Relaxation Time of Chemical Reactions from Network Thermodynamics

The relationship for the relaxation time(s) of a chemical reaction in terms of concentrations and rate constants has been derived from the network thermodynamic approach developed by Oster, Perelson, and Katchalsky.Generally, it is necessary to draw the bond graph and the “network analogue” of the reaction scheme, followed by loop or nodal analysis of the network and finally solving of the resulting differential equations. In the case of single-step reactions, however, it is possible to obtain an expression for the relaxation time. This approach is simpler and elegant and has certain advantages over the usual kinetic method. The method has been illustrated by taking different reaction schemes as examples.

Chemical ordering in As-Se glasses: X-ray absorption edge and XPES studies

X-ray absorption edge and X-ray photoelectron spectroscopic studies of As-Se glasses seem to support a chemical ordering model.

Managing resistance to chemical treatments in stored products pests

This review focuses on key trends in resistance to chemical treatments in stored product pests, and advances in resistance management, with an emphasis on resistance to the fumigant phosphine. Findings: Phosphine resistance continues to be a major concern. In particular, phosphine resistance in Cryptolestes ferrugineus has emerged as a serious issue, with some populations exhibiting the strongest level detected so far for this fumigant. In response, a 'quick knock down test' has been established to deliver industry and scientists 'same day' advice on the resistance status of field samples; sulfuryl fluoride is being developed as a 'resistance breaker' and phosphine dosages are being revised to manage this problem. There has been major progress in identifying the genes responsible for phosphine resistance and the development of molecular resistance diagnostics for key pests. Several studies on Rhyzopertha dominica have demonstrated that molecular screening can be used to determine the frequency of resistance alleles in samples collected from farm storages. Despite on-going research in several pests, there is no definitive answer to the question of whether there is a fitness cost associated phosphine resistance, with some studies showing a clear cost and others none. Evidence continues to emerge of resistance to grain protectants, including the juvenile hormone analogue methoprene. The development and adoption of spinosad, as a next generation 'green' treatment, and the use of protectant combinations provides opportunities to counter the problem of protectant resistance.Directions for future research: A uniform set of protocols should be developed for phosphine resistance detection for all major species. It should combine 'quick tests' and molecular diagnostics to be adopted internationally. Research is required on the establishment of a decision making system that integrates newly developed grain protectants and fumigants, other alternative control methods, as well as an accurate and rapid resistance detection system for early warning of the emergence of new resistances.

Chemical containment and eradication of screw− worm incursions in Australia

Screwworms are obligate, invasive parasites of warm-blooded animals. The female flies lay batches of eggs at the edge of wounds or other lesions. These eggs hatch to larvae or screw-worms which feed on affected animals for 6-7 days, burrowing deeply into subcutaneous tissues and causing severe trauma to animals, production loss and potentially death. Susceptible sites include wounds resulting from management practices such as castration, de-horning and ear tagging and lesions caused by the activities of other parasites such as buffalo flies and ticks. The navels of the new born and the vulval region of their mothers following parturition are highly susceptible and body orifices such as nose and ears are also frequent targets for ovipositing screwworm flies. The Old World screw-worm, Chrysomya bezziana (OWS) is considered one of the most serious exotic insect pest threatening Australia's livestock industries and is endemic in a number of our closest neighbouring countries. New World screwworm (NWS), Cochliomyia hominivorax, endemic to South America, has also entered Australia on at least 2 occasions. Many tropical and subtropical areas of Australia are suitable for the establishment of OWS and the potential range is expected to increase with climate change. The Australian screwworm preparedness strategy indicates a program of containment with chemical treatments followed by eradication of OWS using sterile male release and parasiticides. However, there is no longer an operational OWS sterile insect screw-worm facility anywhere in the world and establishing a large scale production facility would most optimistically take at least 2 years. In the interim, containment would be almost totally dependent on the availability of effective chemical controls. A review of chemical formulations available for potential use against OWS in Australia found that currently only one chemical, ivermectin administered by subcutaneous injection (s.c.) is registered for use against OWS and that many of the chemicals previously shown to be effective against OWS were no longer registered for animal use in Australia.18 From this review a number of Australian-registered chemicals were recommended as a priority for testing against OWS. The Australian Pesticides and Veterinary Medicines Authority (APVMA) can issue an emergency use permit for use of pesticides if they are registered in Australia for other animal uses and shown to be effective against OWS. This project tested the therapeutic and prophylactic efficacy of chemicals with potential for use in the treatment and control of OWS.

