Nonstationary Positive Definite Tapering On The Plane

A common problem in spatial statistics is to predict a random field f at some spatial location t ₀ using observations f(t ₁), …, f(t_n ) at . Recent work by Kaufman et al. and Furrer et al. studies the use of tapering for reducing the computational burden associated with likelihood-based estimation and prediction in large spatial datasets. Unfortunately, highly irregular observation locations can present problems for stationary tapers. In particular, there can exist local neighborhoods with too few observations for sufficient accuracy, while others have too many for computational tractability. In this article, we show how to generate nonstationary covariance tapers T(s, t) such that the number of observations in {t: T(s, t) > 0} is approximately a constant function of s. This ensures that tapering neighborhoods do not have too many points to cause computational problems but simultaneously have enough local points for accurate prediction. We focus specifically on tapering in two dimensions where quasi-conformal theory can be used. Supplementary materials for the article are available online.     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.     

Polymeric coacervate coating for flame retardant paper

Cellulose - Cellulosic paper (from wood fibers) is a highly flammable material that is used in corrugated carboard, packaging, printing, and construction. While there is significant work focused on...     

Supramolecular liquid crystals displaying competitive hydrogen bonding: Small molecule mesogens assembled through different hydrogen bond assemblies

A series of supramolecular assemblies created through competitive hydrogen bonding of a n-alkoxy benzoic acid hydrogen bond donor and a mixture of hydrogen bond acceptors: a liquid crystal-forming rigid bi-pyridyl and a non-mesogenic tetrafunctional pyridyl species. The associative chain structures displayed mesogenic characteristics at loadings dependent on the concentration of the disruptive tetrafunctional agent- systems eliminated liquid crystallinity at 85% inclusion in heating transitions and 90% in cooling. The assembled structures displayed considerable mesophase stability. This was observed through long liquid crystalline lifetimes even at high compositions of 4PD, which generally dampened due to a generalized eutectic effect. It is believed that the freedom of mobility inherent in the C8 Acid allows for the reorganization of the hydrogen bonds in the liquid crystalline state providing for a very high loading of disruptor and long mesophase lifetimes.     

Mapping the fly Malpighian tubule lipidome by imaging mass spectrometry

Matrix‐assisted laser/desorption ionization imaging mass spectrometry (MALDI IMS) is an analytical technique for understanding the spatial distribution of biomolecules across a sample surface. Originally employed for mammalian tissues, this technology has been adapted to study specimens as diverse as microbes and cell cultures, food such as strawberries, and invertebrates including the vinegar fly Drosophila melanogaster. As an ideal model organism, Drosophila has brought greater understanding about conserved biological processes, organism development, and diseased states and even informed management practices of agriculturally and environmentally important species. Drosophila displays anatomically separated renal (Malpighian) tubules that are the physiological equivalent to the vertebrate nephron. Insect Malpighian tubules are also responsible for pesticide detoxification. In this article, we first describe an effective workflow and sample preparation method to study the phospholipid distribution of the Malpighian tubules that initially involves the manual microdissection of the tubules in saline buffer followed by a series of washes to remove excess salt and enhances the phospholipid signals prior to matrix deposition and IMS at 25‐μm spatial resolution. We also established a complementary methodology for lipid IMS analysis of whole‐body fly sections using a dual‐polarity data acquisition approach at the same spatial resolution after matrix deposition by sublimation. Both procedures yield rich signal profiles from the major phospholipid classes. The reproducibility and high‐quality results offered by these methodologies enable cohort studies of Drosophila through MALDI IMS.     

Chiral separation of benzoporphyrin derivative mono- and diacids by laser induced fluorescence-capillary electrophoresis

A method for the separation of benzoporphyrin derivative mono- and diacid (BPDMA, BPDDA) enantiomers by laser induced fluorescence-capillary electrophoresis (LIF-CE) has been developed. By using 300 mM borate buffer, pH 9.2, 25 mM sodium cholate and 10% acetronitrile as electrolyte, +10 kV electrokinetic sampling injection of 2 s and an applied +20 kV voltage across the ends of a 37 cm capillary (30 cm to the detector, 50 microm ID), all six BPD stereoisomers were baseline-separated within 20 min. Formation constants, free electrophoretic and complexation mobilities with borate and cholate were determined based on dynamic complexation capillary electrophoresis theory. The BPD enantiomers can be quantitatively determined in the range of 10(-2)-10(-5) mg mL(-1). The correlation coefficients (r2) of the least-squares linear regression analysis of the BPD enantiomers are in the range of 0.9914-0.9997. Their limits of detection are 2.18-3.5 x 10(-3) mg mL(-1). The relative standard deviations for the separation were 2.90-4.64% (n = 10). In comparison with high-performance liquid chromatography (HPLC), CE has better resolution and efficiency. This separation method was successfully applied to the BPD enantiomers obtained from a matrix of bovine serum and from liposomally formulated material as well as from studies with rat, dog and human microsomes.     

Cross-metathesis reactions of vinyl-chlorins and -porphyrins catalyzed by a "second generation" Grubbs' catalyst

The first application of olefin cross-metathesis with vinylchlorins and vinylporphyrins using a "second generation" Grubbs' catalyst is reported. Cross-metathesis products were obtained in good yields with high E-stereoselectivity.     

An efficient synthesis of a probe for protein function: 2,3-diaminopropionic acid with orthogonal protecting groups

[reaction: see text] An efficient and cost-effective synthesis of N(alpha)-Boc2-N(beta)-Cbz-2,3-diaminopropionic acid is reported. The synthesis starts from commercially available N(alpha)-Boc-Asp(OBn)-OH and employs a Curtius rearrangement to establish the beta-nitrogen. Proper protection of the alpha-nitrogen is essential for the success of the Curtius rearrangement.     

Graphene Defects in Saccharide Carbon Dots Govern Electrochemical Sensitivity

Galactose (Gal), lactose (Lac), and glucose (Glu) derived carbon dots (CDs) were evaluated for their utility as electrochemical sensing composites using acetaminophen (APAP) as a probe molecule. The goal of this work is to ascertain the role of graphene defects on electrochemical activity. Higher sp²-to-sp³ hybridized carbon ratios (in parentheses) in the CDs correlated with higher sensitivity in the order according to measured Raman I_G/I_D intensities: GluCDs (6.53)<LacCDs (9.30)<GalCDs (10.18). A dynamic measurement in the 0–2.0 mmol dm⁻³ APAP range at pH=7.0 was achieved, suitable for practical APAP toxicity monitoring. Defect density within the GalCDs provided the highest sensitivity.