Reaction Energetics and ¹³C Fractionation of Alanine Transamination in the Aqueous and Gas Phases

The alanine transaminase (ALT) enzyme catalyzes the transfer of an amino group from alanine to α-ketoglutarate to produce pyruvate and glutamate. Isotope fractionation factors (IFFs) for the reaction ⁺H₃NCH(CH₃)COO⁻ + ⁻OOCCH₂CH₂C(O)COO⁻ ↔ CH₃C(O)COO⁻ + ⁻H₃NCH(CH₂CH₂COO⁻)COO⁻ (zwitterionic neutral alanine + doubly deprotonated α-ketoglutarate ↔ pyruvate + zwitterionic glutamate anion) were calculated from the partition functions of explicitly and implicitly solvated molecules at 298 K. Calculations were done for alanine (non-charge separated, zwitterion, deprotonated,), pyruvic acid (neutral, deprotonated), glutamic acid (non-charge separated, zwitterion, deprotonated, doubly deprotonated), and α-ketoglutaric acid (neutral, deprotonated, doubly deprotonated). The computational results, calculated from gas phase and aqueous optimized clusters with explicit H₂O molecules at the MP₂/aug-cc-pVDZ and MP₂/aug-cc-pVDZ/COSMO levels, respectively, predict that substitution of ¹³C at the C2 position of alanine and pyruvic acid and their various forms leads to the C2 position of pyruvic acid/pyruvate being enriched in ¹³C/¹²C ratio by 9 ‰. Simpler approaches that estimate the IFFs based solely on changes in the zero-point energies (ZPEs) are consistent with the higher-level model. ZPE-based IFFs calculated for simple analogues formaldehyde and methylamine (analogous to the C₂ positions of pyruvate and alanine, respectively) predict a ¹³C enrichment in formaldehyde of 7 to 8 ‰ at the MP₂/aug-cc-pVDZ and aug-cc-pVTZ levels. A simple predictive model using canonical functional group frequencies and reduced masses for ¹³C exchange between R₂C=O and R₂CH-NH₂ predicted enrichment in R₂C=O that is too large by a factor of two, but is qualitatively accurate compared with the more sophisticated models. Our models are all in agreement with the expectation that pyruvate and formaldehyde will be preferentially enriched in ¹³C due to the strength of their >C=O bond relative to that of the ≡C-NH₂ in alanine and methylamine. ¹³C/¹²C substitution is also modeled at the methyl and carboxylic acid sites of alanine and pyruvic acid, respectively

Academic Problem-Solving and Students’ identities as engineers

Socially constructed identities and language practices influence the ways students perceive themselves as learners, problem solvers, and future professionals. While research has been conducted on individuals’ identity as engineers, less has been written about how the language used during engineering problem solving influences students’ perceptions and their construction of identities as learners and future engineers. This study investigated engineering students’ identities as reflected in their use of language and discourses while engaged in an engineering problem solving activity. We conducted interviews with eight engineering students at a large southeastern university about their approaches to open and closed-ended materials engineering problems. A modification of Gee’s analysis of language-in-use was used to analyze the interviews. We found that pedagogical and engineering problem solving uses of language were the most common. Participants were more likely to perceive themselves as students highlighting the practices, expectations, and language associated with being a student rather than as emerging engineers whose practices are affected by conditions of professional practice. We suggest that problem solving in an academic setting may not encourage students to consider alternative discourses related to industry, professionalism, or creativity; and, consequently, fail to promote connections to social worlds beyond the classroom. By learning about the ways in which language in particular settings produces identities and shapes problem solving practices, educators and engineering professionals can gain deeper understanding of how language shapes the ways students describe themselves as problem-solvers and make decisions about procedures and techniques to solve engineering problems

The Sky is Falling: Chemical Characterization and Corrosion Evaluation of Deposition Produced During the Static Testing of Solid Rocket Motors

Static tests of horizontally restrained rocket motors at the ATK facility in Promontory UT, USA result in the deposition of entrained soil and fuel combustion products, referred to as Test Fire Soil (TFS), over areas as large as 30–50 mile2 (80–130 km2) and at distances up to 10–12 miles (16–20 km) from the test site. Chloride is the main combustion product generated from the ammonium perchlorate–aluminum based composite propellant. Deposition sampling/characterization and a 6-month field corrosivity study using mild steel coupons were conducted in conjunction with the February 25th 2010 FSM-17 static test. The TFS deposition rates at the three study sites ranged from 1 to 5 g/min/m2. TFS contained significantly more chloride than the surface soil collected from the test site. The TFS collected during two subsequent tests had similarly elevated chloride, suggesting that the results obtained in this study are applicable to other tests assuming that the rocket fuel composition remains similar. The field-deployed coupons exposed to the TFS had higher corrosion rates (3.6–5.0 mpy) than paired non-exposed coupons (1.6–1.8 mpy). Corrosion rates for all coupon

NOGO-A induction and localization during chick brain development indicate a role disparate from neurite outgrowth inhibition

