Many high-yielding reactions for forming peptide bonds have been developed but these are complex, requiring activated amino-acid precursors and heterogeneous supports. Herein we demonstrate the programmable one-pot dehydration–hydration condensation of amino acids forming oligopeptide chains in around 50% yield. A digital recursive reactor system was developed to investigate this process, performing these reactions with control over parameters such as temperature, number of cycles, cycle duration, initial monomer concentration and initial pH. Glycine oligopeptides up to 20 amino acids long were formed with very high monomer-to-oligomer conversion, and the majority of these products comprised three amino acid residues or more. Having established the formation of glycine homo-oligopeptides, we then demonstrated the co-condensation of glycine with eight other amino acids (Ala, Asp, Glu, His, Lys, Pro, Thr and Val), incorporating a range of side-chain functionality.
12 March 2014 in Angewandte Chemie International Edition
The synthesis of chiral polyoxometalates (POMs) is a challenge because of the difficulty to induce the formation of intrin-sically chiral metal-oxo frameworks. Herein we report the stereoselective synthesis of a series of gigantic chiral Mo Blue (MB) POM clusters 1-5 that form by exploiting the synergy between coordinating lanthanides ions as symmetry breakers to produce MBs with chiral frameworks decorated with amino acids ligands; these promote the selective formation of en-antiopure MBs. All the compounds share the same framework archetype, based on {Mo124Ce4}, which forms an intrinsical-ly chiral or configurations controlled by the configurations of functionalized chiral amino acids. The chirality and stability of 1-5 in solution are confirmed by CD, 1H NMR and Electrospray Ion Mobility-Mass Spectrometry (ESI-IMS-MS) study. In addition, the framework of the {Mo124Ce4} MB not only behaves as host, able to trap a chiral {Mo8} cluster that is not accessible by traditional synthesis, but also exhibits an enzyme-like selective oxidation of tryptophan to kynurenine in-situ. This work demonstrates the potential and applicability of our synthetic strategy produce gigantic chiral POM clusters capable of host-guest chemistry and selective synthetic transformations.
There is a growing need for chemical analyses to be performed in the field, at the point of need. Tools and techniques often found in analytical chemistry laboratories are necessary in performing these analyses, yet have, historically, been unable to do so owing to their size, cost and complexity. Technical advances in miniaturisation and liquid chromatography are enabling the translation of these techniques out of the laboratory, and into the field. Here we examine the advances that are enabling portable liquid chromatography (LC). We explore the evolution of portable instrumentation from its inception to the most recent advances, highlighting the trends in the field and discussing the necessary criteria for developing in-field solutions. While instrumentation is becoming more capable it has yet to find adoption outside of research.
4 September 2014 in Journal of the American Chemical Society