Determination of oxidative stability of oils and fats

In a new approach to evaluating the oxidative stability of oils and fats, the consumption of oxygen by a sample confined in a reactor of adjustable temperature is monitored with a gas-phase flow injection analysis (FIA) system. Temperature-dependent data are collected in a low-oxygen-content atmosphere. For a variety of samples, log(oxygen consumption) is linearly related to the reciprocal of the absolute temperature (minimum linear r(2) > 0.99). This makes it possible to extrapolate the temperature-dependent data to predict the stability of the samples at other temperatures, e.g., typical ambient storage temperatures at which the direct determination of oxidative stability would be too slow for most samples. The proposed method is instrumentally simple and is easily automated. The sample throughput rate is an order of magnitude faster relative to current alternatives; temperature-dependent stability characterization for a sample (three temperatures, triplicate measurement at each temperature) requires ≤ 2 h. The reproducibility of the results is excellent. For a cottonseed-oil sample studied over 3 days, the slope and intercept of the log(O(2) consumption) vs 1/T linear plot (for all the 45 measurements made) exhibited uncertainties of 2.1% and 2.0% for the slope and the intercept, respectively, with a linear r(2) value of 0.9929. In a high-temperature (160 °C) oxidation experiment with various oils, the oxygen consumption was well-correlated (linear r(2) 0.9692) with the concomitant decrease in iodine absorption number (IAN). In contrast, it was poorly and negatively correlated with an increase in the peroxide value.     

Stability of Interesterified Fats

The stability characteristics of a number of interesterified fat products made from vegetable oil-mixtures were studied and compared to those of a commercial hydrogenated stuff, vanaspati. It was found that the interesterified products, after addition of antioxidants had comparable stability to vanaspati in most cases, and, hence would not offer any storage problem.     

Asymmetric membrane fiber-based carbon dioxide removal devices for ion chromatography

The application of hollow and filament-filled single asymmetric membrane fibers, consisting of a thin silicone layer on a tubular microporous support, for removing CO(2) in suppressed ion chromatography effluents is described. With appropriate choice of the removal device and operating conditions, the CO(2) can be essentially quantitatively (99+%) removed. For carbonate-based eluents, the use of such devices greatly reduces or eliminates the water dip, permitting better quantitation of poorly retained anions that elute close to the dip, allows practical gradient chromatography, and improves noise levels and attainable detection limits. In hydroxide eluent chromatography, the device largely removes the response from CO(2) present in the samples; this greatly aids atmospheric trace gas analysis by IC. Device dimensions are such that the dispersion introduced by the device is small.     

Glyceride Composition in Interesterified Fats

The positional distribution of acyl groups in interesterified fats obtained from a number of vegetable oil-mixtures was studied by the selective deacylation reaction of Pancreatic Lipase. In the case of randomised fats, there was almost equal distribution of fatty acids in the three positions, which indicated completeness of randomisation and destruction of the selective orientation of acyl groups present in natural fats. On the other hand, there was little or no change in positional distribution during directed interesterification. It was found that for natural and randomised fats, the glyceride compositions calculated from the Lipase hydrolysis data agreed quite well with those obtained by argentation thin-layer chromatography (TLC) followed by gas-liquid chromatography (GLC) with an internal standard. The glyceride compositions of directed interesterified fats, found by argentation TLC followed by GLC, indicated that the proportions of GS₃ and GU₃ increase to a considerable extent with simultaneous decrease in GSU₂, while that of GS₂U increases to a comparatively small extent, or remains unchanged.     

