Search

The ability of Cu-H complexes to undergo selective insertion of unsaturated hydrocarbons under mild conditions has rendered them valuable, versatile catalysts. The direct formation of Cu allyl intermediates from unfunctionalized 1,3-dienes and transient Cu hydrides is an appealing strategy for upgrading conjugated diene feedstocks. However, empirical mechanistic studies of the underlying elementary steps and characterization of key intermediates in Cu-H catalysis are sparse. Using [(NHC)CuH]

Moral injury is a complex phenomenon characterized by spiritual, psychological, and moral distress caused by actions or acts of omission inconsistent with an individual’s moral and ethical values. We present two cases from an ongoing randomized controlled trial of a spiritually integrated structured intervention delivered by chaplains for individuals suffering from moral injury. Chaplains met with Veterans for twelve 50-min sessions that each focused on a specific domain of moral injury. Participants were asked to complete validated scales assessing symptoms of moral injury and PTSD, including the PTSD Checklist for DSM-5 (PCL-5), Moral Injury Symptom Scale-Military Version Short Form, and Moral Injury Symptom Scale-Military Version Long Form. We report on two Veterans who completed the intervention and demonstrated significant improvement in moral injury and PTSD symptoms.

Most ligand designs for reactions catalyzed by (NHC)Cu–H (NHC = N-heterocyclic carbene ligand) have focused on introducing steric bulk near the Cu center. Here, we evaluate the effect of remote ligand modification in a series of [(NHC)CuH]2 in which the para substituent (R) on the N-aryl groups of the NHC is Me, Et, tBu, OMe or Cl. Although the R group is distant (6 bonds away) from the reactive Cu center, the complexes have different spectroscopic signatures. Kinetics studies of the insertion of ketone, aldimine, alkyne, and unactivated α-olefin substrates reveal that Cu–H complexes with bulky or electron-rich R groups undergo faster substrate insertion. The predominant cause of this phenomenon is destabilization of the [(NHC)CuH]2 dimer relative to the (NHC)Cu–H monomer, resulting in faster formation of Cu–H monomer. These findings indicate that remote functionalization of NHCs is a compelling strategy for accelerating the rate of substrate insertion with Cu–H species.

We report the hydrogenation of CO2 to MeOH by a Ru(triphos) catalyst containing a cationic tetraalkylammonium moiety in the outer coordination sphere. This catalyst affords higher TON and TOF value...

Epileptogenic seizures, or status epilepticus (SE), leads to excitotoxic injury in hippocampal and limbic neurons in the kainic acid (KA) animal model of temporal lobe epilepsy (TLE). Here, we have further characterized neural activity regulated methylaminoisobutryic acid (MeAIB)/glutamine transport activity in mature rat hippocampal neurons in vitro that is inhibited by riluzole (IC50=1 μM), an anti-convulsant benzothiazole agent. We screened a library of riluzole derivatives and identified SKA-41 followed by a second screen and synthesized several novel chlorinated aminothiazoles (SKA-377, SKA-378, SKA-379) that are also potent MeAIB transport inhibitors in vitro, and brain penetrant following systemic administration. When administered before KA, SKA-378 did not prevent seizures but still protected the hippocampus and several other limbic areas against SE-induced neurodegeneration at 3d. When SKA-377 - 379, (30mg/kg) were administered after KA-induced SE, acute neural injury in the CA3, CA1 and CA4/hilus was also largely attenuated. Riluzole (10mg/kg) blocks acute neural injury. Kinetic analysis of SKA-378 and riluzoles' blockade of Ca2+-regulated MeAIB transport in neurons in vitro indicates that inhibition occurs via a non-competitive, indirect mechanism. Sodium channel NaV1.6 antagonism blocks neural activity regulated MeAIB/Gln transport in vitro (IC50=60nM) and SKA-378 is the most potent inhibitor of NaV1.6 (IC50=28μM) compared to NaV1.2 (IC50=118μM) in heterologous cells. However, pharmacokinetic analysis suggests that sodium channel blockade may not be the predominant mechanism of neuroprotection here. Riluzole and our novel aminothiazoles are agents that attenuate acute neural hippocampal injury following KA-induced SE and may help to understand mechanisms involved in the progression of epileptic disease.

