COMPONENTS OF PREDICTION ERRORS FOR A STATIONARY PROCESS WITH ESTIMATED PARAMETERS

Abstract. An alternative approach to the estimation of prediction error using linear time series models, whose parameters are also estimated, is presented. Recurrence relationships are given which are rather less unwieldy operationally than the Kronecker matrix forms used by Yamamoto and Reinsel. We extend somewhat the class of models to other than the purely finite autoregressive models studied by these authors.     

Carbohydrate polymers of chirata (Swertia chirata) leaves: Structural features, in vitro anti-oxidant activity and fluorescence quenching study

Chirata (Swertia chirata) is widely used in Indian folk medicine for the prevention of various disorders. Herein, we analyzed the water-extracted carbohydrate polymer (WECP) of this herb using chemical, chromatographic, and spectroscopic methods. The anti-oxidant capacity of this fraction was studied by ferric reducing anti-oxidant power (FRAP) and DPPH radical assays. Effect of WECP on bovine serum albumin spectrum (BSA) was determined using excitation wavelength of 282 nm. Anion exchange chromatography of WECP yielded 5 fractions (F1–F5) with different chemical compositions. The major fraction (F5) was homogeneous, had an apparent molecular mass of 4.5 kDa, and contains both carbohydrates (57%) and phenolics (34%). The anti-oxidant capacities of WECP and F5 were comparable to standard anti-oxidants. Notably, activities of the carbohydrate polymers (F1–F5) correlate with their phenolics content. Fluorescence quenching measurement suggests that F5 can form complex with BSA and the value of the binding constant is K=6.28×10⁵/M.     

Chemistry of small organic molecules on snow grains: the applicability of artificial snow for environmental studies

The utilization of artificial snow for environmentally relevant (photo)chemical studies was systematically investigated. Contaminated snow samples were prepared by various methods: by shock freezing of the aqueous solutions sprayed into liquid nitrogen or inside a large walk-in cold chamber at -35 °C, or by adsorption of gaseous contaminants on the surface of artificially prepared pure or natural urban snow. The specific surface area of artificial snow grains produced in liquid nitrogen was determined using valerophenone photochemistry (400-440 cm(2) g(-1)) to estimate the surface coverage by small hydrophobic organic contaminants. The dynamics of recombination/dissociation (cage effect) of benzyl radical pairs, photochemically produced from 4-methyldibenzyl ketone on the snow surface, was investigated. The initial ketone loading, c = 10(-6)-10(-8) mol kg(-1), only about 1-2 orders of magnitude higher than the contaminant concentrations commonly found in nature, was already well below monolayer coverage. We found that the efficiency of out-of-cage reactions decreased at much higher temperatures than those previously determined for frozen solutions; however, the cage effect was essentially the same no matter what technique of snow production or ketone deposition/uptake was used, including the experiments with collected natural snow. The experimental observation that the contaminant molecules are initially self-associated even at the lowest concentrations was supported by DFT calculations. We conclude that, contrary to frozen aqueous solutions, in which the impurities reside in a 3D cage (micropocket), contaminant molecules located on the artificial snow grain surface at low concentrations can be visualized in terms of a 2D cage. Artificial snow thus represents a readily available study matrix that can be used to emulate the natural chemical processes of trace contaminants occurring in natural snow.     

A generalist herbivore in a specialist mode Metabolic,sequestrative, and defensive consequences

Adults of a generalist herbivore, the lubber grasshopper,Romalea guttata, can be converted to functional specialists by feeding them exclusively on catnip,Nepeta cataria. No obvious adverse effects on adult development resulted from this enforced monophagy. Notwithstanding the fact thatR. guttata has had no coevolutionary relationship with this Eurasian mint, it readily sequesters compounds that are identical to or derived from the terpenoid lactones that are characteristic ofN. cataria. R. guttata appears to both biomagnify minor allelochemicals and to sequester metabolites of theNepeta terpenes in its paired defensive glands. The levels of autogenously produced phenolics are not affected by feeding onN. cataria and the defensive secretions of catnip-fed grasshoppers are more repellent to ants than those of wild-fed acridids. Metabolites of theN. cataria monoterpenes are sequestered in the defensive glands when catnip is added to the natural diet ofR. guttata. The ability of a generalist,R. guttata, to facilely bioaccumulate a potpourri of foreign allelochemicals when feeding in a specialist mode is analyzed in terms of its biochemical, physiological, and functional significance. Sequestration is examined as a response to the enteric effronteries represented by the phytochemicals that can be characteristic of the overload in a monophagous diet.     

Glass Formation and Properties in the System Calcia-Gallia-Silica

The glass-formation region of the calcia-gallia-silica system was determined. The glasses within this region were measured to have a density of 3 to 4 g/cm³, a refractive index of 1.6 to 1.73, an Abbe number between 35 and 58, a thermal expansion coefficient of 6.5 × 10⁻⁷/°C to 11.5 × 10⁻⁷/°C, softening temperatures between 730° and 790°C, and a Vickers microhardness of 5.2 to 7.3 GPa. Crystalline phases were identified along the glass-formation boundary. Infrared transmission spectra were used to explain glass structures and their effect on glass properties. The results suggest that the role of calcia in the glass structure is similar to that for calcia in calcium aluminosilicate glasses.     

Color and Selected Properties of PbO─BiO1.5─GaO1.5 Glasses

The density; molar volume; thermal expansion coefficient; dissolution rate in water, HC1, and NaOH; glass transition and crystallization temperatures; and the absorption edge in the ultraviolet-visible and infrared were measured for PbO─BiO1.5─GaO1.5 glasses. The range of compositions investigated was x PbO (100 − (x + y) )BiO_1.5. yGaO_1.5 for x between 20 and 60 cat% and y of 20, 25, 30, and 35 cat%. The glass-forming tendency increased with increased GaO_1.5 and decreased with increased PbO or BiO_1.5. The compositional dependence of these properties was consistent with the weight, size, charge, and bond strength of the cations. The Ga^{3 +} ions in these glasses are believed to act primarily as network-forming cations, whereas the majority of the Bi³⁺ and Pb²⁺ ions behave as network-modifying cations. It is suggested that a small friction of the lead ions are present as Pb⁴⁺. Depending upon melting conditions, these glasses ranged in color from brown to yellow. Various attempts, including containerless melting, were made to obtain colorless glasses, but no conditions were found which totally eliminated the color. The least color (pale yellow) was obtained when the glasses were melted in an air or nitrogen atmosphere in an alumina or gold crucible.     

Modelling of addition polymerization processes — Free radical,ionic, group transfer,and ziegler–natta kinetics

A brief review of addition polymerization processes is presented with a summary of the key characteristics classified by kinetic mechanism (free-radical, anionic, cationic, group transfer, or Ziegler–Natta), phase behavior, and reactor type. A practical approach to modelling in the industrial R & D environment is discussed in terms of a CAD package for polymerization processes.     

A microscopic model for catalytic surfaces—I. Catalytic wires and gauzes

A new “fuzzy wire” model of catalytic wires and gauzes is presented which is in good agreement with observed ignition, extinction, and flickering phenomena. The model predicts both simple harmonic oscillations as well as a wide variety of nonperiodic chaotic oscillations. Quantitative comparisons with data for butane oxidation and cyclohexene oxidation are quite good; however, the very long period oscillations observed for H₂ and CO oxidation are not predicted by the simplest forms of the model.