Kinetics and mechanism of sequential ring methyl C–H activation in cyclopentadienyl rhodium(iii) complexes

We have studied activation of the methyl C–H bonds in the cyclopentadienyl ligands of half-sandwich Rh(III) complexes [η5-CpXRh(N,N′)Cl]+ by observing the dependence of sequential H/D exchange on variations in CpX = Cp* (complexes 1 and 2), Me4PhCp (CpXPh, 3) or Me4PhPhCp (CpXPhPh, 4), and chelated ligand N,N′ (bpy, 1; phen, 2–4). H/D exchange was fastest in d4-MeOD (t1/2 = 10 min, 37 °C, complex 1), no H/D exchange was observed in DMSO/D2O, and d4-MeOD enhanced the rate in CD3CN. The proposed Rh(I)–fulvene intermediate was trapped by [4 + 2] Diels–Alder reactions with conjugated dienes and characterized. The Rh(I) oxidation state was confirmed by X-ray photoelectron spectroscopy (XPS). Influence of solvent on the mechanisms of activation and Diels–Alder adduct formation was modelled using DFT calculations with the CAM-B3LYP functional and CEP-31 g basis set, and influence on the reaction profile of the dimiine ligand and phenyl substituent using the larger qzvp basis set. The Rh(III)–OH intemediate is stabilised by H-bonding with methanol and a Cp* CH3 hydrogen. The Rh(I)(Me4fulvene) species, stabilised by interaction of methanol with a coordinated water, again by two H-bonds H2O–HOMe (1.49 Å) and fulvene CH2 (1.94 Å), arises from synchronous transfer of the methanol OH proton to a Rh(III)–OH ligand and Cp* methyl hydrogen to the methanol oxygen. Additionally, the observed trend in catalytic activity for complexes 1–4 was reproduced by DFT calculations. These complexes form a novel class of catalytic molecular motors with a tunable rate of operation that can be stalled in a given state. They provide a basis for elucidation of the effects of ligand design on the contributions of electronic, rotational and vibrational energies to each step in the reaction pathway at the atomic level, consideration of which will enhance the design principles for the next generation of molecular machines

Losing Our Minds? New Research Directions on Skilled Migration and Development

This paper critiques the last decade of research on the effects of high-skill emigration from developing countries, and proposes six new directions for fruitful research. The study singles out a core assumption underlying much of the recent literature, calling it the Lump of Learning model of human capital and development, and describes five ways that research has come to challenge that assumption. It assesses the usefulness of the Lump of Learning model in the face of accumulating evidence. The axioms of the Lump of Learning model have shaped research priorities in this literature, but many of those axioms do not have a clear empirical basis. Future research proceeding from established facts would set different priorities, and would devote more attention to measuring the effects of migration on skilled-migrant households, rigorously estimating human capital externalities, gathering microdata beyond censuses, and carefully considering optimal policy among others. The recent literature has pursued a series of extensions to the Lump of Learning model. This study urges discarding the Lump of Learning model, pointing toward a new paradigm for research on skilled migration and development

Para-infectious brain injury in COVID-19 persists at follow-up despite attenuated cytokine and autoantibody responses

To understand neurological complications of COVID-19 better both acutely and for recovery, we measured markers of brain injury, inflammatory mediators, and autoantibodies in 203 hospitalised participants; 111 with acute sera (1–11 days post-admission) and 92 convalescent sera (56 with COVID-19-associated neurological diagnoses). Here we show that compared to 60 uninfected controls, tTau, GFAP, NfL, and UCH-L1 are increased with COVID-19 infection at acute timepoints and NfL and GFAP are significantly higher in participants with neurological complications. Inflammatory mediators (IL-6, IL-12p40, HGF, M-CSF, CCL2, and IL-1RA) are associated with both altered consciousness and markers of brain injury. Autoantibodies are more common in COVID-19 than controls and some (including against MYL7, UCH-L1, and GRIN3B) are more frequent with altered consciousness. Additionally, convalescent participants with neurological complications show elevated GFAP and NfL, unrelated to attenuated systemic inflammatory mediators and to autoantibody responses. Overall, neurological complications of COVID-19 are associated with evidence of neuroglial injury in both acute and late disease and these correlate with dysregulated innate and adaptive immune responses acutely

A prenylated dsRNA sensor protects against severe COVID-19

Inherited genetic factors can influence the severity of COVID-19, but the molecular explanation underpinning a genetic association is often unclear. Intracellular antiviral defenses can inhibit the replication of viruses and reduce disease severity. To better understand the antiviral defenses relevant to COVID-19, we used interferon-stimulated gene (ISG) expression screening to reveal that OAS1, through RNase L, potently inhibits SARS-CoV-2. We show that a common splice-acceptor SNP (Rs10774671) governs whether people express prenylated OAS1 isoforms that are membrane-associated and sense specific regions of SARS-CoV-2 RNAs, or only express cytosolic, nonprenylated OAS1 that does not efficiently detect SARS-CoV-2. Importantly, in hospitalized patients, expression of prenylated OAS1 was associated with protection from severe COVID-19, suggesting this antiviral defense is a major component of a protective antiviral response

Are we parent-friendly? Social Workers’ Views of Parents of Children with Emotional and Behavioral Disabilities

A current model of family-centered practice emphasizes empowerment of parents, an approach that brings together a strengths perspective, a constructivist emphasis on consumer voices, and knowledge derived from neuroscience of the last two decades. This study explored the extent to which a national random sample of National Association of Social Workers members hold beliefs and attitudes congruent with the parent empowerment perspective. Two profiles emerged from the data. Respondents who disagree with statements attributing blame to parents agree with sharing information openly with parents; believe that parents are doing their best, are credible reporters, and are experts about their own children; agree that workers need research knowledge; and disagree that the child is usually the identified patient in a a dysfunctional family. By contrast, respondents who believe parents cause their children\u27s emotional and behavioral problems disagree with open information sharing; disagree that parents are doing their best or are experts about their own children; agree that the child is an identified patient in a dysfunctional family; and agree that parents\u27 ideas are important mostly to give the worker clues about family dynamics. The majority of the sample reported parent-friendly views, but a substantial minority of respondents reported beliefs antithetical to parent empowerment

Produtividade agregada brasileira (1970-2000): declínio robusto e fraca recuperação

Este artigo discute o comportamento da Produtividade Total dos Fatores (PTF) no Brasil entre 1970 e 1998. É feita uma análise de quanto da queda da PTF pode ser explicado a partir de mudanças na forma tradicional de cálculo desta variável. Entre as variações serão consideradas: utilização da capacidade instalada, modificações no uso do capital, mensuração do capital por meio do consumo de eletricidade, distorções no preço relativo, capital humano e investimento específico à determinada tecnologia. O único caso no qual a PTF apresenta uma modificação em seu comportamento é o de correção de distorções no preço relativo, em que a PTF se recupera mais rapidamente.<br>This study explores the productivity performance of the Brazilian economy between 1970 and 1998. We assess how much of the TFP downfall can be explained by some departures from the standard procedure. We incorporate to the standard measure utilization of capacity, changes in the workweek of capital, services of capital from electricity consumption, relative prices distortions, human capital, and investment in specific technology. We conclude that the downfall in productivity is quite robust to those specifications. The only case that presents a marked difference from the standard TFP measure occurs when relative prices of capital are corrected. The implications of this finding are a topic for future research