Exploring chemoselective S-to-N acyl transfer reactions in synthesis and chemical biology.

-to- acyl transfer is a high-yielding chemoselective process for amide bond formation. It is widely utilized by chemists for synthetic applications, including peptide and protein synthesis, chemical modification of proteins, protein-protein ligation and the development of probes and molecular machines. Recent advances in our understanding of -to- acyl transfer processes in biology and innovations in methodology for thioester formation and desulfurization, together with an extension of the size of cyclic transition states, have expanded the boundaries of this process well beyond peptide ligation.

Glycosylated lanthanide cyclen complexes as luminescent probes for monitoring glycosidase enzyme activity.

The development of synthetic chemical probes for the detection of enzymes is extremely important for biological, medicinal, and industrial applications. Here we report the synthesis of an array of novel glycosylated Tb(iii) complexes, their photophysical properties in solution, and their ability to function as luminescent probes for observing glycosidase enzyme activity in real time. Our initial studies into the application of these complexes for the detection of the Concanavalin A (ConA) lectin is also reported, highlighting the broad scope of these novel chemical probes.

Recent advances in the development of synthetic chemical probes for glycosidase enzymes.

The emergence of synthetic glycoconjugates as chemical probes for the detection of glycosidase enzymes has resulted in the development of a range of useful chemical tools with applications in glycobiology, biotechnology, medical and industrial research. Critical to the function of these probes is the preparation of substrates containing a glycosidic linkage that when activated by a specific enzyme or group of enzymes, irreversibly releases a reporter molecule that can be detected. Starting from the earliest examples of colourimetric probes, increasingly sensitive and sophisticated substrates have been reported.

A copper-catalyzed Petasis reaction for the synthesis of tertiary amines and amino esters.

We have developed a copper-catalyzed process for the coupling of aldehydes, amines, and boronic acids. This allows greater reactivity with simple aryl boronic acids and allows coupling reactions to proceed that previously failed. Initial mechanistic studies support a process involving transmetalation from boron to copper.

Patient experiences of structured heart failure programmes.

Objectives. Patient experiences of structured heart failure rehabilitation and their views on the important components of heart failure services were examined. Methods.