Rh-catalysed NH carbene insertion reactions were exported to living cells with help of amphiphilic polymeric nanoparticles. Hereto, hydrophobic dirhodium carboxylate catalysts were efficiently encapsulated in amphiphilic polymeric nanoparticles comprising dodecyl and Jeffamine as side grafts. The developed catalytic nanoparticles promoted NH carbene insertions between α-keto diazocarbenes and 2,3-diaminonaphthalene, followed by intramolecular cyclisation to form fluorescent or biologically active benzoquinoxalines.
View Article and Find Full Text PDFEnzymatic DNA synthesis (EDS) is a promising benchtop and user-friendly method of nucleic acid synthesis that, instead of solvents and phosphoramidites, uses mild aqueous conditions and enzymes. For applications such as protein engineering and spatial transcriptomics that require either oligo pools or arrays with high sequence diversity, the EDS method needs to be adapted and certain steps in the synthesis process spatially decoupled. Here, we have used a synthesis cycle comprising a first step of site-specific silicon microelectromechanical system inkjet dispensing of terminal deoxynucleotidyl transferase enzyme and 3' blocked nucleotide, and a second step of bulk slide washing to remove the 3' blocking group.
View Article and Find Full Text PDFThe hexagonally close-packed (HCP) sphere phase is predicted to be stable across a narrow region of linear block copolymer phase space, but the small free energy difference separating it from face-centered cubic spheres usually results in phase coexistence. Here, we report the discovery of pure HCP spheres in linear block copolymer melts with A = poly(2,2,2-trifluoroethyl acrylate) ("F") and B = poly(2-dodecyl acrylate) ("2D") or poly(4-dodecyl acrylate) ("4D"). In 4DF diblocks and F4DF triblocks, the HCP phase emerges across a substantial range of A-block volume fractions (circa = 0.
View Article and Find Full Text PDFA versatile and scalable strategy is reported for the rapid generation of block copolymer libraries spanning a wide range of compositions starting from a single parent copolymer. This strategy employs automated and operationally simple chromatographic separation that is demonstrated to be applicable to a variety of block copolymer chemistries on multigram scales with excellent mass recovery. The corresponding phase diagrams exhibit increased compositional resolution compared to those traditionally constructed via multiple, individual block copolymer syntheses.
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