Model Reactions Involving Ester Functional Groups during Thermo‐Oxidative Degradation of Biodiesel

Biodiesel is a renewable fuel used in diesel engines that is typically blended with diesel fuel. However, biodiesel is susceptible to oxidation, which has the potential to produce higher molecular weight materials that may adversely impact vehicle fuel‐system performance. To investigate the chemical reactions potentially important in biodiesel oxidation, four different types of chemical reactions involving esters were studied: (1) ester formation (reactions of acids with alcohols), (2) alcoholysis (reactions of alcohols with esters), (3) acidolysis (reaction of acids with esters), and (4) ester exchange (reactions between two esters). Experiments with representative model compounds were used to evaluate these reactions at 90 °C with aeration; conditions previously used to simulate thermo‐oxidative degradation during biodiesel aging. Reactions were monitored using gas chromatography, fourier transform infrared (FTIR) spectroscopy, and total acid number (TAN). Evidence is presented suggesting that alcoholysis and ester formation (Reactions 1 and 2), catalyzed by carboxylic acids, are important reactions of esters that could lead to larger molecules. Acidolysis (Reaction 3) proceeded at a comparatively slow rate and ester exchange reaction products (Reaction 4) were not detected under these aging conditions.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/151841/1/aocs12277_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/151841/2/aocs12277.pd

Metastable and localized Ising magnetism in α−CoV2O6 magnetization plateaus

$\alpha$-CoV$_{2}$O$_{6}$ consists of $j_{\mathrm{eff}}={1 \over 2}$ Ising spins located on an anisotropic triangular motif with magnetization plateaus in an applied field. We combine neutron diffraction with low temperature magnetization to investigate the magnetic periodicity in the vicinity of these plateaus. We find these steps to be characterized by metastable and spatially short-range ($\xi\sim$ 10 $\r{A}$) magnetic correlations with antiphase boundaries defining a local periodicity of $\langle \hat{T}^{2} \rangle =\ \uparrow \downarrow$to$\langle \hat{T}^{3} \rangle =\ \uparrow \uparrow \downarrow$, and$\langle \hat{T}^{4} \rangle=\ \uparrow \uparrow \downarrow \downarrow$or$\uparrow \uparrow \uparrow \downarrow$ spin arrangements. This shows the presence of spatially short range and metastable/hysteretic, commensurate magnetism in Ising magnetization steps.Comment: 9 pages, 6 figures, to be published in Phys. Rev.

BCS to Bose Crossover in Anisotropic Superconductors

In this work we use functional integral techniques to examine the nearest neighbour attractive Hubbard model on a quasi-2D lattice. It is a simple phenomenological model for the high-Tc cuprates that allows both extended (non-local) s- and d-wave singlet superconductivity as well as mixed symmetry states. The Hartree-Gor'kov mean field theory of the model has a finite temperature phase diagram which shows a transition from pure s-wave to pure d-wave superconductivity, via a mixed symmetry s+id state, as a function of doping. Including Gaussian fluctuations we examine the crossover from weak-coupling BCS superconductivity to the strong-coupling Bose-Einstein condensation of composite s- or d-wave bosons and comment on the origin and symmetry of the pseudogap.Comment: 20 pages inc. 13 figure

Viral inhibition of bacterial phagocytosis by human macrophages: redundant role of CD36

Macrophages are essential to maintaining lung homoeostasis and recent work has demonstrated that influenza-infected lung macrophages downregulate their expression of the scavenger receptor CD36. This receptor has also been shown to be involved in phagocytosis of Streptococcus pneumoniae, a primary agent associated with pneumonia secondary to viral infection. The aim of this study was to investigate the role of CD36 in the effects of viral infection on macrophage phagocytic function. Human monocyte-derived macrophages (MDM) were exposed to H3N2 X31 influenza virus, M37 respiratory syncytial virus (RSV) or UV-irradiated virus. No infection of MDM was seen upon exposure to UV-irradiated virus but incubation with live X31 or M37 resulted in significant levels of viral detection by flow cytometry or RT-PCR respectively. Infection resulted in significantly diminished uptake of S. pneumoniae by MDM and significantly decreased expression of CD36 at both the cell surface and mRNA level. Concurrently, there was a significant increase in IFN? gene expression in response to infection and we observed a significant decrease in bacterial phagocytosis (p = 0.031) and CD36 gene expression (p = 0.031) by MDM cultured for 24 h in 50IU/ml IFN?. Knockdown of CD36 by siRNA resulted in decreased phagocytosis, but this was mimicked by transfection reagent alone. When MDM were incubated with CD36 blocking antibodies no effect on phagocytic ability was observed. These data indicate that autologous IFN? production by virally-infected cells can inhibit bacterial phagocytosis, but that decreased CD36 expression by these cells does not play a major role in this functional deficiency

