Inhibition by red phosphorus of unimolecular thermal chain-scission in poly(methyl methacrylate): Investigation by NMR,FT-IR and laser desorption/fourier transform mass spectroscopy

The reaction of red phosphorus with poly(methyl methacrylate) under pyrolysis conditions was investigated with a number of physical techniques. A random methyl methacrylate/cyclic anhydride copolymer is formed from atatic PMMA, whereas a random methyl methacrylate/methacrylic acid copolymer is obtained with isotactic PMMA. The backbones of both these copolymers are more stable toward depolymerization than that of PMMA. The flame-retardant activity of red phosphorus with PMMA may arise in part from stabilization of the polymer toward depolymerization via modification of the sidechains.     

Raman spectroscopy based on a single-crystal sapphire fiber

We demonstrate the advantages of using a single-crystal sapphire fiber to perform Raman spectroscopy over using a standard glass fiber. The narrow Raman peaks and the low background signal of a single-crystal sapphire fiber allow for the detection of weaker Raman signals or Raman signals much closer to the incident laser wavelength than with a standard glass fiber, which has a strong broadband Raman spectrum of its own. The Raman spectra of calcite, single-walled carbon nanotubes, and aqueous sodium carbonate solution were collected using a 50 cm long, 200 μm diameter sapphire fiber, and then they were compared with the results using a 50 cm long, 100 μm diameter glass fiber. The Raman spectrum of each tested material becomes indistinguishable due to the background Raman signal of the glass fiber but can easily be seen using the sapphire fiber, which has only a few narrow Raman peaks of its own.     

Structural and magnetic properties of FIB-irradiated microstructures on a Pt/Co multilayer

We present a study of the structural and magnetic effects induced by focused 30 keV Ga⁺ ion beam irradiation on a Pt(2.8 nm)/[Pt(0.6 nm)/Co(0.3 nm)]₆/Pt(6.5 nm) ferromagnetic multilayer, using transmission electron microscopy, optical and magneto-optical microscopy. The work is of relevance to high-density data-storage applications, where media planarity is crucial for device reliability.     

Unstrained C–C bond activation and directed fluorination through photocatalytically-generated radical cations

Expanding the repertoire of controlled radical fluorination techniques, we present a photosensitized unstrained C–C bond activation/directed monofluorination method using Selectfluor and 9-fluorenone. The reaction is amenable to the opening of multiple 1-acetal-2-aryl substituted rings to yield ω-fluoro carboxylic acids, esters, alcohols, and ketones with relative ease. Initial mechanistic insight suggests radical ion intermediates.     

Hydroxylation of the silica in microfabricated thin layer chromatography plates as probed by time‐of‐flight secondary ion mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy

Microfabricated silica thin layer chromatography (TLC) plates have previously been prepared on patterned carbon nanotube forests. The high temperatures used in their fabrication reduce the number of hydroxyl groups on their surfaces. Fortunately, silica can be rehydroxylated. In diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), a silanol peak below 3740 cm^?1 indicates a well‐hydroxylated silica surface that is fit for chromatography. Hydroxylations of our materials with HF are so effective that it is not possible to discern the position of this peak. In contrast, this signal is discernable when the plates are treated with NH₄OH. To find a more convenient method for studying the surfaces of TLC plates, time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) was considered. ToF‐SIMS is advantageous because multiple microfabricated TLC plates must be scraped to obtain enough silica for one DRIFT analysis, while static SIMS can be performed on very small regions (500 × 500 µm² or less) of individual plates. Ratios of the SiOH⁺ and Si⁺ ToF‐SIMS signals for microfabricated TLC plates correlated well with ~3740 cm^?1 silanol peaks from DRIFT. Thus, SIMS allows direct analysis of all of our treated and untreated plates, including those hydroxylated with HF. The best hydroxylation condition for HF, which was better than any studied for NH₄OH, was around 150 ppm at room temperature. The best hydroxylation condition for NH₄OH was 50 °C for 72 h. ToF‐SIMS versus DRIFT results of commercial TLC plates were also obtained and evaluated. Copyright © 2014 John Wiley & Sons, Ltd.     