A Theoretical Analysis of Query Selection for Collaborative Filtering

We consider the problem of determining which of a set of experts has tastes most similar to a given user by asking the user questions about his likes and dislikes. We describe a simple algorithm for generating queries for a theoretical model of this problem. We show that the algorithm requires at most opt(F)(ln(|F|/opt(F)) + 1) + 1 queries to find the correct expert, where opt(F) is the optimal worst-case bound on the number of queries for learning arbitrary elements of the set of experts F. The algorithm runs in time polynomial in |F| and |X| (where X is the domain) and we prove that no polynomial-time algorithm can have a significantly better bound on the number of queries unless all problems in NP have n ^{O(log log n)} time algorithms. We also study a more general case where the user ratings come from a finite set Y and there is an integer-valued loss function on Y that is used to measure the distance between the ratings. Assuming that the loss function is a metric and that there is an expert within a distance from the user, we give a polynomial-time algorithm that is guaranteed to find such an expert after at most 2opt(F, ) ln + 2( + 1)(1 + deg(F, )) queries, where deg(F, ) is the largest number of experts in F that are within a distance 2 of any f F.     

Determination of trace perchlorate in high-salinity water samples by ion chromatography with on-line preconcentration and preelution

A simple, automated system for the determination of trace perchlorate by ion chromatography (IC) with an online preconcentration technique is reported. The sample is preconcentrated, and less strongly held ions preeluted before the analyte is transferred to the principal separation system. This approach provides low limits of detection (LOD) and is particularly robust toward the effect of high concentrations of common anions, such as those present in groundwater samples. It compares favorably with currently promulgated EPA method 314.0. The LOD (S/N = 3) is 0.77 microg/L for a 2-mL reagent water sample and decreases more-or-less proportionately with increasing sample volume, at least up to 20 mL. Even with a sample of conductivity 14.7 mS/cm (approximately that of 0.1 M Na2SO4), the recovery of added perchlorate at the 25.0 microg/L level was still 92%. The concentration of added perchlorate in the range of 1-400 microg/L was linearly correlated to the peak area, with an r2 value of 0.9997. The recovery of perchlorate from artificial samples with different conductivity by the present method compares favorably with those from the currently recommended EPA Method. The ability of this approach to remove matrix interferences suggests that it would be also promising for perchlorate analysis in other challenging samples.     

Silver-induced enhancement of thiochrome-based peroxide measurements

Thiamine is presently one of the most attractive substrates used for sensitive fluorometric measurements of peroxides. Thiochrome (TC), a highly fluorescent product, is formed in enzyme-mediated oxidations. It is assumed that H(2)O(2) is nearly quantitatively converted to TC. The reaction cannot differentiate H(2)O(2) from many other peroxides such as methylhydroperoxide (MHP); to perform differential measurements, H(2)O(2) can first be selectively destroyed by a suitable catalyst such as MnO(2). In substituting Ag(2)O for MnO(2) to accomplish the selective destruction of H(2)O(2), we achieved the stated objective but were puzzled by a 3-fold increase in the MHP response in the presence of Ag(2)O. It was soon discovered that traces of dissolved Ag(+) and Hg(2+) can dramatically increase the yield of TC in this reaction from either H(2)O(2) or MHP; the normal yield in fact is only 20%. We present here a reaction scheme and kinetic model that adequately describes this behavior and should provide a path to substantially increase the sensitivity of this important assay method.     

Trace gas measurement with an integrated porous tube collector/long-path absorbance detector

Porous membrane tubes filled with an absorbing solution that change colors upon selective reactions with specific gases provide high sensitivity inexpensive gas sensors. These can be routinely used for ambient monitoring in a fully automated manner. We consider both stopped and continuous flow operations and show the superiority of the stopped flow mode theoretically and experimentally. Light throughput through various membrane tubes is presented, and superior performance of such tubes over Teflon AF is shown. Sensors for NO2 and for O3 were based on Griess-Saltzman and indigotrisulfonate chemistries, respectively. A computer-controlled two-LED absorbance measurement system (one wavelength monitors the signal, the other references the system) that also governs automated reagent refilling was implemented. Sub-parts-per-billion-volume detection limits are attainable within a few minutes for both gases. Comparative data with a commercial UV-photometry-based ozone monitor showed excellent agreement with the response pattern of the present instrument. Low cost, ready applicability to the measurement of different gases by merely changing the light source and chemistry, and high sensitivity makes this instrument attractive for both pedagogic and practical purposes.     

