Assessing Competitive Reaction Rates in the Nitration of 2-Methylbiphenyl, Biphenyl, and Toluene to Determine Steric Restriction in Resonance-Stabilized Planarization of the Carbocation Intermediates

Electrophilic aromatic substitution (EAS) reactions have long been a fundamental addition to sophomore-level organic chemistry classes, allowing students the opportunity to explore the electron donating and withdrawing effects of electrons contained in the substituents of the aromatic reactant. In this paper we present preliminary findings on the nitration of methylated biphenyls using kinetic and regioselective assessments to analyze steric influences on the planarization of 2-methylbiphenyl after EAS nitration. Our preliminary findings show that nitration favors the methylated phenyl ring of 2-methylbiphenyl, indicating that the steric influence of the methyl group restricts planarization of the carbocation intermediate. Furthermore, a competition nitration reaction between biphenyl and toluene provides proof of concept for kinetic assessment of nitration rates that will eventually be applied to 2-methylbiphenyl; this competitive nitration showed that biphenyl nitrates 1.87 ± 0.61 (95% C.I.) times faster than toluene

Climatization-Negligent Attribution of Great Salt Lake Desiccation: A Comment on Meng (2019)

A recent article reviewed data on Great Salt Lake (Utah) and concluded falsely that climate changes, especially local warming and extreme precipitation events, are primarily responsible for lake elevation changes. Indeed climatically influenced variation of net inflows contribute to huge swings in the elevation of Great Salt Lake (GSL) and other endorheic lakes. Although droughts and wet cycles have caused lake elevation changes of over 4.5 m, they have not caused a significant long-term change in the GSL stage. This recent article also suggests that a 1.4 °C rise in air temperature and concomitant increase in the lake\u27s evaporative loss is an important reason for the lake\u27s decline. However, we calculate that a 1.4 °C rise may have caused only a 0.1mdecrease in lake level. However, since 1847, the lake has declined 3.6 m and the lake area has decreased by ≈50%, despite no significant change in precipitation (p = 0.52) and a slight increase, albeit insignificant, in river flows above irrigation diversions (p = 0.085). In contrast, persistent water extraction for agriculture and other uses beginning in 1847 now decrease water flows below diversions by 39%. Estimates of consumptive water use primarily for irrigated agriculture in the GSL watershed suggest that approximately 85% (2500 km2) of the reduced lake area can be attributed to human water consumption. The recent article\u27s failure to calculate a water budget for the lake that included extensive water withdrawals misled the author to focus instead on climate change as a causal factor for the decline. Stable stream flows in GSL\u27s headwaters, inadequate temperature increase to explain the extent of its observed desiccation, stable long-term precipitation, and the magnitude of increased water consumption from GSL together demonstrate conclusively that climatic factors are secondary to human alterations to GSL and its watershed. Climatization, in which primarily non-climatic processes are falsely attributed to climatic factors, is a threat to the credibility of hydrological science. Despite a recent suggestion to the contrary, pressure to support Earth\u27s rising human population-in the form of increasing consumption of water in water-limited regions, primarily to support irrigated agriculture-remains the leading driver of desiccation of inland waters within Earth\u27s water-limited regions

Further insights into the floral character of Touriga Nacional Wines

Higher-quality Touriga Nacional (TN) wines are characterized by a fruity-citric aroma described as sweet and fresh citrus evoking the bergamot fruit (Citrus bergamia). In fact, “bergamot-like” descriptor is currently employed to rate higher quality TN wines. The aim of thiswork was to identify among volatile compounds present in bergamot fruit extracts (mainly terpenes) which of them contributes the most to the bergamot overall perception, and relate these data with the volatile composition of TN wines. The identification of the most important descriptors was done by sensory analysis. Among 18 descriptors 3were selected: bergamot-like aroma, orange like, and violet. A GCO of a typical TN wine extract allows the identification of 3 related odorant zones ZO1, ZO2, and ZO3 related with bergamot-like aroma. Using AEDA, ZO2 was confirmed to be one of the most important odorant zones. Using AEDA the presence of linalool and linalyl acetate was confirmed. A similarity test was performedwith a non-TN wine added with linalool and linalyl acetate alone or in combinations. The highest similarity value was observed when linalool (SV = 5.9) was added. In fact, results obtained from the analysis of several red wines from different varieties show that terpenols are present in higher amounts in wines coming from TN variety, which proves that these compounds can be the clue to the varietal aroma of TN wines

