Immunological Detection of N‐formylkynurenine in Porphyrin‐Mediated Photooxided Lens α‐crystallin

Crystallin proteins are responsible for maintaining lens transparency and allowing the lens to focus light undistorted onto the retina. The α‐crystallins are the major lens crystallins, and function as both structural proteins and chaperones to protect all lens proteins from damage leading to lens deterioration. Because lens crystallin proteins do not turn over, the damage they accumulate can lead to cataracts, the world’s leading cause of blindness. Photosensitizing porphyrins can accumulate in the eye through either endogenous metabolism or through therapeutic or diagnostic procedures. Porphyrin buildup exacerbates lens aging through increased levels of singlet oxygen, resulting in protein polymerization and amino acid residue alteration. Tryptophans oxidize to kynurenine and N‐formylkynurenine (NFK) causing irreversible changes in the refractive index of the normally transparent lens, leading to development of cataracts. Additionally, NFK is itself a photosensitizer, and its presence exacerbates lens deterioration. This work uses anti‐NFK antiserum to study porphyrin‐facilitated photooxidation of α‐crystallin tryptophan residues. In vitro experiments show that four biologically interesting porphyrins mediate α‐crystallin polymerization and accumulation of both protein radicals and NFK. Confocal microscopy of cultured human lens epithelial cells indicates that while all four porphyrins photosensitize cellular proteins, not all oxidize the tryptophans of cellular α‐crystallin to NFK.     

Optimal Scaling of Random Walk Metropolis Algorithms with Non-Gaussian Proposals

The asymptotic optimal scaling of random walk Metropolis (RWM) algorithms with Gaussian proposal distributions is well understood for certain specific classes of target distributions. These asymptotic results easily extend to any light tailed proposal distribution with finite fourth moment. However, heavy tailed proposal distributions such as the Cauchy distribution are known to have a number of desirable properties, and in many situations are preferable to light tailed proposal distributions. Therefore we consider the question of scaling for Cauchy distributed proposals for a wide range of independent and identically distributed (iid) product densities. The results are somewhat surprising as to when and when not Cauchy distributed proposals are preferable to Gaussian proposal distributions. This provides motivation for finding proposal distributions which improve on both Gaussian and Cauchy proposals, both for finite dimensional target distributions and asymptotically as the dimension of the target density, d → ∞. Throughout we seek the scaling of the proposal distribution which maximizes the expected squared jumping distance (ESJD).     

Low loss broadband transmission in hypocycloid-core Kagome hollow-core photonic crystal fiber

We report on the fabrication of a seven-cell-core and three-ring-cladding large-pitch Kagome-lattice hollow-core photonic crystal fiber (HC-PCF) with a hypocycloid-shaped core structure. We demonstrate experimentally and theoretically that the design of this core shape enhances the coupling inhibition between the core and cladding modes and offers optical attenuation with a baseline of ～180?dB/km over a transmission bandwidth larger than 200?THz. This loss figure rivals the state-of-the-art photonic bandgap HC-PCF while offering an approximately three times larger bandwidth and larger mode areas. Also, it beats the conventional circular-core-shaped Kagome HC-PCF in terms of the loss. The development of this novel (to our knowledge) HC-PCF has potential for a number of applications in which the combination of a large optical bandwidth and a low loss is a prerequisite.     

Competing liquid phase instabilities during pulsed laser induced self-assembly of copper rings into ordered nanoparticle arrays on SiO2

Nanoscale copper rings of different radii, thicknesses, and widths were synthesized on silicon dioxide thin films and were subsequently liquefied via a nanosecond pulse laser treatment. During the nanoscale liquid lifetimes, the rings experience competing retraction dynamics and thin film and/or Rayleigh-Plateau types of instabilities, which lead to arrays of ordered nanodroplets. Surprisingly, the results are significantly different from those of similar experiments carried out on a Si surface. We use hydrodynamic simulations to elucidate how the different liquid/solid interactions control the different instability mechanisms in the present problem.     

On the existence of regular antichains

A $k$-regular antichain in the Boolean lattice of subsets is one in which each point occurs in exactly $k$ sets. The existence and construction of $k$-regular antichains on $m$ points for each positive integer pair $(k,m)$ is determined for all $m$ and most $k$.     