Infecting approximately one-third of the world’s population, the neurotropic protozoan Toxoplasma gondii has been associated with cognition and several neuropsychiatric diseases including schizophrenia and bipolar disorder. Findings have been mixed, however, about the relationship between Toxoplasma gondii and depression, with some studies reporting positive associations and others finding no associations. To further investigate the association between Toxoplasma gondii and depression, we used data from the UK Biobank and the National Health and Examination Survey (NHANES). Results from adjusted multiple-regression modeling showed no significant associations between Toxoplasma gondii and depression in either the UK Biobank or NHANES datasets. Further, we found no significant interactions between Toxoplasma gondii and age, sex, educational attainment, and income in either dataset that affected the association between Toxoplasma gondii and depression. These results from two community-based datasets suggest that in these samples, Toxoplasma gondii is not associated with depression. Differences between our findings and other findings showing an association between Toxoplasma gondii and depression could be due to several factors including differences in socioeconomic variables, differences in Toxoplasma gondii strain, and use of different covariates in statistical modeling.

Background The hippocampus is important for memory processing. Several neuropsychiatric diseases including Alzheimer’s disease are associated with reduced hippocampal volume, and further the hippocampus appears vulnerable to environmental insult. Air pollution has been associated with cardiovascular disease, abnormal brain structure, and cognitive deficits. Objective Because of hippocampal vulnerability to environmental insults and based on the association between exposure to air pollution and cognitive function and brain structure, we evaluated the association between exposure to toxins in air pollution and left and right hippocampal volume using brain-imaging and air-pollution data from the UK Biobank, a large community-based dataset. Methods We used regression modelling to evaluate the association between exposure to nitrogen dioxide, nitrogen oxides, PM 2.5 , PM 2.5-10 , and PM 10. and left and right hippocampal volume controlling for age, sex, body-mass index, overall health, alcohol use, smoking, educational attainment, socioeconomic status, inverse distance from the nearest major road, and a measure of total brain volume. Results In these models, PM 2.5 concentration was associated with smaller left hippocampal volume. None of the other measures of air pollution was associated with either left or right hippocampal volume, although interaction models provided some evidence that sex might moderate the relationship between air pollution and hippocampal volume. In adjusted models, age, sex, educational attainment, income, overall health, current smoking, alcohol intake, and body-mass index were associated with hippocampal volume. Conclusions PM 2.5 at levels found in the United Kingdom was associated with smaller left hippocampal volume. Additional associations between several covariates and hippocampal volumes indicate that hippocampal volume might be associated with several potentially modifiable variables.

Background: Being overweight or obese is one of the most harmful risk factors to the health of a population. The cause of obesity is complex and multifactorial, but the primary cause is a nutrient poor diet. Despite excess intake of calories, obese individuals commonly have a lack of phytonutrients. Phytonutrients such as chlorophyll, carotenoids, and anthocyanins have all been shown to have anti-obesity effects. National data shows that states in with the lowest intakes of fruit and vegetable intake also have higher obesity rates. The data available depicts that a low fruit and vegetable intake, thus low phytonutrient intake, is correlated with excess adiposity.Methods: Fifty subjects from Thibodaux, Louisiana were randomly selected to participate. Three 24-hour food recalls were used to calculate phytonutrient content of the diets using the phytonutrient index. A food frequency questionnaire was also administered to determine intake of specific phytonutrients (carotenoids, anthocyanins, and carotenoids). Body adiposity was measured using body mass index (BMI), waist circumference, and fat percentage. Pearson correlation was used to assess correlations between phytonutrient index and body adiposity measures. Analysis of variance (ANOVA) with post-hoc tests was used to determine differences in PI and phytonutrient intakes among the BMI, waist circumference and percent body fat groups.Results: Participants who met healthy standards for BMI, waist circumference, and fat percentage all averaged much higher PI scores compared to those classified as obese/overweight. The data showed a strong inverse relationship between PI and BMI (r = -0.753, p = 0.00), waist circumference (r = -0.730, p = 0.00), and body fat percentage (r = -0.701, p = 0.00). Higher weekly intakes of chlorophyll, carotenoid, and anthocyanin rich foods had better body composition in comparison to those who consumed less (p

