Optimized preprocessing of ultra-performance liquid chromatography/mass spectrometry urinary metabolic profiles for improved information recovery

Ultra-performance liquid chromatography coupled to mass spectrometry (UPLC/MS) has been used increasingly for measuring changes of low molecular weight metabolites in biofluids/tissues in response to biological challenges such as drug toxicity and disease processes. Typically samples show high variability in concentration, and the derived metabolic profiles have a heteroscedastic noise structure characterized by increasing variance as a function of increased signal intensity. These sources of experimental and instrumental noise substantially complicate information recovery when statistical tools are used. We apply and compare several preprocessing procedures and introduce a statistical error model to account for these bioanalytical complexities. In particular, the use of total intensity, median fold change, locally weighted scatter plot smoothing, and quantile normalizations to reduce extraneous variance induced by sample dilution were compared. We demonstrate that the UPLC/MS peak intensities of urine samples should respond linearly to variable sample dilution across the intensity range. While all four studied normalization methods performed reasonably well in reducing dilution-induced variation of urine samples in the absence of biological variation, the median fold change normalization is least compromised by the biologically relevant changes in mixture components and is thus preferable. Additionally, the application of a subsequent log-based transformation was successful in stabilizing the variance with respect to peak intensity, confirming the predominant influence of multiplicative noise in peak intensities from UPLC/MS-derived metabolic profile data sets. We demonstrate that variance-stabilizing transformation and normalization are critical preprocessing steps that can benefit greatly metabolic information recovery from such data sets when widely applied chemometric methods are used.     

Contribution of ozone to airborne aldehyde formation in Paris homes

Indoor aldehydes may result from ozone-initiated chemistry, mainly documented by experimental studies. As part of an environmental investigation included in the PARIS birth cohort, the aim of this study was to examine ozone contribution to airborne aldehyde formation in Paris homes. Formaldehyde, acetaldehyde and hexaldehyde levels, as well as styrene, nitrogen dioxide and nicotine concentrations, comfort parameters and carbon dioxide levels, were measured twice during the first year of life of the babies. Ambient ozone concentrations were collected from the closest background station of the regional air monitoring network. Traffic-related nitrogen oxide concentrations in front of the dwellings were estimated by an air pollution dispersion model. Home characteristics and families' way of life were described by questionnaires. Stepwise multiple linear regression models were used to link aldehyde levels with ambient ozone concentrations and a few aldehyde precursors involved in oxidation reactions, adjusting for other indoor aldehyde sources, comfort parameters and traffic-related nitrogen oxides. A 4 and 11% increase in formaldehyde and hexaldehyde levels was pointed out when 8-hour ozone concentrations increased by 20 μg/m³. The influence of potential precursors such as indoor styrene level and frequent use of air fresheners, containing unsaturated volatile organic compounds as terpenes, was also found. Thus, our results suggest that ambient ozone can significantly impact indoor air quality, especially with regard to formaldehyde and hexaldehyde levels.     

Solution Processing Route to Multifunctional Titania Thin Films: Highly Conductive and Photcatalytically Active Nb:TiO2

This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO₂) films from the decomposition of Ti(OEt)₄ with dopant quantities of Nb(OEt)₅ by aerosol‐assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n‐type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO₂ films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 10²¹ cm^?3 with a mobility of 2 cm² V^–1 s^–1 . The corresponding sheet resistance is as low as 6.5 Ω sq^–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO₂ films synthesized by vapour deposition. The doped films are also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO₂ lattice. Computational methods also confirmed experimental results of both delocalized (Ti⁴⁺) and localized polaronic states (Ti³⁺) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO₂ combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.     

A general doubly curved laminate shell theory

The aim of the work summarized in this paper is the theoretical modelling of laminated composite shells of arbitrary shape, in order to: improve the calculus of shear stresses, and especially to avoid shear correction factors; account for continuity conditions of displacements and transverse shear stresses at layer interfaces as well as compatibility conditions of transverse shear stresses on the bonding surfaces; estimate the relevance of shear refinements, of membrane refinements and of the transverse stretching beyond standard kinematics; and to analyse the sensitivity to edge effects for significant boundary conditions.     

