The nuts and bolts of distance determination and zero- and double-quantum coherence in photoinduced radical pairs

We describe in some detail the new method of distance determination for a photoinduced radical pair. Emphasis is on giving the nuts and bolts of the calculations that result in analytical expressions for in- and out-of-phase electron spin echo (ESE) envelope modulations, pulse flip-angle dependencies, zero- and double-quantum coherences, and the distance between the two radicals. The theoretical results are illustrated by a set of recent experiments on photosynthetic reaction centers.     

Gyromagnetic ratios of collective states of166Er

The static hyperfine field ofB _hf ^4.2k (ErHo) = 739(18)T of a ferromagnetic holmium single crystal polarized in an external magnetic field of ± 0.48T at ～4.2K was used for integral perturbed γ-γ angular correlation (IPAQ measurements of the g-factors of collective states of¹⁶⁶Er. The 1,200y ^166m Ho activity was used which populates the ground state band and the γ vibrational band up to high spins. The results: $$\begin{gathered} g(4_g^ + ) = + 0.315(16) \hfill \\ g(6_g^ + ) = + 0.258(11) \hfill \\ g(8_g^ + ) = + 0.262(47)and \hfill \\ g(6_\gamma ^ + ) = + 0.254(32) \hfill \\ \end{gathered}$$ exhibit a significant reduction of the g-factors with increasing rotational angular momentum. The followingE2/M1 mixing ratios of interband transitions were derived from the angular correlation coefficients: $$\begin{gathered} 5_\gamma ^ + \Rightarrow 4_g^ + :\delta (810keV) = - (36_{ - 7}^{ + 11} ) \hfill \\ 7_\gamma ^ + \Rightarrow 6_g^ + :\delta (831keV) = - (18_{ - 2}^{ + 3} )and \hfill \\ 7_\gamma ^ + \Rightarrow 8_g^ + :\delta (465keV) = - (63_{ - 12}^{ + 19} ). \hfill \\ \end{gathered}$$ The results are discussed and compared with theoretical predictions.     

Photocaged pendent thiol polymer brush surfaces for postpolymerization modifications via thiol‐click chemistry

In this work, a postpolymerization surface modification approach is reported that provides pendent thiol functionality along the polymer brush backbone using the photolabile protection chemistry of both o‐nitrobenzyl and p‐methoxyphenacyl thioethers. Poly(2‐hydroxyethyl methacrylate) (pHEMA) brushes were synthesized via surface‐initiated atom transfer radical polymerization, after which the pHEMA hydroxyl groups were esterified with 3‐(2‐nitrobenzylthio)propanoic acid or 3‐(2‐(4‐methoxyphenyl)‐2‐oxoethylthio)propanoic acid to provide the photolabile protected pendent thiols. Addressing the protecting groups with light not only affords spatial control of reactive thiol functionality but enables a plethora of thiol‐mediated transformations with isocyanates and maleimides providing a modular route to create functional polymer surfaces. This concept was extended to block copolymer brush architectures enabling the modification of the chemical functionality of both the inner and outer blocks of the block copolymer surface. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Use of capillary electrophoresis with laser-induced fluorescence detection to screen and liquid chromatography–tandem mass spectrometry to confirm sulfonamide residues: Validation according to European Union 2002/657/EC

A multiresidue method is described for determining six sulfonamides (SAs) (sulfadiazine, sulfathiazole, sulfamethazine, sulfamethoxazole, sulfaquinoxaline and sulfadimethoxine) in liver by a capillary electrophoresis screening method and a liquid chromatography coupled to tandem mass spectrometry confirmatory assay. Samples were prepared by homogenizing the tissue, with sodium hydroxide and acetonitrile. After evaporation, extracts were injected in the capillary electrophoresis system or mass spectrometry system for confirmatory analysis. The detection of analytes was achieved by laser-induced fluorescence in capillary electrophoresis. Procedures were validated according to the European Union regulation 2002/657/EC determining specificity, selectivity and detection capability for screening method and decision limit, detection capability, specificity, selectivity, trueness and precision for confirmation method. The results of validation process demonstrate that the method is suitable for application in Brazilian statutory veterinary drug residue surveillance programs. Capillary electrophoresis was proved to be a fast, robust method with low time and reagents consumption.     

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Discontinuous solutions of the Navier-Stokes equations for compressible flow

We prove local existence and study properties of discontinuous solutions of the Navier-Stokes equations for one-dimensional, compressible, nonisentropic flow. We assume that, modulo a step function, the initial data is in L² and the initial velocity and density are in the space BV. We show that the velocity and the temperature become smoothed out in positive time, and that discontinuities in the density, pressure, and gradients of the velocity and temperature persist for all time. We also show that for stable gases these discontinuities decay exponentially in time, more rapidly for smaller viscosities.     

Solid-phase microextraction as a novel air sampling technology for improved, GC-olfactometry-based assessment of livestock odors

Air sampling and characterization of odorous livestock gases is one of the most challenging analytical tasks. This is because of low concentrations, physicochemical properties, and problems with sample recoveries for typical odorants. Livestock operations emit a very complex mixture of volatile organic compounds (VOCs) and other gases. Many of these gases are odorous. Relatively little is known about the link between characteristic VOCs/gases and, specifically, about the impact of characteristic odorants downwind from sources. In this research, solid-phase microextraction (SPME) is used for field air sampling of odors downwind from swine and beef cattle operations. Sampling time ranges from 20 min to 1 h. Samples are analyzed using a commercial gas chromatography-mass spectrometry-olfactometry system. Odor profiling efforts are directed at odorant prioritization, with respect to distance from the source. The results indicate the odor downwind is increasingly defined by a smaller number of high-priority odorants. These "character defining" odorants appear to be dominated by compounds of relatively low volatility, high molecular weight, and high polarity. In particular, p-cresol alone appears to carry much of the overall odor impact for swine and beef cattle operations. Of particular interest is the character-defining odor impact of p-cresol as far as 16 km downwind of the nearest beef cattle feedlot. The findings are highly relevant to scientists and engineers working on improved air sampling and analysis protocols and on improved technologies for odor abatement. More research evaluating the use of p-cresol and a few other key odorants as a surrogate for overall odor dispersion modeling is warranted.