Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

The reversible oxidation of methionine residues in proteins has emerged as a biologically important post-translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2-mercaptoimidazole or pyridine-2-thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by ¹³C NMR spectroscopy. These provide evidence for an α-chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.     

Depressive symptoms in early marriage: Predictions from relationship confidence and negative marital interaction.

The authors proposed a model of depressive symptoms in early marriage in which relationship confidence, defined as perceived couple-level efficacy to manage conflicts and maintain a healthy relationship, mediates the effect of negative marital interactions on depressive symptoms. The model was tested in a sample of 139 couples assessed prior to marriage and 1 year later. As predicted, relationship confidence demonstrated simple negative associations with negative marital interaction and depressive symptoms for all participants. Longitudinal path analyses supported the mediational model for women only. In women but not men, negative marital interaction indirectly had an impact on depressive symptoms through the mediator of relationship confidence. Findings suggest that relationship confidence may be important to understanding links between marital distress and depressive symptoms, especially in women. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Preview benefit and parafoveal-on-foveal effects from word n + 2.

Using the gaze-contingent boundary paradigm with the boundary placed after word n, the experiment manipulated preview of word n + 2 for fixations on word n. There was no preview benefit for 1st-pass reading on word n + 2, replicating the results of K. Rayner, B. J. Juhasz, and S. J. Brown (2007), but there was a preview benefit on the 3-letter word n + 1, that is, after the boundary but before word n + 2. Additionally, both word n + 1 and word n + 2 exhibited parafoveal-on-foveal effects on word n. Thus, during a fixation on word n and given a short word n + 1, some information is extracted from word n + 2, supporting the hypothesis of distributed processing in the perceptual span. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Characterizing nicotine withdrawal in pregnant cigarette smokers.

Maternal smoking is a leading preventable cause of poor pregnancy outcomes and infant morbidity and mortality. Whereas pregnancy has been thought of as a "window of opportunity" when women are more motivated to change health behaviors such as smoking, only 20% of pregnant women quit smoking upon learning they are pregnant and remain abstinent at the end of the pregnancy. Greater understanding of possible obstacles to smoking during pregnancy, such as nicotine withdrawal, is needed. The symptoms of nicotine withdrawal have been well characterized in nonpregnant smokers, but there has been only 1 report conducted during pregnancy, and that was a retrospective study. The aim of the present study was to characterize nicotine withdrawal and craving in pregnant cigarette smokers. These data were collected as part of prospective clinical trials assessing the efficacy of voucher-based incentives to promote abstinence from cigarette smoking during pregnancy and postpartum. The authors examined results from the Minnesota Nicotine Withdrawal Scale (J. R. Hughes & D. K. Hatsukami, 1998) in 27 abstainers (reported no or very low levels of smoking, which was confirmed biochemically) and 21 smokers (smoked at >80% of their baseline smoking level) during the first 5 days of a cessation attempt. Abstainers reported more impatience, anger, and difficulty concentrating than did smokers. The results also suggest that pregnant smokers generally may have elevated baseline levels of withdrawal, which need to be considered in the design and analysis of future studies. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

High-maintenance interaction: Inefficient social coordination impairs self-regulation.

Tasks requiring interpersonal coordination permeate all spheres of life. Although social coordination is sometimes efficient and effortless (low maintenance), at other times it is inefficient and effortful (high maintenance). Across 5 studies, participants experienced either a high- or a low-maintenance interaction with a confederate before engaging in an individual-level task requiring self-regulation. Self-regulation was operationalized with measures of (a) preferences for a challenging task with high reward potential over an easy task with low reward potential (Study 1) and (b) task performance (anagram performance in Study 1, Graduate Record Exam performance in Studies 2 and 3, physical stamina in Study 4, and fine motor control in Study 5). Results uniformly supported the hypothesis that experiencing high-maintenance interaction impairs one's self-regulatory success on subsequent, unrelated tasks. These effects were not mediated through participants' conscious processes and emerged even with a nonconscious manipulation of high-maintenance interaction. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Intergroup relations and group solidarity: Effects of group identification and social beliefs on depersonalized attraction.