Sustainable development from rhetoric to practice? A New Zealand perspective

This article explores the changing conceptions of sustainable development with reference to planning policy and practice in New Zealand. In 1991, when New Zealand introduced its Resource Management Act 1991, the country was seen as being a leader internationally in promoting sustainable development planning approaches. Twelve years later the early optimism has waned and New Zealand is if anything now a laggard rather than a leader in this field. This article explores the ambivalent and uneven relationship with sustainable development that has been evident in central government and within local government planning practice in New Zealand. It goes on to examine the potential that the Long Term Council Community Plans, introduced in the new Local Government Act 2002, offer in delivering sustainable development and transcending the implementation gap between policy statements in support of sustainable development and practice. The example of the city of Dunedin, the first local authority in New Zealand to produce a Long Term Council Community Plan, is used to demonstrate some of the difficulties inherent in achieving sustainable development goals in practice.     

Kinetics of vanillin oxidation

Vanillin can be produced by oxidation of kraft lignin, with air, in alkaline medium. The optimal conditions for vanillin production strongly depend on pH and temperature. This paper addresses the effect of temperature and pH on vanillin degradation by oxidation. Experiments were carried out in a wide range of vanillin concentration, oxygen partial pressure, temperature and pH. Simple models are proposed to explain the observed rate of vanillin consumption under conditions of high alkalinity (pH>12) and lower alkalinity (pH<12). At pH>12,the reaction rate of vanillin oxidation is first order in dissolved oxygen concentration [O₂] and in vanillin concentration [C], i.e., (?r_C) ∝[O₂][C]; at pH<12, the rate is zero order in oxygen concentration and second order in vanillin concentration, i.e., (?r_C)∝f(pH)[C]².     

Nocturnal Hemodialysis in Australia

Background: Because home hemodialysis has long been a common Australian support modality, the advent of home‐based nocturnal hemodialysis (NHD) in Canada stimulated the extension of our existing home‐ and satellite‐based conventional hemodialysis (CHD) programs to NHD. As a result, the first government‐funded, home‐based, 6‐nights‐per‐week NHD program in Australia began in July 2001. Methods: Sixteen patients have been trained for NHD; 13 dialyzed at home 8 to 9 hr per night for 6 nights per week, whereas 3 preferred to train for NHD at home using an 8‐ to 9‐hr alternate‐night regime. Results: The program experience to March 1, 2003, was 655 patient‐weeks. Two patients had withdrawn for transplantation and 2 for social reasons, although 1 continues on alternate‐night NHD. There hade been no deaths. Ten patients had dialyzed without partners. All patients ceased phosphate binders at entry. Thirteen of 16 discontinued all antihypertensive drugs. There were no fluid or dietary restrictions. Phosphate was added to the dialysate to prevent hypophosphatemia. Pre‐ and postdialysis urea and phosphate levels were broadly within the normal ranges. All patients reported restorative sleep; similarly partners reported stable sleep patterns and noted improved mood, cognitive function, and marital relationships in their NHD partners. Preliminary cost analyses show that whereas consumables had doubled, and epoetin and iron expenditures had risen by 28.9%, other pharmaceutical costs had fallen by 47%, and nursing wage costs were 48% of the notional cost had these patients remained on CHD. Three patients on NHD were retired, 7 worked full‐time, 3 worked part‐time, and 3 drew disability support, whereas previously on CHD, 3 were retired, 3 had worked full‐time, 3 had worked part‐time, and 7 had drawn disability support. Conclusion: We believe that NHD is viable, safe, effective, and well accepted with significant lifestyle benefits and reemployment outcomes. Although initial setup costs are significant, NHD cost advantage over CHD progressively accrues as program numbers exceed 12 to 15 patients.