Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

Atmospheric chemical reactions are often initiated by ultraviolet (UV) solar radiation since absorption in that wavelength range coincides to typical chemical bond energies. In this review, we present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons. We focus on the O–H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical reactions. Experimental and theoretical O–H intensities of several carboxylic acids, alcohols, and peroxides are presented. The importance of combination bands in spectra at chemically relevant energies is examined in the context of atmospheric photochemistry. Candidate systems for overtone-initiated chemistry are provided, and their lowest energy barrier for reaction and the minimum quanta of O–H stretch required for reaction are calculated. We conclude with a discussion of the major pathways available for overtone-induced reactions in the atmosphere

First sequence-confirmed case of infection with the new influenza A(H1N1) strain in Germany

Here, we report on the first sequence-confirmed case of infection with the new influenza A(H1N1) virus in Germany. Two direct contacts of the patient were laboratory-confirmed as cases and demonstrate a chain of direct human-to-human transmission

Comparison of four different treatment strategies in teeth with molar-incisor hypomineralization-related enamel breakdown–A retrospective cohort study

Background There is little information available on the longevity of non-invasive glass ionomer cement (GIC) and composite restorations as well as conventional composite and ceramic restorations placed on permanent teeth with enamel breakdowns due to molar-incisor hypomineralization (MIH). Aim To compare the longevity of the abovementioned treatment procedures. Design Of 377 identified MIH patients, 118 individuals received restorative treatment and were invited for clinical examination, including caries and MIH status. Finally, survival data from 204 MIH-related restorations placed on 127 teeth were retrospectively collected from 52 children, monitored between 2010 and 2018. Descriptive and explorative analyses were performed, including Kaplan-Meier estimators and the Cox regression model. Results The mean patient observation time was 42.9 months (SD = 35.1). The cumulative survival probabilities after 36 months—7.0% (GIC, N = 28), 29.9% (non-invasive composite restoration, N = 126), 76.2% (conventional composite restoration, N = 27) and 100.0% (ceramic restoration, N = 23)—differed significantly in the regression analysis. Conclusions Conventional restorations were associated with moderate-to-high survival rates in MIH teeth. In contrast, non-invasive composite restorations, which were predominately used in younger or less cooperative children, were linked to lower survival rates

Photosynthetic electron flow affects H2O2 signaling by inactivation of catalase in Chlamydomonas reinhardtii

A specific signaling role for H2O2 in Chlamydomonas reinhardtii was demonstrated by the definition of a promoter that specifically responded to this ROS. Expression of a nuclear-encoded reporter gene driven by this promoter was shown to depend not only on the level of exogenously added H2O2 but also on light. In the dark, the induction of the reporter gene by H2O2 was much lower than in the light. This lower induction was correlated with an accelerated disappearance of H2O2 from the culture medium in the dark. Due to a light-induced reduction in catalase activity, H2O2 levels in the light remained higher. Photosynthetic electron transport mediated the light-controlled down-regulation of the catalase activity since it was prevented by 3-(3′4′-dichlorophenyl)-1,1-dimethylurea (DCMU), an inhibitor of photosystem II. In the presence of light and DCMU, expression of the reporter gene was low while the addition of aminotriazole, a catalase inhibitor, led to a higher induction of the reporter gene by H2O2 in the dark. The role of photosynthetic electron transport and thioredoxin in this regulation was investigated by using mutants deficient in photosynthetic electron flow and by studying the correlation between NADP-malate dehydrogenase and catalase activities. It is proposed that, contrary to expectations, a controlled down-regulation of catalase activity occurs upon a shift of cells from dark to light. This down-regulation apparently is necessary to maintain a certain level of H2O2 required to activate H2O2-dependent signaling pathways

A Systematic Review of Argumentation Related to the Engineering-Designed World

Background Across academic disciplines, researchers have found that argumentation‐based pedagogies increase learners\u27 achievement and engagement. Engineering educational researchers and teachers of engineering may benefit from knowledge regarding how argumentation related to engineering has been practiced and studied. Purpose/Hypothesis Drawing from terms and concepts used in national standards for K‐12 education and accreditation requirements for undergraduate engineering education, this study was designed to identify how arguments and argumentation related to the engineering‐designed world were operationalized in relevant literature. Methodology Specified search terms and inclusion criteria were used to identify 117 empirical studies related to engineering argumentation and educational research. A qualitative content analysis was used to identify trends across these studies. Findings Overall, engineering‐related argumentation was associated with a variety of positive learner outcomes. Across many studies, arguments were operationalized in practice as statements regarding whether an existing technology should be adopted in a given context, usually with a limited number of supports (e.g., costs and ethics) provided for each claim. Relatively few studies mentioned empirical practices, such as tests. Most studies did not name the race/ethnicity of participants nor report engineering‐specific outcomes. Conclusions Engineering educators in K‐12 and undergraduate settings can create learning environments in which learners use a range of epistemic practices, including empirical practices, to support a range of claims. Researchers can study engineering‐specific outcomes while specifying relevant demographics of their research participants

Effects of Precursor Concentration and Acidic Sulfate in Aqueous Glyoxal−OH Radical Oxidation and Implications for Secondary Organic Aerosol

Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30−3000 μM) and the presence of acidic sulfate (0−840 μM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 μM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA

Impact of the California Lead Ammunition Ban on Reducing Lead Exposure in Golden Eagles and Turkey Vultures

Predatory and scavenging birds may be exposed to high levels of lead when they ingest shot or bullet fragments embedded in the tissues of animals injured or killed with lead ammunition. Lead poisoning was a contributing factor in the decline of the endangered California condor population in the 1980s, and remains one of the primary factors threatening species recovery. In response to this threat, a ban on the use of lead ammunition for most hunting activities in the range of the condor in California was implemented in 2008. Monitoring of lead exposure in predatory and scavenging birds is essential for assessing the effectiveness of the lead ammunition ban in reducing lead exposure in these species. In this study, we assessed the effectiveness of the regulation in decreasing blood lead concentration in two avian sentinels, golden eagles and turkey vultures, within the condor range in California. We compared blood lead concentration in golden eagles and turkey vultures prior to the lead ammunition ban and one year following implementation of the ban. Lead exposure in both golden eagles and turkey vultures declined significantly post-ban. Our findings provide evidence that hunter compliance with lead ammunition regulations was sufficient to reduce lead exposure in predatory and scavenging birds at our study sites