Dynamic algorithm selection for pareto optimal set approximation

This paper presents a meta-algorithm for approximating the Pareto optimal set of costly black-box multiobjective optimization problems given a limited number of objective function evaluations. The key idea is to switch among different algorithms during the optimization search based on the predicted performance of each algorithm at the time. Algorithm performance is modeled using a machine learning technique based on the available information. The predicted best algorithm is then selected to run for a limited number of evaluations. The proposed approach is tested on several benchmark problems and the results are compared against those obtained using any one of the candidate algorithms alone.     

Explicit Solutions of Quadratic FBSDEs Arising From Quadratic Term Structure Models

We provide explicit solutions of certain forward-backward stochastic differential equations (FBSDEs) with quadratic growth. These particular FBSDEs are associated with quadratic term structure models of interest rates and characterize the zero-coupon bond price. The results of this paper are naturally related to similar results on affine term structure models of Hyndman (Math. Financ. Econ. 2(2):107–128, 2009) due to the relationship between quadratic functionals of Gaussian processes and linear functionals of affine processes. Similar to the affine case a sufficient condition for the explicit solutions to hold is the solvability in a fixed interval of Riccati-type ordinary differential equations. However, in contrast to the affine case, these Riccati equations are easily associated with those occurring in linear-quadratic control problems. We also consider quadratic models for a risky asset price and characterize the futures price and forward price of the asset in terms of similar FBSDEs. An example is considered, using an approach based on stochastic flows that is related to the FBSDE approach, to further emphasize the parallels between the affine and quadratic models. An appendix discusses solvability and explicit solutions of the Riccati equations.     

Aqueous-phase deactivation and intramolecular [2 + 2 + 2] cycloaddition of oxanorbornadiene esters

Both inter- and intramolecular degradation pathways were identified for the aqueous phase deactivation of oxanorbornadiene (OND) electrophiles, and propargylic OND esters were found to undergo facile intramolecular [2 + 2 + 2] homo-Diels-Alder cycloaddition in polar media.     

Intracellular pH mapping with SNARF-1 and confocal microscopy. I: A quantitative technique for living tissue and isolated cells

A fluorescent pH indicator in conjunction with confocal microscopy, was used to map intracellular pH in a variety of cells and tissues with high spatial resolution. The new pH-sensitive fluorescent probe SNARF-1 was excited with the 488 nm band of the argon ion laser of a Bio-Rad MRC-500 confocal microscope. Ratio images were created with pixel-by-pixel division, with the intensity of these images representing a function of pH, that is independent of dye concentration, photobleaching or path length. Cell cultures of rat aortic smooth muscle were loaded with 20 μм SNARF-1/AM for 20 min at 37°C. Intracellular pH levels were calibrated in situ by treatment of each cell with nigericin (20 μм) in solutions of known pH. The cytosolic pH of the majority of cells was uniform, however, pH gradients were evident between the cytosol and nuclear regions, indicating the ability of this technique to map intracellular and intraorganelle pH. Rat C6 glioblastoma spheroids were cultured then loaded with SNARF-1/AM at 10°C for 90 min. The pH values were calibrated in vitro, using SNARF-1 acid in buffered solutions of known pH. Ratio images of the bisected spheroids showed a marked gradient in pH from the outer cells compared with central necrotic cells. The degree of involvement of acidification in muscle fatigue was investigated by simultaneously determining force generation and intracellular pH in individual fibres of an intact rat muscle. The investigation was performed during a stimulation protocol which induced significant fatigue in the force response of the muscle. The fatigue protocol induced little change in cytosolic pH in the fibres. We show that the use of SNARF-1, in conjunction with confocal microscopy is a powerful technique for accurately mapping pH within single cells, multicellular tissues and intact organs, as well as for accurately recording dynamic changes in pH.