BACKGROUND: Nogo-A, a myelin-associated protein, inhibits neurite outgrowth and abates regeneration in the adult vertebrate central nervous system (CNS) and may play a role in maintaining neural pathways once established. However, the presence of Nogo-A during early CNS development is counterintuitive and hints at an additional role for Nogo-A beyond neurite inhibition. RESULTS: We isolated chicken NOGO-A and determined its sequence. A multiple alignment of the amino acid sequence across divergent species, identified five previously undescribed, Nogo-A specific conserved regions that may be relevant for development. NOGO gene transcripts (NOGO-A, NOGO-B and NOGO-C) were differentially expressed in the CNS during development and a second NOGO-A splice variant was identified. We further localized NOGO-A expression during key phases of CNS development by in situ hybridization. CNS-associated NOGO-A was induced coincident with neural plate formation and up-regulated by FGF in the transformation of non-neural ectoderm into neural precursors. NOGO-A expression was diffuse in the neuroectoderm during the early proliferative phase of development, and migration, but localized to large projection neurons of the optic tectum and tectal-associated nuclei during architectural differentiation, lamination and network establishment. CONCLUSION: These data suggest Nogo-A plays a functional role in the determination of neural identity and/or differentiation and also appears to play a later role in the networking of large projection neurons during neurite formation and synaptogenesis. These data indicate that Nogo-A is a multifunctional protein with additional roles during CNS development that are disparate from its later role of neurite outgrowth inhibition in the adult CNS

Recommended core items to assess e-cigarette use in population-based surveys

A consistent approach using standardised items to assess e-cigarette use in both youth and adult populations will aid cross-survey and cross-national comparisons of the effect of e-cigarette (and tobacco) policies and improve our understanding of the population health impact of e-cigarette use. Focusing on adult behaviour, we propose a set of e-cigarette use items, discuss their utility and potential adaptation, and highlight e-cigarette constructs that researchers should avoid without further item development. Reliable and valid items will strengthen the emerging science and inform knowledge synthesis for policy-making. Building on informal discussions at a series of international meetings of 65 experts from 15 countries, the authors provide recommendations for assessing e-cigarette use behaviour, relative perceived harm, device type, presence of nicotine, flavours and reasons for use. We recommend items assessing eight core constructs: e-cigarette ever use, frequency of use and former daily use; relative perceived harm; device type; primary flavour preference; presence of nicotine; and primary reason for use. These items should be standardised or minimally adapted for the policy context and target population. Researchers should be prepared to update items as e-cigarette device characteristics change. A minimum set of e-cigarette items is proposed to encourage consensus around items to allow for cross-survey and cross-jurisdictional comparisons of e-cigarette use behaviour. These proposed items are a starting point. We recognise room for continued improvement, and welcome input from e-cigarette users and scientific colleagues

Simpson's Paradox, Lord's Paradox, and Suppression Effects are the same phenomenon – the reversal paradox

This article discusses three statistical paradoxes that pervade epidemiological research: Simpson's paradox, Lord's paradox, and suppression. These paradoxes have important implications for the interpretation of evidence from observational studies. This article uses hypothetical scenarios to illustrate how the three paradoxes are different manifestations of one phenomenon – the reversal paradox – depending on whether the outcome and explanatory variables are categorical, continuous or a combination of both; this renders the issues and remedies for any one to be similar for all three. Although the three statistical paradoxes occur in different types of variables, they share the same characteristic: the association between two variables can be reversed, diminished, or enhanced when another variable is statistically controlled for. Understanding the concepts and theory behind these paradoxes provides insights into some controversial or contradictory research findings. These paradoxes show that prior knowledge and underlying causal theory play an important role in the statistical modelling of epidemiological data, where incorrect use of statistical models might produce consistent, replicable, yet erroneous results

Apoptosis Regulates ipRGC Spacing Necessary for Rods and Cones to Drive Circadian Photoentrainment

SummaryThe retina consists of ordered arrays of individual types of neurons for processing vision. Here, we show that such order is necessary for intrinsically photosensitive retinal ganglion cells (ipRGCs) to function as irradiance detectors. We found that during development, ipRGCs undergo proximity-dependent Bax-mediated apoptosis. Bax mutant mice exhibit disrupted ipRGC spacing and dendritic stratification with an increase in abnormally localized synapses. ipRGCs are the sole conduit for light input to circadian photoentrainment, and either their melanopsin-based photosensitivity or ability to relay rod/cone input is sufficient for circadian photoentrainment. Remarkably, the disrupted ipRGC spacing does not affect melanopsin-based circadian photoentrainment but severely impairs rod/cone-driven photoentrainment. We demonstrate reduced rod/cone-driven cFos activation and electrophysiological responses in ipRGCs, suggesting that impaired synaptic input to ipRGCs underlies the photoentrainment deficits. Thus, for irradiance detection, developmental apoptosis is necessary for the spacing and connectivity of ipRGCs that underlie their functioning within a neural network

Exploring Alternative Terrain in the Rehabilitation and Treatment of Offenders: Findings from a Prison-based Music Project

The arts in prison settings have provided an alternative or complimentary component to rehabilitation. Despite increased interest, studies capturing the voice of offenders participating in projects and the long-term impact are limited. Data from semistructured interviews with 18 men who had taken part in a music-based project while incarcerated, including one group of five participants who were tracked for 18 months with supplemented data from correctional staff and official documentation, is presented. Participants of the art-based projects comment on changes they believe to have derived from participating in the project, particularly relating to emotions, self-esteem, self-confidence, communication and social skills. An exoffender sample of participants reported that participation in art projects provide experiences that promote beneficial skills that have been useful for post prison life