Dual catalytic decarboxylative allylations of α-amino acids and their divergent mechanisms

This is the peer reviewed version of the following article: Lang, S. B., O'Nele, K. M., Douglas, J. T. and Tunge, J. A. (2015), Dual Catalytic Decarboxylative Allylations of α-Amino Acids and Their Divergent Mechanisms. Chem. Eur. J., 21: 18589–18593. doi:10.1002/chem.201503644, which has been published in final form at http://doi.org/10.1002/chem.201503644. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.The room temperature radical decarboxylative allylation of N-protected α-amino acids and esters has been accomplished via a combination of palladium and photoredox catalysis to provide homoallylic amines. Mechanistic investigations revealed that the stability of the α-amino radical, which is formed by decarboxylation, dictates the predominant reaction pathway between competing mechanisms

Motivational Interviewing as Evidence-Based Practice? An Example from Sexual Risk Reduction Interventions Targeting Adolescents and Young Adults

This paper critically examines sexual risk reduction interventions, more specifically how they are evaluated and the implications that this has for sexual health policy. The focus is on motivational interviewing (MI) interventions which aim to promote protective behaviors related to sexual risk on the part of young people. MI has become increasingly popular, largely due to it being a highly flexible counseling approach that may, with adequate staff training, and fidelity in implementation, be tailored to many different settings (e.g., health care, schools and in community work). Following a scoping review that comprised 34 papers, of which 29 were unique studies, the range and type of existing research were examined. The results show a wide range of study designs and evaluation procedures, MI conceptualizations, modes of MI delivery, and the particular sub-populations of youth and sexual risk behaviors targeted. While this makes it difficult to draw any generalized conclusions about “what works” in prevention, it provides important insights about the complexity of sexual risk behavior as well as complex behavioral treatment approaches like MI. We therefore problematize the political drive to implement evidence-based methods without adequate resource allocation and contextual adaptation

Control of Hepatic Gluconeogenesis through the Transcriptional Coactivator PGC-1

Blood glucose levels are maintained by the balance between glucose uptake by peripheral tissues and glucose secretion by the liver. Gluconeogenesis is strongly stimulated during fasting and is aberrantly activated in diabetes mellitus. Here we show that the transcriptional coactivator PGC-1 is strongly induced in liver in fasting mice and in three mouse models of insulin action deficiency: streptozotocin-induced diabetes, ob/ob genotype and liver insulin-receptor knockout. PGC-1 is induced synergistically in primary liver cultures by cyclic AMP and glucocorticoids. Adenoviral-mediated expression of PGC-1 in hepatocytes in culture or in vivo strongly activates an entire programme of key gluconeogenic enzymes, including phosphoenolpyruvate carboxykinase (PEPCK) and glucose-6-phosphatase, leading to increased glucose output. Full transcriptional activation of the PEPCK promoter requires coactivation of the glucocorticoid receptor and the liver-enriched transcription factor HNF-4alpha (hepatic nuclear factor-4alpha) by PGC-1. These results implicate PGC-1 as a key modulator of hepatic gluconeogenesis and as a central target of the insulin–cAMP axis in liver