The active template synthesis of mechanically interlocked molecular architectures exploits the dual ability of various structural elements (metals or, in the case of metal-free active template synthesis, particular arrangements of functional groups) to serve as both a template for the organisation of building blocks and as a catalyst to facilitate the formation of covalent bonds between them. This enables the entwined or threaded intermediate structure to be covalently captured under kinetic control. Unlike classical passive template synthesis, the intercomponent interactions transiently used to promote the assembly typically do not 'live on' in the interlocked product, meaning that active template synthesis can be traceless and used for constructing mechanically interlocked molecules that do not feature strong binding interactions between the components.
View Article and Find Full Text PDFChallenges for the development of efficacious new superbases include their ease of synthesis, chemical stability, and high basicity, while minimizing nucleophilicity is important for reducing unwanted side reactions. Here, we introduce a new family of organic superbases, compact amine-crown ether rotaxanes, which show desirable characteristics in all these respects. Metal-free active template synthesis provides access to a range of rotaxanes with as little as three atoms between the stoppering groups, locking the location of a small crown ether (21C7 and 24C8 derivatives) over the amine group of the axle.
View Article and Find Full Text PDFAs interlocutors in national level discourse with the power to influence public opinion and inform policy, the news media are an important data source in understanding the constitutive roles played by culture and discourse in shaping health experiences and outcomes. This paper reports on a critical discourse analysis of news media coverage of HIV in the Republic of Ireland between 2006 and 2016. This period is significant because of the considerable increase in new HIV diagnoses that occurred in Ireland after the 2008 recession.
View Article and Find Full Text PDFHexafluoroisopropanol (HFIP) is a solvent with unique properties that has recently gained attention for promoting a wide range of challenging chemical reactions. It was initially believed that HFIP was almost exclusively involved in the stabilization of cationic intermediates, owing to its high polarity and low nucleophilicity. However, in many cases, the mechanism of action of HFIP appears to be more complex.
View Article and Find Full Text PDFStigma in healthcare settings remains a barrier to accessing screening, treatment and care for HIV and is a driver of the global HIV epidemic. This study examined the stigma experiences in healthcare settings of people living with HIV (PLHIV) in Ireland. Semi-structured interviews were carried out with 4 women and 10 men living with HIV.
View Article and Find Full Text PDFThe timely delivery of the most up-to-date medicines and drug products is essential for patients throughout the world. Successful scaling of the bioreactors used within the biopharmaceutical industry plays a large part in the quality and time to market of these products. Scale and topology differences between vessels add a large degree of complication and uncertainty within the scaling process.
View Article and Find Full Text PDFPhosphorylation is one of the most important post-translational modifications, playing a crucial role in regulating many cellular processes, including transcription, cytoskeletal rearrangement, cell proliferation, differentiation, apoptosis, and signal transduction. However, to date, little work has been carried out on the phosphoproteome in CHO cells. In this study we have carried out a large scale differential phosphoproteomic analysis of recombinant CHO cells following a reduction of culture temperature (temperature shift).
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