Infrared absorption cross-sections in HITRAN2016 and beyond: expansion for climate, environment, and atmospheric applications

Spectroscopic analysis of hydrocarbons, halocarbons and related species is required in atmospheric applications such as climate-change research, tracking of pollution and biomass burning, and remote sensing. Critically evaluated line-by-line spectroscopic data are needed for such analyses. To address this need we report the large addition of spectra to the HITRAN2016 database. This extension increases the number of molecules in the database by almost a factor of 6 from that in HITRAN2012. Spectra from the Pacific Northwest National Laboratory database (Appl. Spectrosc. 2004;58:1452–61) and the Hodnebrog et al. compilation (Rev Geophys 2013;51:300–78) have been integrated into HITRAN2016. Spectra from high-resolution laboratory observations, predominantly from Fourier transform spectrometers, are now provided for 328 compounds in the IR spectral range. Spectra for atmospherically-important compounds organized by chemical category are presented. The HITRAN infrastructure (www.hitran.org), HITRAN Application Programming Interface (HAPI), and best practices for searching and downloading data are discussed

Cosmological distance indicators

We review three distance measurement techniques beyond the local universe: (1) gravitational lens time delays, (2) baryon acoustic oscillation (BAO), and (3) HI intensity mapping. We describe the principles and theory behind each method, the ingredients needed for measuring such distances, the current observational results, and future prospects. Time delays from strongly lensed quasars currently provide constraints on $H_0$ with < 4% uncertainty, and with 1% within reach from ongoing surveys and efforts. Recent exciting discoveries of strongly lensed supernovae hold great promise for time-delay cosmography. BAO features have been detected in redshift surveys up to z <~ 0.8 with galaxies and z ~ 2 with Ly-$\alpha$ forest, providing precise distance measurements and $H_0$ with < 2% uncertainty in flat $\Lambda$CDM. Future BAO surveys will probe the distance scale with percent-level precision. HI intensity mapping has great potential to map BAO distances at z ~ 0.8 and beyond with precisions of a few percent. The next years ahead will be exciting as various cosmological probes reach 1% uncertainty in determining $H_0$, to assess the current tension in $H_0$ measurements that could indicate new physics.Comment: Review article accepted for publication in Space Science Reviews (Springer), 45 pages, 10 figures. Chapter of a special collection resulting from the May 2016 ISSI-BJ workshop on Astronomical Distance Determination in the Space Ag

Gravitational Lensing at Millimeter Wavelengths

With today's millimeter and submillimeter instruments observers use gravitational lensing mostly as a tool to boost the sensitivity when observing distant objects. This is evident through the dominance of gravitationally lensed objects among those detected in CO rotational lines at z>1. It is also evident in the use of lensing magnification by galaxy clusters in order to reach faint submm/mm continuum sources. There are, however, a few cases where millimeter lines have been directly involved in understanding lensing configurations. Future mm/submm instruments, such as the ALMA interferometer, will have both the sensitivity and the angular resolution to allow detailed observations of gravitational lenses. The almost constant sensitivity to dust emission over the redshift range z=1-10 means that the likelihood for strong lensing of dust continuum sources is much higher than for optically selected sources. A large number of new strong lenses are therefore likely to be discovered with ALMA, allowing a direct assessment of cosmological parameters through lens statistics. Combined with an angular resolution <0.1", ALMA will also be efficient for probing the gravitational potential of galaxy clusters, where we will be able to study both the sources and the lenses themselves, free of obscuration and extinction corrections, derive rotation curves for the lenses, their orientation and, thus, greatly constrain lens models.Comment: 69 pages, Review on quasar lensing. Part of a LNP Topical Volume on "Dark matter and gravitational lensing", eds. F. Courbin, D. Minniti. To be published by Springer-Verlag 2002. Paper with full resolution figures can be found at ftp://oden.oso.chalmers.se/pub/tommy/mmviews.ps.g

