Robust partial least squares regression: Part I,algorithmic developments

The work summarized in this paper presents the first part of a three‐paper series on robust partial least squares (RPLS) regression. Motivated by recent research activities in this area, this part provides a detailed algorithmic analysis of associated techniques, showing that existing work (i) may not represent a true robust formulation of partial least squares (PLS), (ii) may lead to convergence problems or (iii) may be insensitive to a certain type of outlier. On the basis of this analysis, Part I introduces a new conceptual RPLS algorithm that overcomes the deficiencies of existing work. The second part of this work details this new RPLS technique, compares its peformance with existing RPLS methods and provides an analysis on the computational efficiency and sensitivity of these algorithms. Whilst the first two parts of this work discuss algorithmic developments of RPLS, the final part concentrates on practical issues of RPLS implementations. This third part is devoted to practitioners of chemistry and chemical engineering covering a wide range of applications involving a calibration experiment, the analysis of recorded data from an industrial debutanizer process and data from a number of Raman spectroscopy experiments. Copyright © 2007 John Wiley & Sons, Ltd.     

The upward flow of air betweem two waterfalls: An unusual choked flow problem

An experimental and theoretical investigation of the effect of air rising between two opposed waterfalls is presented. It is found experimentally that as the air flow is increased, the waterfalls are drawn more closely together until a critical air flow rate is reached at which the waterfalls collapse together. A theoretical analysis of this phenomenon is presented and the collapse condition is shown to be analogous to the choked flow of air through a nozzle the cross-sectional area of which is strongly pressure dependent. This dependency results in a very low effective “sonic” velocity and “choked” flow and the theoretical predictions are in reasonable agreement with the experiment results. The relevance of this work to the PWR refill problem is discussed.     

Thermal analysis studies on the boron-potassium perchlorate-nitrocellulose pyrotechnic system

Studies have been carried out on the boron-potassium perchlorate-nitrocellulose pyrotechnic system by DSC, simultaneous TG-DTA-mass spectrometry and chemical analysis. Quantitative measurements have been made on the exothermic pre-ignition reaction which took place above 360°C and the results have been compared with those obtained previously for the corresponding systems containing zirconium and a zirconium/nickel alloy.     

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO2

We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO₂ reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron-hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO₂ to CO. The interfacial dynamics and catalytic behavior are clearly revealed by time-resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine-captured CO₂, namely carbamates, for direct photochemical conversion without additional energy input.     

Synthesis of novel hydrophobically modified water soluble polymers by ring-opening metathesis polymerization

Ring-opening metathesis polymerization has been used to prepare a series of water soluble polymers based on the Diels-Alder adducts of furan and cyclopentadiene. Hydrophobically modified forms of these polymers were obtained either by copolymerization with 5-decylbicyclo[2.2.1]hept-2-ene, post-polymerization modification of the acid forms of the polymers with 1-decylamine or chain transfer to 1-hexadecene. Polymers were characterized by NMR specroscopy and viscometry.     

Vacuum moulding of a superplastic in two dimensions

A mathematical model is proposed for the process of vacuum superplasticforming. The model exploits the fact that in most industrialapplications the sheet aspect ratio (thickness/sheet width)is small. After an initial consideration of some of the moregeneral properties and the literature of superplastic materials,the elastic/plastic deformation of an internally-inflated thin-walledcylinder is examined. Plates of arbitrary geometry are thenconsidered. A quasisteady model in which the sheet moves througha sequence of steady states is developed. Some simplified closed-formsolutions are examined, but for general cases a system of nonlinearpartial differential equations must be solved numerically. Anefficient and accurate semi-explicit numerical scheme is proposedand a simplified stability analysis is presented; the methodis then used to compute properties of superplastic vacuum mouldedsheets in a number of practically motivated cases.     

Constraints, Constitutive Limits, and Instability in Finite Thermoelasticity

This paper examines all the possible types of thermomechanical constraints in finite-deformational elasticity. By a thermomechanical constraint we mean a functional relationship between a mechanical variable, either the deformation gradient or the stress, and a thermal variable, temperature, entropy or one of the energy potentials; internal energy, Helmholtz free energy, Gibbs free energy or enthalpy. It is shown that for the temperature-deformation, entropy-stress, enthalpy-deformation, and Helmholtz free energy-stress constraints equilibrium states are unstable, in the sense that certain perturbations of the equilibrium state grow exponentially. By considering the constrained materials as constitutive limits of unconstrained materials, it is shown that the instability is associated with the violation of the Legendre–Hadamard condition on the internal energy. The entropy-deformation, temperature-stress, internal energy-stress, and Gibbs free energy-deformation constraints do not exhibit this instability. It is proposed that stability of the rest state (or equivalently convexity of internal energy) is a necessary requirement for a model to be physically valid, and hence entropy-deformation, temperature-stress, internal energy-stress, and Gibbs free energy-deformation constraints are physical, whereas temperature-deformation constraints (including the customary notion of thermal expansion that density is a function of temperature only), entropy-stress constraints, enthalpy-deformation constraints, and Helmholtz free energy-stress constraints are not.     

The Effect of High Fat Diet on Cerebrovascular Health and Pathology: A Species Comparative Review

In both humans and animal models, consumption of a high-saturated-fat diet has been linked to vascular dysfunction and cognitive impairments. Laboratory animals provide excellent models for more invasive high-fat-diet-related research. However, the physiological differences between humans and common animal models in terms of how they react metabolically to high-fat diets need to be considered. Here, we review the factors that may affect the translatability of mechanistic research in animal models, paying special attention to the effects of a high-fat diet on vascular outcomes. We draw attention to the dissociation between metabolic syndrome and dyslipidemia in rodents, unlike the state in humans, where the two commonly occur. We also discuss the differential vulnerability between species to the metabolic and vascular effects of macronutrients in the diet. Findings from animal studies are better interpreted as modeling specific aspects of dysfunction. We conclude that the differences between species provide an opportunity to explore why some species are protected from the detrimental aspects of high-fat-diet-induced dysfunction, and to translate these findings into benefits for human health.