Low-Stress Abrasive Wear Behaviour of a 0.2% C Steel: Influence of Microstructure and Test Parameters

A low (0.2%) carbon steel has been subjected to heat treatment to form varying quantities of ferrite plus martensite in its microstructure. This was achieved by holding the samples in the two-phase (ferrite plus austenite) region at three different temperatures (750, 780, and 810°C) for a specific duration followed by quenching in ice water. In another exercise, the steel was also subjected to annealing treatment by austenitizing at 890°C followed by furnace cooling for comparison purposes. The samples were subjected to low-stress (three-body) abrasion tests using an ASTM rubber wheel abrasion test apparatus at different wheel speeds (150, 273 and 400rpm corresponding to linear speeds of 1.79, 3.26 and 4.78m/s respectively) for different sliding distances at a fixed load of 49N. Crushed silica sand particles of size ranging from 212 to 300 m were used as the abrasive medium. The wear rate of samples decreased progressively with sliding distance until a (nearly) steady-state condition was attained. This was considered to be due to abrasion-induced work hardening of subsurface regions as well as the greater tendency of protrusion of the harder martensite/pearlite phase at longer sliding distances, thereby providing greater resistance to wear. Decreasing wear rate with increasing treatment temperature 750–810°C could be attributed to the greater volume fraction of the hard martensite phase in the samples containing ferrite plus martensite. The lower wear rate observed in the case of the samples containing ferrite plus martensite over the annealed ones comprising ferrite and pearlite was attributed to the higher bulk hardness of the former. Increasing linear speed from 1.79 to 3.26m/s led to an increase in wear rate. This could be attributed to greater tendency of the abrasive particles to create deeper scratches and scouping (digging). A reduction in wear rate with a further increase in the linear speed from 3.26 to 4.78m/s could be due to a change in the mechanism of wear from predominantly sliding to rolling of the abrasive particles in view of the increased plastic deformability characteristics of the specimens due to higher frictional heating. The present investigation clearly suggests that it is possible to attain a desired combination of bulk hardness and microstructure (consisting of ferrite plus martensite) leading to optimum abrasion resistance in low-carbon steels. The quantity of the two phases in turn could be varied by suitably controlling the heat-treatment temperature.     

Virus Matryoshka: A Bacteriophage Particle—Guided Molecular Assembly Approach to a Monodisperse Model of the Immature Human Immunodeficiency Virus

Immature human immunodeficiency virus type 1 (HIV‐1) is approximately spherical, but is constructed from a hexagonal lattice of the Gag protein. As a hexagonal lattice is necessarily flat, the local symmetry cannot be maintained throughout the structure. This geometrical frustration presumably results in bending stress. In natural particles, the stress is relieved by incorporation of packing defects, but the magnitude of this stress and its significance for the particles is not known. In order to control this stress, we have now assembled the Gag protein on a quasi‐spherical template derived from bacteriophage P22. This template is monodisperse in size and electron‐transparent, enabling the use of cryo‐electron microscopy in structural studies. These templated assemblies are far less polydisperse than any previously described virus‐like particles (and, while constructed according to the same lattice as natural particles, contain almost no packing defects). This system gives us the ability to study the relationship between packing defects, curvature and elastic energy, and thermodynamic stability. As Gag is bound to the P22 template by single‐stranded DNA, treatment of the particles with DNase enabled us to determine the intrinsic radius of curvature of a Gag lattice, unconstrained by DNA or a template. We found that this intrinsic radius is far larger than that of a virion or P22‐templated particle. We conclude that Gag is under elastic strain in a particle; this has important implications for the kinetics of shell growth, the stability of the shell, and the type of defects it will assume as it grows.