An intergroup extension of M. A. Hogg's (1992, 1993) social attraction hypothesis is proposed. Netball teams were investigated with measures assessing the relationship between (a) objective status; (b) "social beliefs" about intergroup status, stability, legitimacy, and permeability; (c) group identification, self-categorization, and prototypicality; (d) interpersonal relations and similarity; (e) depersonalized social attraction; and (f) true personal attraction. As predicted, group-membership based social attraction was directly influenced by self-categorization; indirectly influenced, through self-categorization, by intergroup status and stability beliefs; and uninfluenced by interpersonal relations. Social attraction (related to prototypicality and group identification) was relatively independent of personal attraction (related to similarity and interpersonal variables). Legitimacy, permeability, and the empirical co-occurrence of social and personal attraction in cohesive groups are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Liquefaction of coal using supercritical fluid mixtures

Powhatan No. 5 and Bruceton coals were liquefied for 15–60 min at 653 K and 30 MPa in supercritical aqueous mixtures containing 10–20 wt% tetrahydroquinoline (THQ), quinoline or tetralin. The THQ-water mixtures produced the highest conversion to tetrahydrofuran (THF) soluble products (up to 74%). Tetralin-water, quinoline-water and pure water solvents gave increasingly lower yields of THF solubles. Addition of hydrogen to the quinoline-water solvent mixture increased yields slightly, but not to the level obtained using the THQ-water mixture.The yields of THF solubles in all instances depended upon the concentration of solvent in the mixture, with the 10 wt% THQ and 10 wt% tetralin (in water) giving higher yields than either 0 or 20 wt% concentrations. The nitrogen-containing solvents were chemically bonded to the THF-soluble product, as observed by g.p.c.     

Bi-material strip based temperature sensor design and optimization through thermo-mechanical multi-physics modeling

ABSTRACT

With the capability of additive manufacturing, complex structures are easily fabricated to achieve various design purposes. In this work, a bi-material strip temperature sensor with complex periodic pattern design is purposed and investigated through both the analytical modeling and multi-physics finite element analysis. Three design patterns are considered: standard, E-shape and S-shape. In the standard solid strip design, the curvature of the bi-material strip under temperature variation is in a linear relationship with the coefficient of thermal expansion (CTE) difference, but in a reciprocal relationship with the strip thickness. The curvature of the bi-material strip depends on the Young’s modulus ratio and layer thickness ratio of the two materials, but is independent of the magnitude of the materials’ Young’s modulus. Based on analytical derivation and numerical validation, the optimized design parameters can be provided. Compared to S-shape pattern design, E-shape pattern design can significantly increase the temperature sensitivity of the bi-material strip. An analytical prediction of the E-shape pattern’s temperature sensitivity is introduced and discussed. This work proves the concept that new design space becomes available with the capability of additive manufacturing, and provides the general design guideline for a bi-material strip based temperature sensor with possible design patterns.     

Synthesis and evaluation of tetra(2,7-octadienyl) titanate as a reactive diluent for air-drying alkyd paints

Environmental regulations are forcing the reformulation of many decorative and protective coatings systems. In particular, air-drying solventborne alkyd paints need to meet increasingly stringent emission limits and often must be reformulated with suitable exempt solvents or reactive diluents to achieve volatile organic compound (VOC) reduction. In the research summarized in this article, a new reactive diluent, tetra(2,7-octadienyl) titanate, was synthesized and evaluated in alkyd formulations for VOC reduction and property enhancement. A soy-based long-oil alkyd resin; a soy-based high-solids, long-oil alkyd resin; and a linseed-based, high-solids long-oil alkyd resin were evaluated in combination with the new reactive diluent at weight percentages ranging from 10% to 50%. Characterization included measuring viscosity, film dry times, and film performance of the reactive diluent formulations in comparison to neat alkyd resins used as control. The tetra(2,7-octadienyl) titanate formulations consistently exhibited reduced viscosities and dry times as a function of concentration. The resulting films were harder and more thoroughly cured than the control systems.     

Enhanced expression and purification of fungal galactose oxidase in Escherichia coli and use for analysis of a saturation mutagenesis library

Galactose oxidase (GO) displays broad primary alcohol substrate specificity and so offers potential for engineering new substrate specificity by directed evolution. Producing variant libraries of sufficient complexity ideally requires expression of functional protein in a host such as Escherichia coli. Wild-type GO is produced by the fungus Fusarium graminiarum and is expressed poorly in E. coli. We introduced silent mutations within codons 2-7 of the mature GO coding sequence to enhance GO translation and have combined these with other expression-enhancing mutations. We selected the best E. coli host strain, autoinduction medium, induction temperature, harvest time and cell lysis procedure to produce active recombinant GO. Although normally secreted by the fungus, we have expressed GO in the cytoplasm of E. coli and have used a C-terminal Streptag II sequences for single-step affinity purification. This resulted in purification of 240 mg of functional GO per litre of shake flask culture. We have generated a saturation mutagenesis library at residue Cys383, known to influence substrate binding, and have used the optimised expression conditions to purify and characterise the resulting enzymes.