Trajectory generation for autonomous soaring UAS

This article was published in the International Journal of Automation and Computing [© Springer Verlag and the Institute of Automation, Chinese Academy of Sciences ]. The definitive version is available at: http://link.springer.com/article/10.1007/s11633-012-0641-5As unmanned aerial vehicles are expected to do more and more advanced tasks, improved range and persistence is required. This paper presents a method of using shallow layer cumulus convection to extend the range and duration of small unmanned aerial vehicles. A simulation model of an X-models XCalubur electric motor-glider is used in combination with a refined 4D parametric thermal model to simulate soaring flight. The parametric thermal model builds on previous successful models with refinements to more accurately describe the weather in northern Europe. The implementation of the variation of the MacCready setting is discussed. Methods for generating efficient trajectories are evaluated and recommendations are made regarding implementation

Tropospheric Ozone Assessment Report : A critical review of changes in the tropospheric ozone burden and budget from 1850 to 2100

Our understanding of the processes that control the burden and budget of tropospheric ozone has changed dramatically over the last 60 years. Models are the key tools used to understand these changes, and these underscore that there are many processes important in controlling the tropospheric ozone budget. In this critical review, we assess our evolving understanding of these processes, both physical and chemical. We review model simulations from the International Global Atmospheric Chemistry Atmospheric Chemistry and Climate Model Intercomparison Project and Chemistry Climate Modelling Initiative to assess the changes in the tropospheric ozone burden and its budget from 1850 to 2010. Analysis of these data indicates that there has been significant growth in the ozone burden from 1850 to 2000 (approximately 43 + 9%) but smaller growth between 1960 and 2000 (approximately 16 +/- 10%) and that the models simulate burdens of ozone well within recent satellite estimates. The Chemistry Climate Modelling Initiative model ozone budgets indicate that the net chemical production of ozone in the troposphere plateaued in the 1990s and has not changed since then inspite of increases in the burden. There has been a shift in net ozone production in the troposphere being greatest in the northern mid and high latitudes to the northern tropics, driven by the regional evolution of precursor emissions. An analysis of the evolution of tropospheric ozone through the 21st century, as simulated by Climate Model Intercomparison Project Phase 5 models, reveals a large source of uncertainty associated with models themselves (i.e., in the way that they simulate the chemical and physical processes that control tropospheric ozone). This structural uncertainty is greatest in the near term (two to three decades), but emissions scenarios dominate uncertainty in the longer term (2050- 2100) evolution of tropospheric ozone. This intrinsic model uncertainty prevents robust predictions of near-term changes in the tropospheric ozone burden, and we review how progress can be made to reduce this limitation

United Nations Environment Programme (UNEP), Plastics in the environment in the context of UV radiation, climate change and the Montreal Protocol. 2023 Assessment Update of the UNEP Environmental Effects Assessment Panel

This Assessment Update by the Environmental Effects Assessment Panel (EEAP) of the United Nations Environment Programme (UNEP) considers the interactive effects of solar UV radiation, global warming, and other weathering factors on plastics. The Assessment illustrates the significance of solar UV radiation in decreasing the durability of plastic materials, degradation of plastic debris, formation of micro- and nanoplastic particles and accompanying leaching of potential toxic compounds. Micro- and nanoplastics have been found in all ecosystems, the atmosphere, and in humans. While the potential biological risks are not yet well-established, the widespread and increasing occurrence of plastic pollution is reason for continuing research and monitoring. Plastic debris persists after its intended life in soils, water bodies and the atmosphere as well as in living organisms. To counteract accumulation of plastics in the environment, the lifetime of novel plastics or plastic alternatives should better match the functional life of products, with eventual breakdown releasing harmless substances to the environment