Objective Insomnia is associated with suicidality, although the mechanisms of this association are unclear. This study sought to replicate previous findings showing that insomnia symptoms but not sleep duration are associated with frequency of suicidal ideation in adults. We further investigated whether depression or sleep duration moderates the association between insomnia symptoms and frequency of suicidal ideation. Materials and Methods We used the 2005–2006 cycle of the National Health and Nutrition Examination Survey to replicate previously reported findings from the 2007–2008 cycle. We used ordered logistic regression to determine whether insomnia symptoms were associated with frequency of suicidal ideation independently of depression and other potential confounds. To extend these findings, we tested whether depression or sleep duration moderated the association between insomnia symptoms and frequency of suicidal ideation. We further replicated these findings in parallel analyses using the combined data from the 2005–2006 and 2007–2008 cycles. Results This study replicated previous results showing that insomnia symptoms are associated with frequency of suicidal ideation in the NHANES 2005–2006 cycle (OR = 1.09, p < 0.05), even after adjusting for potentially confounding variables, including depression. Neither depression nor sleep duration moderated this association. Difficulty with sleep maintenance insomnia symptoms were most robustly associated with frequency of suicidal ideation (OR ≥ 1.97, p < 0.05). Sleep duration was not robustly associated with suicidal ideation. Conclusions In this study, we found that insomnia symptoms were uniquely associated with frequency of suicidal ideation. This association cannot be explained by the shared association with depression or sleep duration.

Studies of meat allergic patients have shown that eating meat poses a serious acute health risk that can induce severe cutaneous, gastrointestinal, and respiratory reactions. Allergic reactions in affected individuals following meat consumption are mediated predominantly by IgE antibodies specific for galactose-α-1,3-galactose (α-gal), a blood group antigen of non-primate mammals and therefore present in dietary meat. α-gal is also found within certain tick species and tick bites are strongly linked to meat allergy. Thus, it is thought that exposure to tick bites promotes cutaneous sensitization to tick antigens such as α-gal, leading to the development of IgE-mediated meat allergy. The underlying immune mechanisms by which skin exposure to ticks leads to the production of α-gal-specific IgE are poorly understood and are key to identifying novel treatments for this disease. In this review, we summarize the evidence of cutaneous exposure to tick bites and the development of mammalian meat allergy. We then provide recent insights into the role of B cells in IgE production in human patients with mammalian meat allergy and in a novel mouse model of meat allergy. Finally, we discuss existing data more generally focused on tick-mediated immunomodulation, and highlight possible mechanisms for how cutaneous exposure to tick bites might affect B cell responses in the skin and gut that contribute to loss of oral tolerance.

Total brain gray-matter and white-matter volumes can be indicators of overall brain health. Among the factors associated with gray-matter and white-matter volumes is exposure to air pollution. Using data from the UK Biobank, we sought to determine associations between several components of air pollution&mdash, PM2.5, PM2.5&ndash, 10, PM10, nitrogen dioxide, and nitrogen oxides&mdash, and total gray-matter and total white-matter volumes in multivariable regression models in a large sample of adults. We found significant inverse associations between PM2.5 concentration and total white-matter volume and between PM2.5, PM2.5&ndash, 10, PM10, nitrogen dioxide, and nitrogen oxide concentrations and total gray-matter volume in models adjusted for age, sex, body-mass index, self-assessment of overall health, frequency of alcohol use, smoking status, educational attainment, and income. These findings of pollutant-associated decreases in total gray-matter and total white-matter volumes are in the context of mean PM2.5 concentrations near the upper limit of the World Health Organization&rsquo, s recommendations. Similarly, mean PM10 concentrations were below the recommended upper limit, and nitrogen dioxide concentration was slightly above. Still, there are many areas in the world with much higher concentrations of these pollutants, which could be associated with larger effects. If replicated, these findings suggest that air pollution could be a risk factor for neurodegeneration.

