Search

Sample preparation and instrument parameters have regularly been demonstrated to impact upon the observed results in atmospheric pressure photoionization, mass spectrometry (MS), and analytical techniques in general but may be overlooked when such methods are applied to the characterization of real-world samples. An initial investigation into different solvent systems demonstrated that the inclusion of ethyl acetate inverted the ratio of relative intensities of radical and protonated species (R/P). Design of experiments was performed and indicated that the injection flow rate is also a significant factor. The impact of the solvent system and flow rate on signal intensity, the observed compositional profile, and R/P of selected molecular groups is demonstrated further. An inversion of R/P is observed at higher flow rates in solvent systems commonly used in petroleomics studies, effecting a loss of molecular speciation. The findings presented reiterate the critical importance in considering experimental parameters when interpreting the results of analytical procedures.

This paper explores the development of Augmented Spaces that involve embedding within the built environment, digitally responsive recognition of human presence. Contemporary digital media provides the opportunity to enhance physical space with the property of immediate interaction, which results in a high level of user engagement and responsiveness. Through the addition of digital media, emotional and reflective value can be added to the built form. If space is designed to be reactive, rather than passive, a dialogue can be established between the user/inhabitant and the environment. We report on the establishment and analysis of a set of prototype digital interventions in urban space that react to human presence. One is in a building threshold space; one an urban street. We describe the development of a digital particle system with two inputs; the first being the geometry that generates the particles and the second being the geometry that displaces the particles. The research goals that we report on are driven by three overriding response criteria, Visceral, Behavioural and Reflective.

Radical polymers are an emerging class of non-conjugated, charge-conducting macromolecules that are capable of transporting charge through localized oxidation–reduction (redox) reactions that occur at the stable radical groups present as the pendant groups of the macromolecular chains. The chemical nature and oxidation state of these pendant radical groups are critical to the charge transporting abilities of radical polymers in the solid state. To date, however, the control of this chemistry has been limited to external oxidizing agents, and the concept of intramolecular dopants has not been explored fully. To this end, we have synthesized poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-co-poly(vinylsulfonic acid sodium salt) (PTMA-co-PVS). Then, electron paramagnetic resonance spectroscopy and attenuated total reflectance-Fourier transform infrared spectroscopy are implemented to evaluate the exact chemical nature of the pendant groups as a function of the PVS intramolecular dopants and exposure of the materials to external oxidation reactions. We correlate these changes in pendant group chemistry to charge transport ability, and we establish that the inclusion of a moderate amount of PVS dopants can improve the solid-state hole mobility of the material. Conversely, a large amount of sulfonic acidic dopants can be detrimental to the transport of the polymer relative to the homopolymer PTMA. Therefore, refinement of pendant group chemistry and careful addition of intramolecular dopants can enhance the solid-state transport ability of a radical polymer system. These fundamental principles, in turn, provide a vital foothold by which to optimize the solid-state charge transporting ability of current and next-generation radical polymer designs.

To determine an appropriate empiric oral sirolimus dose adjustment when given concurrently with posaconazole oral suspension in patients who undergo hematopoietic stem cell transplant (HSCT).Retrospective cohort study.Comprehensive cancer center in the United States.Seventy five allogeneic HSCT patients who received posaconazole oral suspension and oral sirolimus concurrently between 2009 and 2011.Sirolimus concentrations were recorded at baseline and for up to 28 days after posaconazole initiation. The sirolimus concentration/dose (C/D) ratio was determined for each sirolimus concentration obtained. Following analysis of patient data and based on the initial empiric sirolimus dose reduction, patients were stratified into two groups: ≥50% sirolimus dose reduction (Group 1) and50% sirolimus dose reduction (Group 2). The mean sirolimus C/D ratio was 2.29 ng/mL/mg prior to posaconzole initiation. Coadministration of posaconazole and sirolimus resulted in an increase in the steady state sirolimus C/D ratio to 6.24 ng/mL/mg, which occurred approximately 17-20 days after initiation of posaconazole. The mean maximum sirolimus concentration was significantly higher in Group 2 compared to Group 1 (12.64 ng/mL vs. 9.24 ng/mL, p=0.001). Significantly more patients in Group 2 than Group 1 experienced at least one sirolimus concentration15 ng/mL (27% vs. 2.6%, p=0.003).Coadministration of posaconazole oral suspension with oral sirolimus increases the sirolimus C/D ratio by approximately 2.7-fold in HSCT patients. An initial empiric oral sirolimus dose reduction between 50% and 65% may be recommended for most clinically stable patients with close sirolimus concentration monitoring for at least 3 weeks following posaconazole initiation.