Subsurface damage in alumina and alumina–silicon carbide nanocomposites

The subsurface plastic deformation below alumina (Al₂O₃) and Al₂O₃–silicon carbide (SiC) nanocomposite surfaces subjected to grinding, polishing and annealing has been measured by high-resolution grazing-incidence parallel-beam X-ray powder diffraction and transmission electron microscopy. The variation with angle in the full width at half-height maximum (FWHM) of the X-ray Bragg peaks was successfully modelled by a FWHM distribution that fell exponentially with increasing depth. Consistent parameters were extracted from data taken using both prism and pyramidal reflecting planes. Correlation was found between the depth at which the FWHM fell to 1/e of the surface value and the depth of damage observed by transmission electron microscopy. The associated surface strain in the nanocomposite was found to increase linearly with increasing diameter of the diamond polishing particles. In ground 5?vol.%?SiC nanocomposite, these random surface strains fell by a factor of 7 and the depth of damage increased by a factor of 3 after annealing at 1250°C for 2?h. No differences were observed in the Bragg peak FWHM as a function of angle for material polished with 1?µm diamond grit before and after annealing.     

Strain-rate dependence of the brittle-to-ductile transition temperature in tungsten

We have investigated the strain-rate dependence of the brittle-to-ductile transition (BDT) temperature in pre-cracked tungsten single-crystals and polycrystals. There is an unambiguous Arrhenius relationship over four decades of strain rate, giving an activation energy for the process controlling the BDT of 1.05?eV. This is equal to the activation energy for double-kink formation on screw dislocations, suggesting that their motion controls the brittle–ductile transition.     

Crude glycerol combustion: Particulate,acrolein, and other volatile organic emissions

Crude glycerol is an abundant by-product of biodiesel production. As volumes of this potential waste grow, there is increasing interest in developing new value added uses. One possible use, as a boiler fuel for process heating, offers added advantages of energy integration and fossil fuel substitution. However, challenges to the use of crude glycerol as a boiler fuel include its low energy density, high viscosity, and high autoignition temperature. We have previously shown that a refractory-lined, high swirl burner can overcome challenges related to flame ignition and stability. However, critical issues related to ash behavior and the possible formation of acrolein remained. The work presented here indicates that the presence of dissolved catalysts used during the esterification and transesterification processes results in extremely large amounts of inorganic species in the crude glycerol. For the fuels examined here, the result is a submicron fly ash comprised primarily of sodium carbonates, phosphates, and sulfates. These particles report to a well-developed accumulation mode (0.3–0.7 μm diameter), indicating extensive ash vaporization and particle formation via nucleation, condensation, and coagulation. Particle mass emissions were between 2 and 4 g/m³. These results indicate that glycerol containing soluble catalyst is not suitable as a boiler fuel. Fortunately, process improvements are currently addressing this issue. Additionally, acrolein is of concern due to its toxicity, and is known to be formed from the low temperature thermal decomposition of glycerol. Currently, there is no known reliable method for measuring acrolein in sources. Acrolein and emissions of other volatile organic compounds were characterized through the use of a SUMMA canister-based sampling method followed by GC–MS analysis designed for ambient measurements. Results indicate crude glycerol combustion produces relatively small amounts of acrolein (～15 ppbv) and other volatile organic compounds, with emissions comparable to those from natural gas combustion.     

NMR Studies of Drugs: Antipyrine and Analogs. I. Use of Achiral and Chiral Lanthanide Shift Reagents to Examine Hindered Rotation.

The 200 MHz ¹H NMR spectra of the analgesic, antipyrine, 1, have been studied in CDC1₃ solution at ambient temperatures with the achiral lanthanide shift reagent (LSR) tris (6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium (III), Eu(FOD)₃, 2, and with the chiral LSR, tris[3-(heptafluoropropylhydroxymethylene)-(+)-camphorato]europium(III), Eu(HFC)₃, 3., Lanthanide-induced shift (LIS) magnitudes and broadening of selected signals are consistent with predominant LSR binding at the carbonyl oxygen with either 2 or 3. Of the different possible conformational regimes for the N-phenyl group of 1, our results appear to rule out a slow exchange limit (SEL) system with the N-phenyl coplanar with the heterocyclic ring. Perpendicular rings in an SEL regime can not be ruled out. A rapidly-rotating N-phenyl (fast exchange limit, FEL system) would also be consistent with observed results. Accurate chemical shifts for the aryl protons (overlapped in the 200 MHz spectrum of unshifted 1) are determined from spectra with added LSR by extrapolation to zero molar ratios of [LSR]:[1]. Relative slopes in the plots of chemical shift versus [LSR]:[1] molar ratios are calculated for each proton signal of 1.