Conjugated Nanohoop Polymers based on Antiaromatic Dibenzopentalenes for Charge Storage in Organic Batteries

With their bent π-systems, cyclic conjugation and inherent cavities, conjugated nanohoops are attractive for organic electronics applications. For ease of processing and morphological stability, an incorporation into polymers is desirable, but to date was hampered with few exceptions by synthetic difficulties. We herein present a unique strategy for the synthesis of conjugated nanohoop polymers using a dibenzo[a,e]pentalene (DBP) as central connector. We demonstrate this versatility by synthesizing three electronically diverse copolymers with dithienyldiketo(pyrrolopyrrol), fluorene and carbazole comonomers, and report the first donor-acceptor nanohoop polymer. Optoelectronic investigations reveal the prevalence of cyclic or linear conjugation, depending on the comonomer unit, and ambipolar electrochemical properties through the antiaromatic character of the DBP units. As the first report on using conjugated nanohoops for charge storage as positive electrode materials, we show a significant improvement in battery performance in a nanohoop-containing polymer compared to an equivalent nanohoop-free reference polymer. We believe this study will pave the way for the synthesis of a diverse range of nanohoop polymers and further stimulate their exploration for charge storage in batteries.     

Swellable theophylline selective microparticles for sensing applications

Lightly crosslinked theophylline-templated copolymer microparticles of N-isopropylacrylamide and methacrylic acid bind theophylline with high sensitivity and selectivity at high temperatures.     

Photophysical characterization of a cytidine-guanosine tethered phthalocyanine-fullerene dyad

A new non-covalent electron transfer model system, based on the use of cytidine-guanosine hydrogen bonding interactions, is described that incorporates a phthalocyanine photodonor and a C60 fullerene acceptor.     

Expanding the scope of native chemical ligation – templated small molecule drug synthesis via benzanilide formation

We describe a reaction system that enables the synthesis of Bcr–Abl tyrosine kinase inhibitors (TKI) via benzanilide formation in water. The reaction is based on native chemical ligation (NCL). In contrast to previous applications, we used the NCL chemistry to establish aromatic rather than aliphatic amide bonds in coupling reactions between benzoyl and o-mercaptoaniline fragments. The method was applied for the synthesis of thiolated ponatinib and GZD824 derivatives. Acid treatment provided benzothiazole structures, which opens opportunities for diversification. Thiolation affected the affinity for Abl1 kinase only moderately. Of note, a ponatinib-derived benzothiazole also showed nanomolar affinity. NCL-enabled benzanilide formation may prove useful for fragment-based drug discovery. To show that benzanilide synthesis can be put under the control of a template, we connected the benzoyl and o-mercaptoaniline fragments to DNA and peptide nucleic acid (PNA) oligomers. Complementary RNA templates enabled adjacent binding of reactive conjugates triggering a rapid benzoyl transfer from a thioester-linked DNA conjugate to an o-mercaptoaniline-DNA or -PNA conjugate. We evaluated the influence of linker length and unpaired spacer nucleotides within the RNA template on the product yield. The data suggest that nucleic acid-templated benzanilide formation could find application in the establishment of DNA-encoded combinatorial libraries (DEL).

The templated native chemical ligation between benzoyl thioesters and o-mercaptoaniline fragments proceeds in water and provides benzanilides that have nanomolar affinity for Abl1 kinase.