Neighborhood effects, or the development of community by neighborhoods, are often studied in an urban context. Previous research has neglected to examine the influence of neighborhoods in nonurban settings. Our case study, however, contributes to the existing literature as it takes place in a small, rural-to-urban town at an important point in time where the town was urbanizing. We find that neighborhood effects also influence community satisfaction and attachment in Creekdale, an urbanizing town. Using survey data (N = 1006) drawn from the Creekdale Community Citizens Viewpoint Survey (CCVS), we find that, contrary to conventional wisdom, population size and density does not matter necessarily for an individual&rsquo, s community attachment and satisfaction, community experience is shaped by neighborhood effects.

Ecological economics has long claimed distributive justice as a central tenet, yet discussions of equity and justice have received relatively little attention over the history of the field. While ecological economics has aspired to be transdisciplinary, its framing of justice is hardly pluralistic. Feminist perspectives and justice frameworks offer a structure for appraising the human condition that bridges social and ecological issues. Through a brief overview of the uptake of feminist perspectives in other social sciences, this paper outlines an initial justice-integration strategy for ecological economics by providing both a point of entry for readers to the vast and diverse field of feminist economic thought, as well as a context for the process of disciplinary evolution in social sciences. We also critique ecological economics' toleration of neoclassical mainstays such as individualism that run counter to justice goals. The paper concludes with a call for ecological economics practitioners and theorists to learn from other social sciences and elevate their attention to justice, to open possibilities for more dynamic, interdisciplinary, community-oriented, and pluralistic analysis.

Mood disorders are common mental illnesses. Among the factors associated with major depression are exposures to infectious diseases including hepatitis C, influenza, varicella-zoster, and herpes viruses. In this study, we sought to evaluate further associations between viral exposure and depression. From the US Center for Disease Control's National Health and Nutrition Examination Survey, we obtained data about depression status, antidepressant use, exposure to hepatitis A, hepatitis B, herpes simplex virus type 1, herpes simplex virus type 2, human immunodeficiency virus, and cytomegalovirus, and sociodemographic variables and evaluated associations between depression and viral exposure in adjusted multivariable models. Herpes simplex virus type 2 was associated with an increased risk of depression, whereas hepatitis A, hepatitis B, and herpes simplex virus type 1 were not. Higher cytomegalovirus antibody levels were associated with depression in subjects seropositive for cytomegalovirus. In conclusion, exposure to herpes simplex virus type 2 and possibly cytomegalovirus are associated with depression in an adult US sample.

Supportive non-parental adults, particularly non-familial adults, provide critical support during the transition to adulthood, opening doors to educational and career paths. The current study examined whether economic disadvantage shapes access to these relationships. Results showed that low-income adolescents had reduced access to naturally-occurring mentors, and the relationships they did form tended to be close bonds with family and friends, rather than non-familial adults. Their mentors were more likely to focus on practical support, and less likely to serve as role models or provide career advice. These effects of socio-economic status on natural mentoring relationships remained evident, even when accounting for youth race/ethnicity. Findings suggest that networks of support differ depending on a youth’s socio-economic context in ways that could perpetuate social and economic inequalities.

The [8+2] cycloaddition of indene-2-carbaldehydes and nitro olefins is described to provide benzonorbornene scaffolds in a highly peri-, diastereo-, and enantioselective fashion in the presence of a C2-symmetric aminocatalyst. This reaction, which proceeds through a transient semi-aromatic amino isobenzofulvene, represents the first example of catalytic formation and transformation of these species. Quantum chemical calculations suggest a kinetically controlled stepwise mechanism where the stereochemistry is determined in the first bond-forming event. Beyond the useful [8+2] cycloadducts, [10+4] cycloadducts have been identified in silico as potential off-pathway intermediates.