The Preparation and Certification of School Librarians: Using Causal Educational Research About Teacher Characteristics to Probe Facets of Effectiveness

How do we define a high-quality school librarian? Decades of educational researchers have attempted to link teacher characteristics—such as how teachers are prepared, which credentials they carry, and years of experience—to student outcomes. These researchers have contended that individual educator attributes may have a direct effect on what and how much their students learn. School librarians are also teachers who have direct student contact, and although numerous studies have indicated that school librarian preparation, licensure, and other background characteristics are promising areas for further direct exploration, researchers have yet to examine if, how, and why school librarians’ certification or preparation positively impacts students’ learning outcomes. The purpose of this paper is to compare findings from causal educational research to findings from descriptive school librarianship research to discern possible areas of causal alignment that warrant further investigation. In this study, we present a subset of a larger mixed research synthesis of causal educational research related to student achievement, contextualized with existing school librarianship research, to draw relationships between classroom teacher and school librarian preparation and characteristics and to shape researchable conjectures about school librarians’ effects on learner outcomes

Designing a tobacco counter-marketing campaign for African American youth

The objectives of this qualitative study were to: a) identify common marketing themes and tactics used by the tobacco industry to entice African Americans (AA's) and youth to initiate and maintain smoking behavior, especially smoking mentholated brands of cigarettes, and b) determine AA youths' knowledge, attitudes, intentions, and beliefs about smoking and the tobacco industry. Together, these activities could aid in the development of effective tobacco counter-marketing campaigns for AA youth. Using publicly available tobacco industry documents, computerized searches using standardized keywords were run and results were cataloged and analyzed thematically. Subsequently, 5 focus groups were conducted with n = 28 AA middle school-aged youth. Results suggest that the tobacco industry consistently recruited new AA smokers through a variety of means, including social and behavioral marketing studies and targeted media and promotional campaigns in predominantly AA, urban, and low income areas. AA youth interviewed in this study were largely unaware of these tactics, and reacted negatively against the industry upon learning of them. Youth tended to externalize control over tobacco, especially within the AA community. In designing a counter-marketing campaign for this population, partnering knowledge of tobacco industry practices with youth needs and community resources will likely increase their effectiveness

Inflammatory biomarker changes and their correlation with Framingham cardiovascular risk and lipid changes in antiretroviral-naive HIV-infected patients treated for 144 weeks with abacavir/lamivudine/atazanavir with or without ritonavir in ARIES.

Propensity for developing coronary heart disease (CHD) is linked with Framingham-defined cardiovascular risk factors and elevated inflammatory biomarkers. Cardiovascular risk and inflammatory biomarkers were evaluated in ARIES, a Phase IIIb/IV clinical trial in which 515 antiretroviral-naive HIV-infected subjects initially received abacavir/lamivudine + atazanavir/ritonavir for 36 weeks. Subjects who were virologically suppressed by week 30 were randomized 1:1 at week 36 to either maintain or discontinue ritonavir for an additional 108 weeks. Framingham 10-year CHD risk scores (FRS) and risk category o

Influence of pH and ionic strength on the color parameters and antioxidant properties of an ethanolic red grape marc extract

The aim of present study was to investigate the influences of pH and several salts on the antioxidant activity and color of an ethanolic grape marc extract. Furthermore, the phenolic content of the extract was analyzed using HPLC and spectrophotometric methods while the total antioxidant activity was assessed by the reaction with ABTS radical. Gallic acid, procyanidins B1, B2, polydatin, catechin, epicatechin, hyperoside, ferulic, chlorogenic, and salicylic acids were among the main identified polyphenols. Different pH values had slight influence on the antioxidant activity, the highest value being determined for pH 3.7. The redness, chroma, and hue were significantly enhanced at pH 3.7 and 2.6. The chromaticity decreased at pH = 5.5 and pH = 7.4, so the extract should be used with care in products with such media. The presence of salts did not noticeably affect the antioxidant activity, except the higher concentrations of CaCl2, which decreased the antioxidant activity but enhanced the color intensity

Increased Epithelial Gaps in the Small Intestine Are Predictive of Hospitalization and Surgery in Patients With Inflammatory Bowel Disease