Mechanistic Aspects of Shape Selection and Symmetry Breaking during Nanostructure Growth by Wet Chemical Methods

The control of shapes of nanocrystals is crucial for using them as building blocks for various applications. In this paper, we present a critical overview of the issues involved in shape-controlled synthesis of nanostructures. In particular, we focus on the mechanisms by which anisotropic structures of high-symmetry materials (fcc crystals, for instance) could be realized. Such structures require a symmetry-breaking mechanism to be operative that typically leads to selection of one of the facets/directions for growth over all the other symmetry-equivalent crystallographic facets. We show how this selection could arise for the growth of one-dimensional structures leading to ultrafine metal nanowires and for the case of two-dimensional nanostructures where the layer-by-layer growth takes place at low driving forces leading to plate-shaped structures. We illustrate morphology diagrams to predict the formation of two-dimensional structures during wet chemical synthesis. We show the generality of the method by extending it to predict the growth of plate-shaped inorganics produced by a precipitation reaction. Finally, we present the growth of crystals under high driving forces that can lead to the formation of porous structures with large surface areas.

Mammalian brain plasma membranes: Isolation, enzymatic, and chemical characterization

Two variants of a simplified procedure for the isolation of plasma membrane fractions from monkey and rat brains, are described. The preparations show marked enrichments in the marker enzymes, (Na+-K+) adenosine triphosphatase, acetylcholinesterase, 5′-nucleotidase and adenylate cyclase. Lipid analysis and a protein electrophoretic pattern are presented. An enzymatic check has been made to assess for contamination by other cellular organelles. The amino acid composition of brain membrane proteins show a resemblance to the reported composition of erythrocyte ghost proteins but differ from myelin proteins.

The nonplanar peptide unit III. Quantum chemical calculations for related compounds and experimental X-ray diffraction data

The possible nonplanar distortions of the amide group in formamide, acetamide, N-methylacetamide, and N-ethylacetamide have been examined using CNDO/2 and INDO methods. The predictions from these methods are compared with the results obtained from X-ray and neutron diffraction studies on crystals of small open peptides, cyclic peptides, and amides. It is shown that the INDO results are in good agreement with observations, and that the dihedral angles N and defining the nonplanarity of the amide unit are correlated approximately by the relation N = -2, while C is small and uncorrelated with . The present study indicates that the nonplanar distortions at the nitrogen atom of the peptide unit may have to be taken into consideration, in addition to the variation in the dihedral angles (,), in working out polypeptide and protein structures.

Chemical modification studies on Abrus agglutinin Involvement of tryptophan residues in sugar binding

The galactose-binding lectin from the seeds of the jequirity plant (Abrus precatorius) was subjected to various chemical modifications in order to detect the amino acid residues involved in its binding activity. Modification of lysine, tyrosine, arginine, histidine, glutamic acid and aspartic acid residues did not affect the carbohydratebinding activity of the agglutinin. However, modification of tryptophan residues carried out in native and denaturing conditions with N-bromosuccinimide and 2- hydroxy-5-nitrobenzyl bromide led to a complete loss of its carbohydrate-binding activity. Under denaturing conditions 30 tryptophan residues/molecule were modified by both reagents, whereas only 16 and 18 residues/molecule were available for modification by N-bromosuccinimide and 2-hydroxy-5-nitrobenzyl bromide respectively under native conditions. The relative loss in haemagglutinating activity after the modification of tryptophan residues indicates that two residues/molecule are required for the carbohydrate-binding activity of the agglutinin. A partial protection was observed in the presence of saturating concentrations of lactose (0.15 M). The decrease in fluorescence intensity of Abrus agglutinin on modification of tryptophan residues is linear in the absence of lactose and shows a biphasic pattern in the presence of lactose, indicating that tryptophan residues go from a similar to a different molecular environment on saccharide binding. The secondary structure of the protein remains practically unchanged upon modification of tryptophan residues, as indicated by c.d. and immunodiffusion studies, confirming that the loss in activity is due to modification only.

A model for doped-oxide-source diffusion with a chemical reaction at the silicon-silicon dioxide interface

A mathematical model for doped-oxide-source diffusion is proposed. In this model the concept of segregation of impurity at the silicon-silicon dioxide is used and also a constant of “rate limitation” is introduced through a chemical reaction at the interface.