Following a concussion, both cognitive and physical rest are imperative aspects of injury management. The inclusion of academic adjustments and the formation of an interprofessional concussion management team (ICMT) provide a mechanism to manage academic issues following a concussion. As one of the sole healthcare providers presents during school hours, the school nurse may offer unique insight regarding the infrastructure of an ICMT in the secondary school setting. The purpose of this study was to explore school nurses' perceptions of and experiences with an ICMT for adolescents following a concussion in the secondary school setting. The consensual qualitative research approach was used to guide this study. Semi-structured individual telephone interviews were conducted with 15 school nurses employed in the secondary school setting across the United States. During data analysis, themes and categories were established based on a consensus process by the research team. Study findings indicated that school nurses identified several stakeholders regarding the concussion management team that are essential to include in the concussion management process. In addition to the school nurse, participants perceived an ICMT should include a physician, athletic trainer, school counsellor, teachers, and other stakeholders such as the patient and their parents. Additionally, participants discussed their perceptions of their own role as a member of an ICMT in the secondary school setting. The inclusion of an ICMT to aid the recovery following a concussion is vital to ensure proper care for the adolescent patient. Furthermore, the school nurse and athletic trainer must effectively collaborate, when possible, to ensure that concussed adolescents are allowed sufficient cognitive rest via the incorporation of academic adjustments during the recovery process.

Glutamine (Gln) is considered the preferred precursor for the neurotransmitter pool of glutamate (Glu), the major excitatory transmitter in the mammalian CNS. Here, an activity-regulated, high-affinity Gln transport system is described in developing and mature neuron-enriched hippocampal cultures that is potently inhibited by riluzole (IC50 1.3 +/- 0.5μM), an anti-glutamatergic drug, and is blocked by low concentrations of 2-(methylamino)isobutyrate (MeAIB), a system A transport inhibitor. K+-stimulated MeAIB transport displays an affinity (Km) for MeAIB of 37 +/- 1.2 μM, saturates at ~200 μM, is dependent on extracellular Ca2+, and is blocked by inhibition of voltage gated Ca2+-channels (VGCCs). Spontaneous MeAIB transport is also dependent on extracellullar Ca2+ and VGCCs, but is also blocked by the Na+ channel blocker tetrodotoxin, by Glu receptor antagonists, and by GABA indicating its dependence on intact neural circuits driven by endogenous glutamatergic activity. The transport of MeAIB itself does not rely on Ca2+, but on Na+ ions, and is pH-sensitive. Activity-regulated, riluzole-sensitive spontaneous and K+-stimulated transport is minimal at 7-8 days in vitro (DIV), coordinantly induced during the next two weeks, and is maximally expressed by DIV>20; the known period for maturation of the Glu/Gln cycle and regulated presynaptic Glu release. Competition analyses with various amino acids indicate that Gln is the most likely physiological substrate. Activity-regulated Gln/MeAIB transport is not observed in astrocytes. The functional identification of activity-regulated, high-affinity, riluzole-sensitive Gln/MeAIB transport in hippocampal neurons may have important ramifications in the neurobiology of activity stimulated presynaptic Glu release, the Glu/Gln cycle between astrocytes and neurons, and neuronal Glu-induced excitotoxicity. This article is protected by copyright. All rights reserved.

Invasive species raise concern around the globe, and much empirical and theoretical research effort has been devoted to their management. Integrodifference equations are theoretical tools that have been used to understand the spatiotemporal process of a species invasion, with the potential to yield insight into the possible biological control measures. We develop a system of integrodifference equations to explore the potential release of a castrating barnacle parasite Sacculina carcini to control spread and abundance of an invasive species, Carcinus maenas, the European green crab. We find that the parasite does not completely eradicate the green crab population, but has the potential to reduce its density. Our model suggests that the crab population is likely to outrun the spread of the parasite, causing two waves of invasion travelling at different speeds. By performing a sensitivity analysis, we investigate the effects of the demographic parameters on the speed of invasion. To conclude, we discuss the predicted outcomes for the European green crab, and other non-target hosts, of using the castrating barnacle as a biocontrol agent.

