Kinetics of linoleate oxidation in model systems

Oxidation of methyl linoleate, trilinoleate and linoleic acid has been studied in model systems based on various solid supports. Oxidation was followed by measurement of oxygen absorption, peroxide values and products of oxidation as a function of moisture equilibrium relative humidity. Effects of various metals, histidine and the antioxidants propyl gallate and butylated hydroxytoluene were studied. The results indicate: (a) at 50 C oxidation of protein increases with increasing moisture content and the protein interacts with peroxides changing the overall oxidation rate; (b) increasing moisture content shows the same inhibitory effect on oxidation of trilinoleate as it does on methyl linoleate; (c) the effectiveness of antioxidants is increased with increasing humidity but some chelating agents complexed with metals become catalytic at the higher moisture content; and (d) at moisture contents in the region of capillary condensation, mobility of reactants is enhanced since the rate of oxidation increases significantly. Presented at the AOCS Meeting, New York, October, 1968. Contribution No. 1396, Dept. of Nutrition and Food Science, Massachusetts Institute of Technology, Cambridge, Mass.     

Collisions of electrons with hydrogen atoms I. Package outline and high energy code

Being motivated by the applied researchers’ persisting need for accurate scattering data for the collisions of electrons with hydrogen atoms, we developed a computer package–Hex–that is designed to provide trustworthy results for all basic discrete and continuous processes within non-relativistic framework. The package consists of several computational modules that implement different methods, valid for specific energy regimes. Results of the modules are kept in a common database in the unified form of low-level scattering data (partial-wave T$T$-matrices) and accessed by an interface program which is able to produce various derived quantities like e.g. differential and integral cross sections. This article is the first one of a series of articles that are concerned with the implementation and testing of the modules. Here we give an overview of their structure and present (a) the command-line interface program hex-db that can be also easily compiled into a derived code or used as a backend for a web-page form and (b) simple illustrative module specialized for high energies, hex-dwba, that implements distorted and plane wave Born approximation.     

Diffusion controlled kinetics of crosslinking

Reactions of polymer formation and crosslinking become diffusion controlled when, during the reaction, the increasing glass transition temperature T_g comes close to the reaction temperature, the reaction still goes on below T_g but the reaction rate decreases steeply. A theory is presented relating the apparent rate constant to the difference between the reaction temperature and T_g based on the free volume or the Adam-Gibbs theory of glass transition. The theory is correlated with experiments on curing of diglycidyl ether of bisphenol A with 1,3-propanediamine. The implications for formation of protective films chemically crosslinked are discussed. The presence of a solvent and its evaporation affects the reaction rate through a change in concentrations of reactants as well as in T_g.     

Portable bead-based fluorescence detection system for multiplex nucleic acid testing: a case study with Bacillus anthracis

This paper describes the design, functioning and use of a portable detection platform for multiplex nucleic acid testing. The system features a bead-supported DNA hybridization assay performed inside a microfluidic cartridge. Polystyrene particles modified with DNA capture probes are confined in the detection area and exposed to a solution of fluorescently labeled target DNA strands. The cartridge, fabricated from inexpensive thermoplastic polymers, allows for conducting up to eight assays in parallel. The detection instrument is equipped with a pneumatic module and a manifold lid serving as an interface to mediate fluid displacement on the cartridge. The fluorescence signal deriving from each assay is recorded by a semi-confocal fluorescence reader embedded in the detection platform. The compact design of the instrument and its level of integration make it possible to obtain an analytical result in less than 15 min, while only few manual steps need to be performed in between. A proof-of-concept demonstration involving Cy3-labeled, PCR-amplified genomic DNA confirms the ability to detect Bacillus anthracis in a multiplexed single-assay format using lef and capC genes. Limits of quantification are on the order of 1 × 10⁹ copies/μL for lef targets.     

Information Security Risks in Enabling e-Government: The Impact of IT Vendors

The purpose of this article is to identify information systems security risks in local governments resulting from the cooperation with IT vendors. We focus on government-to-government projects where the confidentiality, integrity, and availability of information is a key concern. In our risk identification process, we take a systems thinking approach, taking into account actual and perceived risks. We identified 13 causes of risk in three risk areas and analyzed them using outsourcing literature.     

Rubber substrates and their influence on isomerization of conjugated dienes in pheromone dispensers

Release rate and degree of isomerization of pheromones with conjugated double bonds were studied in dispensers prepared from several rubber substrates. The substrates compared were made of rubber, cured with elemental sulfur or accelerators based on organic sulfur compounds or organic peroxides. Isomerization of the double bonds occurs immediately after impregnation of the substrate, and the degree of isomerization increases during field use and/or storage. The propensity of the isomers to isomerize corresponds to their proportion in the equilibrium mixture. AnE,Z isomer is isomerized faster than theE,E isomer, and finally a near-equilibrium mixture of the four isomers is present. Minimal isomerization was found in non-sulfur-cured substrates which are the material of choice.     

