Both stable intermediates of anhydride and NHS-ester were observed after EDC/NHS activation of PMAA, where NHS-ester waxes, while anhydride wanes complementarily with increasing fragmentation degree of PMAA blocks in PMAA-associated polymer blends.
Thousands of nucleotide(nt)-long single strand DNAs, generated from rolling-circle-amplification (RCA), were used as scaffolds to create DNA nanoscale wires and plates with a few short staple strands by following the origami design principle with a crossover at 1.5 turns. The core sequence of the circle template, for producing tens and hundreds of tandemly repeated copies of it by RCA, was designed according to Seeman's sequence design principle for nucleic acid structural engineering (Seeman, N. C. J. Biomol. Struct. Dyn. 1990, 8, 573). The significance for folding the RCA products into nanoscale shapes lies in the design flexibility of both staple and scaffold strand codes, simplicity of a few short staple strands to fold the periodic sequence of RCA products, and lower cost.
Small circular DNA molecules with designed lengths, for example 64 and 96 nucleotides (nt), after hybridization with a few 32-nt staple strands respectively, can act as rigid motifs for the construction of DNA nanotubes with excellent uniformity in ring diameter. Unlike most native DNA nanotubes, which consist of longitudinal double helices, nanotubes assembled from circular DNAs are constructed from lateral double helices. Of the five types of DNA nanotubes designed here, four are built by alternating two different rings of the same ring size, while one is composed of all the same 96-nt rings. Nanotubes constructed from the same 96-nt rings are 10-100 times shorter than those constructed from two different 96-nt rings, because there are fewer hinge joints on the rings.
Carboranyl aldehydes are among the most useful synthons in derivatization of carboranes. However, compared to the utilization of carboranyl carboxylic acids in selective B-H bond functionalizations, the synthetic application of carboranyl aldehydes is limited due to the weakly coordinating nature of the aldehyde group. Herein, the direct arylation of o-carboranyl aldehydes has been developed via Pd-catalyzed cage B-H bond functionalization. With the help of glycine to generate a directing group (DG) in situ, a series of cage B(4,5)-diarylated- and B(4)-monoarylated-o-carboranyl aldehydes were obtained in good to excellent yields with high selectivity. A wide range of functional groups are tolerated. The aldehyde group in the B-H arylated products could be readily removed or transformed into o-carboranyl methanol. A plausible catalytic cycle for B-H arylation was proposed based on control experiments and stoichiometric reactions, including the isolation of a key bicyclic palladium complex.
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