PCB forensic science is the process of identifying the source(s) of polychlorinated biphenyls (PCBs) at a site in the context of a legal proceeding to aid in identifying the party(s) responsible for the cost of environmental remediation. The PCB forensic scientist should assemble and examine all the evidence and then develop opinions about sources, discharges, deposition, fate, transport, environmental impact, and other issues at dispute among the parties. PCBs are complex mixtures of compounds (Aroclors in USA) that can simultaneously reveal information about the source of the contamination, but also provide confounding and contradictory evidence. The issues are technically complex and the expert must systematically evaluate the facts, employ deep technical expertise, and use dispassionate judgment to provide expert opinions that assist the judge, jury, arbitrator, or allocator in rendering their decision as to the responsible party(s) or an apportionment of that responsibility. Different PCB products were used and disposed of that have characteristic congener mixture profiles. In the environment, these profiles can mix and weather over decades. Sampling and analysis can generate further uncertainties, notably the possible misidentification of Aroclors. The expert’s challenge is to present their opinions clearly and authoritatively without overrepresenting the facts and data. This paper focuses on PCB contamination of sediment in aqueous sediment and uses a case study to illustrate application of forensic principles.

Purpose The purpose of the study was to evaluate a 12-week cooking education class on cooking confidence, dietary habits, weight status, and laboratory data among veterans with prediabetes and diabetes. Methods The sample for this study included 75 veterans within the Overton Brooks Veteran Affairs Medical Center who completed the 12-week class in an in-person group setting in Shreveport, Louisiana, or via Clinical Video Telehealth (CVT) in Longview, Texas. Veterans were referred to the Healthy Teaching Kitchen by their primary care provider or primary care dietitian. Enrollment in the class was on a volunteer basis. The cooking and nutrition education classes included topics such as carbohydrate counting, safety and sanitation, meal planning, and creating budget-friendly recipes. Participants completed 2 questionnaires for assessment of healthy dietary habits and confidence related to cooking. Changes in body weight, lipid panel, and hemoglobin A1C were assessed. Differences in class settings were tested via independent samples t tests. Paired samples t tests were completed to compare changes in mean laboratory results, weight, and questionnaire responses. Results Subjects lost a mean 2.91 ± 5.8 lbs ( P < .001). There was no significant difference in percent change in laboratory data and weight between subjects participating via CVT and subjects in the live class. Overall, there was significant improvement in the confidence questionnaire ratings and Healthy Habits Questionnaire responses. Conclusions Cooking and nutrition education can increase cooking confidence and dietary quality. These results provide support for the need for further research on the long-term effects of nutrition cooking education and for the benefits of using CVT software to provide education to remote facilities.

Clinical Scenario:Eating disorders in female athletes are a commonly underdiagnosed condition. Better screening tools for eating disorders in athletic females could help increase diagnosis and help athletes get the treatment they need.Focused Clinical Question:Should screening tools be used to detect eating disorders in female athletes?Summary of Key Findings:The literature was searched for studies that included information regarding the sensitivity and specificity of screening tools for eating disorders in female athletes. The search returned 5 possible articles related to the clinical question; 3 studies met the inclusion criteria (2 cross-sectional studies, 1 cohort study) and were included. All 3 studies reported sensitivity and specificity for the Athletic Milieu Direct Questionnaire version 2, the Brief Eating Disorder in Athletes Questionnaire version 2, and the Physiologic Screening Test to Detect Eating Disorders Among Female Athletes. All 3 studies found that the respective screening tool was able to accurately identify female athletes with eating disorders; however, the screening tools varied in sensitivity and specificity values.Clinical Bottom Line:There is strong evidence to support the use of screening tools to detect eating disorders in female athletes. Screening tools with higher sensitivity and specificity have demonstrated a successful outcome of determining athletes with eating disorders or at risk for developing an eating disorder.Strength of Recommendation:There is grade A evidence available to demonstrate that screening tools accurately detect female athletes at risk for eating disorders.