Novel Sulfonamide-Based Carbamates as Selective Inhibitors of BChE

A series of 14 target benzyl [2-(arylsulfamoyl)-1-substituted-ethyl]carbamates was prepared by multi-step synthesis and characterized. All the final compounds were tested for their ability to inhibit acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) in vitro, and the selectivity index (SI) was determined. Except for three compounds, all compounds showed strong preferential inhibition of BChE, and nine compounds were even more active than the clinically used rivastigmine. Benzyl {(2S)-1-[(2-methoxybenzyl)sulfamoyl]-4-methylpentan-2-yl}carbamate (5k), benzyl {(2S)-1-[(4-chlorobenzyl)sulfamoyl]-4-methylpentan-2-yl}carbamate (5j), and benzyl [(2S)-1-(benzylsulfamoyl)-4-methylpentan-2-yl]carbamate (5c) showed the highest BChE inhibition (IC₅₀ = 4.33, 6.57, and 8.52 µM, respectively), indicating that derivatives 5c and 5j had approximately 5-fold higher inhibitory activity against BChE than rivastigmine, and 5k was even 9-fold more effective than rivastigmine. In addition, the selectivity index of 5c and 5j was approx. 10 and that of 5k was even 34. The process of carbamylation and reactivation of BChE was studied for the most active derivatives 5k, 5j. The detailed information about the mode of binding of these compounds to the active site of both BChE and AChE was obtained in a molecular modeling study. In this study, combined techniques (docking, molecular dynamic simulations, and QTAIM (quantum theory of atoms in molecules) calculations) were employed.     

Unusual Fatty Acids in the Fat Body of the Early Nesting Bumblebee, <Emphasis Type="Italic">Bombus pratorum</Emphasis>

Unusual fatty acids with 24, 26, and 28 carbon atoms were found in triacylglycerols (TAGs) isolated from fat body tissue of bumblebee Bombus pratorum. The most abundant one was (Z,Z)-9,19-hexacosadienoic acid. Its structure was determined by mass spectrometry after derivatization with dimethyl disulfide and by infrared spectroscopy. ECL (equivalent chain length) values of its methyl ester were determined on both DB-1 and DB-WAX capillary columns. (Z,Z)-9,19-Hexacosadienoic acid is quite rare in nature. So far it has been identified only in marine sponges, and this work is the first evidence of its occurrence in a terrestrial organism. HPLC/MS analysis of the bumblebee TAGs showed that (Z,Z)-9,19-hexacosadienoic acid is present in one third of all TAG molecular species. As it was found in all sn-TAG positions, it is likely that (Z,Z)-9,19-hexacosadienoic acid is transported to tissues. Interestingly, labial gland secretion of B. pratorum was found to contain (Z,Z)-7,17-pentacosadiene, a hydrocarbon with markedly similar double bond positions and geometry. Possible biosynthetic relationships between these two compounds are discussed.     

Electrochemistry and spectro-electrochemistry of dithizonatophenylmercury(II)

The reactions between dithizone (H₂Dz, (1)) or potassium dithizonate (K⁺HDz⁻, (2)) and phenylmercury(II) chloride gives PhHg(HDz), (3). Complex (3) is photochromic. In dichloromethane, the blue photo-exited state of (3) exhibits a first order relaxation process to regenerate the orange ground state with rate constant 0.00053 s⁻¹. The half life of this relaxation is ca. 1300 s. Electrochemically, on cyclic voltammetry time scale, the oxidations of (1) and (3) are different. A comparative voltammetric and spectro-electrochemical study of (1) and (3) in CH₂Cl₂ containing 0.1 mol dm⁻³ [N(ⁿBu)₄][B(C₆F₅)₄] revealed that the mercapto group of (1) can be oxidised in two one-electron transfer steps. A disulphide is first produced and then in a second oxidation step, HDz⁺ is formed. In contrast, complex (3) shows only one ligand-based oxidation step. Upon complexation with phenylmercury the free mercaptan group of (1) becomes a stable “metal thioether”, Hg–S–C, which effectively prevents disulphide formation in (3) upon electrochemical oxidation. Both (1) and (3) shows two reduction steps. The electrochemical fingerprint of blue photo-excited (3) is identical to that of the orange ground state as no new functional groups are introduced upon irradiation; only bond rotation occurs. The different electronic spectra for each of the redox states of (3), obtained from spectro-electrochemical measurements, revealed that only the (3)/(3⁻) couple exhibits electrochromic properties.