Effect of pretreatment on the sublimation of ammonium perchlorate

The effects of pretreatments on the sublimation of pure ammonium perchlorate (AP) were studied by differential thermal analysis. The addition of inorganic salts (doping), or preheating, lead to desensitisation of the sublimation process, whereas it was sensitised by precompression. Sublimation increased with decrease in the particle size of the AP from 500 to 200 microns, but decreased with a further decrease in size from 200 to 100 microns. The results are interpreted in terms of gross imperfections and strain in the AP crystals.

Microbial oil production from sugarcane bagasse hydrolysates by oleaginous yeast and filamentous fungi

This study investigated the potential use of sugarcane bagasse as a feedstock for oil production through microbial cultivation. Bagasse was subjected to dilute acid pretreatment with 0.4 wt% H2SO4 (in liquid) at a solid/liquid ratio of 1:6 (wt/wt) at 170 °C for 15 min, followed by enzymatic hydrolysis of solid residue. The liquid fractions of the pretreatment process and the enzymatic hydrolysis process were detoxified and used as liquid hydrolysate (SCBLH) and enzymatic hydrolysate (SCBEH) for the microbial oil production by oleaginous yeast (Rhodotorula mucilaginosa) and filamentous fungi (Aspergillus oryzae and Mucor plumbeus). The results showed that all strains were able to grow and produce oil from bagasse hydrolysates. The highest oil concentrations produced from bagasse hydrolysates were by M. plumbeus at 1.59 g/L (SCBLH) and 4.74 g/L (SCBEH). The microbial oils obtained have similar fatty acid compositions to vegetable oils, indicating that the oil can be used for the production of second generation biodiesel. On the basis of oil yields obtained by M. plumbeus, from 10 million t (wet weight) of bagasse generated annually from sugar mills in Australia, it is estimated that the total biodiesel that could be produced would be equivalent to about 9% of Queensland’s diesel consumption.

Chemotherapy pretreatment sensitizes solid tumor-derived cell lines to Vα24+ NKT cell-mediated cytotoxicity

There is an increasing awareness of the therapeutic potential for combining immune-based therapies with chemotherapy in the treatment of malignant diseases, but few published studies evaluate possible cytotoxic synergies between chemotherapy and cytotoxic immune cells. Human Vα24 +/Vβ11+ NKT cells are being evaluated for use in cell-based immunotherapy of malignancy because of their immune regulatory functions and potent cytotoxic potential. In this study, we evaluated the cytotoxicity of combinations of chemotherapy and NKT cells to determine whether there is a potential to combine these treatment modalities for human cancer therapy. The cytotoxicity of NKT cells was tested against solid-tumor derived cell lines NCI-H358, DLD-1, HT-29, DU-145, TSU-Pr1 and MDA-MB231, with or without prior treatment of these target cells, with a range of chemotherapy agents. Low concentrations of chemotherapeutic agents led to sensitization of cell lines to NKT-mediated cytotoxicity, with the greatest effect being observed for prostate cancer cells. Synergistic cytotoxicity occurred in an NKT cell in a dose-dependent manner. Chemotherapy agents induced upregulation of cell surface TRAIL-R2 (DR5) and Fas (CD95) expression, increasing the capacity for NKT cells to recognize and kill via TRAIL- and FasL-mediated pathways. We conclude that administration of cytotoxic immune cells after chemotherapy may increase antitumor activities in comparison with the use of either treatment alone.

Modeling of Freezing Phenomena Induced by Chemical Reactions

Spatial variations in the concentration of a reactive solute in solution are often encountered in a catalyst particle, and this leads to variation in the freezing point of the solution. Depending on the operating temperature, this can result in freezing of the solvent oil a portion of catalyst, rendering that part of the active area ineffective Freezing call occur by formation of a sharp front or it mush that separates the solid and fluid phases. In this paper, we model the extent of reduction in the active area due to freezing. Assuming that the freezing point decreases linearly with solute concentration, conditions for freezing to occur have been derived. At steady state, the ineffective fraction of catalyst pellet is found to be the same irrespective of the mode of freezing. Progress of freezing is determined by both the heat of reaction and the latent heat of fusion Unlike in freezing of alloys where the latter plays a dominant role, the exothermicity of the reaction has a significant effect on freezing in the presence of chemical reactions. A dimensionless group analogous to the Stefan number could be defined to capture the combined effect of both of these.