International agricultural carbon market projects face significant challenges in delivering greenhouse gas mitigation objectives whilst also seeking to provide additional benefits for poverty alleviation. The carbon credit producer (the smallholder farmer) and carbon credit buyer in the carbon market transaction typically operate at different spatial and temporal scales. Buyers operate at a global scale, responding to opportunities for financial speculation and both private and public climate action plans. Farmers operate within households, farms, and immediate agricultural landscapes, pursuing livelihood and food security needs. These different scales often result in mismatches of timing, payment, and knowledge in market transactions and can be partially rectified by project developers who serve to broker the relationship between the farmers and the buyers. We examined eight East African agricultural carbon market projects to determine how project developers function as bridging organizations and minimize the mismatches between these actors. Results show that projects better bridged the timing and payment gap between buyers and producers when project developers provided non-monetary benefits or direct monetary assistance to farmers. However, knowledge gaps remained a significant barrier for farmers wishing to participate in the market. We discuss how project developers brokered relationships in ways that reflected their interests and highlight the limitations, trade-offs, and challenges that must be overcome if win-win outcomes of poverty alleviation and climate change mitigation are to be realized.

The tetrylenes Ge(ArMe6)2 and Sn(ArMe6)2 (ArMe6 = C6H3-2,6-(C6H2-2,4,6-(CH3)3)2) reacted with dimethylzinc to afford the insertion products (ArMe6)2Ge(Me)ZnMe (1) and (ArMe6)2Sn(Me)ZnMe (3), which feature Ge–Zn and Sn–Zn bonds as well as two-coordinate zinc atoms. Crystals of 1 were found to be unsuitable for X-ray crystallography, so the ethyl-substituted (ArMe6)2Ge(Et)ZnEt (2) was synthesized in a parallel way to provide crystals suitable for X-ray studies. These showed the structure to be similar to that of 3. The reaction of Pb(ArMe6)2 with dimethylzinc yielded ArMe6ZnMe with a linearly coordinated zinc atom via ligand exchange but no characterizable, new lead product was obtained. The reaction of Sn(ArMe6)2 with dimethylzinc is reversible in hydrocarbon solution at room temperature and displayed a dissociation constant Kdiss and a ΔGdiss of 0.0028(5) and 14(4) kJ mol–1 at 298 K, respectively. Compounds 1–4 were characterized by NMR and IR spectroscopy as well as by X-ray crystallography for 1, 3, and 4.

Under the U.N. Convention on the Rights of the Child, every child is entitled to free primary school education and access to secondary school or occupational training, and education has become one of the basic indicators of child wellbeing. Large scale studies published in the 1990s and early 2000s generally showed that significant educational disparities existed based on orphan status and a child's relationship to the head of the household. Poverty, gender and rural residence were also shown to contribute to the disparities. Since the data relied on by these studies were collected, the global community has conducted major campaigns to close these gaps, through the Education for All (EFA) and Millennium Development Goals (MDGs). This study (N = 124.592) examined these factors using eight country-years from five sub-Saharan African countries, since half of the children out of school live in that region. Findings show that considerable progress has been made to close the disparity based on orphan status, and the gender gap is also closing. However, poverty remains a challenge across all variables, and there are pockets of gender disparity for both boys and girls, particularly in areas where deeply rooted cultural and child raising patterns are retained. Most alarmingly, children who live with non-relatives have the lowest attendance rate. Continued efforts to target these groups of children and their households are urged, as well as research on the underserved children.

An organocatalyzed asymmetric [4+2]-cycloaddition between tropolones and electron-deficient dienophiles is presented. Complex and biologically interesting dihydrohomobarrelenone scaffolds are formed through a Diels-Alder reaction utilizing bifunctional Bronsted-base catalysis, affording the corresponding bridged bicyclic cycloadducts in up to quantitative yields with good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). The synthetic value of the obtained products is explored by downstream transformations, including photoisomerizations, and their biological relevancy by in vivo testing in MCF-7 cancer cells.