We report on a new class of thermoresponsive biodegradable polyesters (TR-PE) inspired by polyacrylamides and elastin-like proteins (ELPs). The polyesters display reversible phase transition with tunable cloud point temperatures (T cp ) in aqueous solution as evidenced by UV−vis spectroscopy, 1 H NMR, and DLS measurements. These polyesters form coacervate droplets above their lower critical solution temperature (LCST). The T cp of the polyesters is influenced by the solutes such as urea, SDS, and NaCl. The T cp of the copolymers shows a linear correlation with the composition of the polyesters indicating the ability to tune the phase change temperature. We also show that such thermoresponsive coacervates are capable of encapsulating small molecules such as Nile Red. Furthermore, the polyesters are hydrolytically degradable.
The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion-transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm-sized, fullerene-shaped molecular cluster Li48+m K12(OH)m [UO2(O2)(OH)]60-(H2O)n (m ≈ 20 and n ≈ 310) (U60) shows selective permeability to different alkali ions. The subnanometer pores on the water-ligand-rich surface of U60 are able to block Rb(+) and Cs(+) ions from passing through, while allowing Na(+) and K(+) ions, which possess larger hydrated sizes, to enter the interior space of U60. An interestingly high entropy gain during the binding process between U60 and alkali ions suggests that the hydration shells of Na(+)/K(+) and U60 are damaged during the interaction. The ion selectivity of U60 is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells.
The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe 28 The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis of the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection.
The symmetry, structure and formation mechanism of the structurally self-complementary {Pd84} = [Pd84O42(PO4)42(CH3CO2)28](70-) wheel is explored. Not only does the symmetry give rise to a non-closest packed structure, the mechanism of the wheel formation is proposed to depend on the delicate balance between reaction conditions. We achieve the resolution of gigantic polyoxopalladate species through electrophoresis and size-exclusion chromatography, the latter has been used in conjunction with electrospray mass spectrometry to probe the formation of the ring, which was found to proceed by the stepwise aggregation of {Pd6}(-) = [Pd6O4(CH3CO2)2(PO4)3Na(6-n)H(n)](-) building blocks. Furthermore, the higher-order assembly of these clusters into hollow blackberry structures of around 50 nm has been observed using dynamic and static light scattering.
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