Objectives: Epithelial gaps resulting from intestinal cell extrusions can be visualized with confocal laser endomicroscopy (CLE) during colonoscopy and increased in normal-appearing terminal ileum of inflammatory bowel disease (IBD) patients. Cell-shedding events on CLE were found to be predictive of disease relapse. The aim of this study was to assess the prognostic value of epithelial gap densities for major clinical events (hospitalization or surgery) in follow-up. Methods: We prospectively followed IBD patients undergoing colonoscopy with probe-based CLE (pCLE) for clinical events including symptom flares, medication changes, hospitalization, or surgery. Survival analysis methods were used to compare event times for the composite outcome of hospitalization or surgery using log-rank tests and Cox proportional hazards models. We also examined the relationship of gap density with IBD flares, need for anti-tumor necrosis factor therapy, disease duration, gender and endoscopic disease severity, and location. Results: A total of 21 Crohn's disease and 20 ulcerative colitis patients with a median follow-up of 14 (11–31) months were studied. Patients with elevated gap density were at significantly higher risk for hospitalization or surgery (log-rank test P=0.02). Gap density was a significant predictor for risk of major events, with a hazard ratio of 1.10 (95% confidence interval=1.01, 1.20) associated with each increase of 1% in gap density. Gap density was also correlated with IBD disease duration (Spearman's correlation coefficient rho=0.44, P=0.004), and was higher in male patients (9.0 vs. 3.6 gaps per 100 cells, P=0.038). Conclusions: Increased epithelial gaps in the small intestine as determined by pCLE are a predictor for future hospitalization or surgery in IBD patients

Increased S-nitrosylation and proteasomal degradation of caspase-3 during infection contribute to the persistence of adherent invasive escherichia coli (AIEC) in immune cells

Adherent invasive Escherichia coli (AIEC) have been implicated as a causative agent of Crohn's disease (CD) due to their isolation from the intestines of CD sufferers and their ability to persist in macrophages inducing granulomas. The rapid intracellular multiplication of AIEC sets it apart from other enteric pathogens such as Salmonella Typhimurium which after limited replication induce programmed cell death (PCD). Understanding the response of infected cells to the increased AIEC bacterial load and associated metabolic stress may offer insights into AIEC pathogenesis and its association with CD. Here we show that AIEC persistence within macrophages and dendritic cells is facilitated by increased proteasomal degradation of caspase-3. In addition S-nitrosylation of pro- and active forms of caspase-3, which can inhibit the enzymes activity, is increased in AIEC infected macrophages. This S-nitrosylated caspase-3 was seen to accumulate upon inhibition of the proteasome indicating an additional role for S-nitrosylation in inducing caspase-3 degradation in a manner independent of ubiquitination. In addition to the autophagic genetic defects that are linked to CD, this delay in apoptosis mediated in AIEC infected cells through increased degradation of caspase-3, may be an essential factor in its prolonged persistence in CD patients

Reactive direction control for a mobile robot: A locust-like control of escape direction emerges when a bilateral pair of model locust visual neurons are integrated

Locusts possess a bilateral pair of uniquely identifiable visual neurons that respond vigorously to the image of an approaching object. These neurons are called the lobula giant movement detectors (LGMDs). The locust LGMDs have been extensively studied and this has lead to the development of an LGMD model for use as an artificial collision detector in robotic applications. To date, robots have been equipped with only a single, central artificial LGMD sensor, and this triggers a non-directional stop or rotation when a potentially colliding object is detected. Clearly, for a robot to behave autonomously, it must react differently to stimuli approaching from different directions. In this study, we implement a bilateral pair of LGMD models in Khepera robots equipped with normal and panoramic cameras. We integrate the responses of these LGMD models using methodologies inspired by research on escape direction control in cockroaches. Using ‘randomised winner-take-all’ or ‘steering wheel’ algorithms for LGMD model integration, the khepera robots could escape an approaching threat in real time and with a similar distribution of escape directions as real locusts. We also found that by optimising these algorithms, we could use them to integrate the left and right DCMD responses of real jumping locusts offline and reproduce the actual escape directions that the locusts took in a particular trial. Our results significantly advance the development of an artificial collision detection and evasion system based on the locust LGMD by allowing it reactive control over robot behaviour. The success of this approach may also indicate some important areas to be pursued in future biological research