading compared to grafts prepared from bulk styrene or from styrene solutions other than methanol.

Evaluation of 99mTc-Sestamibi as a potential tool to investigate PgP activity in inflammation

Introduction: In the XXI Century ’s Society the scientific investigation process has been growing steadily , and the field of the pharmaceutical research is one of the most enthusiastic and relevant . Here, it is very important to correlate observed functional alterations with possibly modified drug bio distribution patterns . Cancer, inflammation and inf ection are processes that induce many molecular intermediates like cytokines, chemokines and other chemical complexes that can alter the pharmacokinetics of many drugs. One cause of such changes is thought to be the modulator action of these complexes in t he P - Glyco p rotein activity, because they can act like inducers/inhibitors of MDR - 1 expression. This protein results from the expression of MDR - 1 gene, and acts as an ATP energy - dependent efflux pump, with their substrates including many drugs , like antiretrovirals, anticancers, anti - infectives, immunosuppressants, steroids or opioids . Objectives: Because of the lack of methods to provide helpful information in the investigation of in vivo molecular changes in Pgp activity during infection/infl ammation processes, and its value in the explanation of the altered drug pharmacokinetic, this paper want to evaluate the potential utility of 99m Tc - Sestamibi scintigraphy during this kind of health sciences investigation. Although the a im is indeed to create a technique to the in vivo study of Pgp activity, this preliminary Project only reaches the in vitro study phase, assumed as the first step in a n evaluation period for a new tool development. Materials and Methods: For that reason , we are performing in vitro studies of influx and efflux of 99m Tc - Sestamibi ( that is a substrate of Pgp) in hepatocytes cell line (HepG2). We are interested in clarify the cellular behavior of this radiopharmaceutical in Lipopolysaccharide(LPS) stimulated cells ( well known in vitro model of inflammation) to possibly approve this methodology. To validate the results, the Pgp expression will be finally evaluated using Western Blot technique. Results: Up to this moment , we still don’t have the final results, but we have already enough data to let us believe that LPS stimulation induce a downregulation of MDR - 1, and consequently Pgp, which could conduce to a prolonged retention of 99m Tc - Sestamibi in the inflamed cells . Conclusions: If and when this methodology demonstrate the promising results we expect, one will be able to con clude that Nuclear Medicine is an important tool to help evidence based research also on this specific field .

Contribuição à organização da pesquisa em Química e os desafios da interação com outras áreas do conhecimento

This article provides some aspects that allow making a current reading of the situation of the Brazilian Chemistry that permit us considerate it as a strategic area. They are still presented some initial proposals related to the organization of the research as well as to win the challenges of the relationship with the other areas of the knowledge.