We herein report the tunable self-assembly of simple block copolymers, namely polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers, into porous cubosomes with inverse Im3‾m or Pn3‾m mesophases of controlled unit cell parameters as well as hexasomes with an inverse hexagonal (p6mm) structure, which have been rarely observed in polymer self-assembly. A new morphological phase diagram was constructed for the solution self-assembly of PS-b-PEO based on the volume fraction of the PS block against the initial copolymer concentration. The formation mechanisms of the cubosomes and hexasomes have also been revealed. This study not only affords a simple system for the controllable preparation and fundamental studies of ordered bicontinuous structures, but also opens up a new avenue towards porous architectures with highly ordered pores.
The viability of 1,3-dipolar cycloadditions of a series of 1,3-dipolar molecules (azomethine ylide, ozone, nitrone, nitrile imine, nitrile ylide, nitrile oxide, diazomethane, and methyl azide) onto the sidewalls of carbon nanotubes has been assessed theoretically by means of a two-layered ONIOM approach. The theoretical calculations predict the following: (i) other than the 18-valence-electron azomethine ylide and ozone, the 16-valence-electron nitrile ylide and nitrile imine are the best candidates for experimentalists to try; (ii) upon 1,3-dipolar cycloaddition, a 1,3-diople molecule is di-sigma-bonded to a pair of carbon atoms on the sidewall of SWNT, forming a five-membered ring surface species; (iii) the as-formed 1,3-dipole-SWNT bonding is much weaker than that in the products of the molecular 1,3-DC reactions and can be plausibly broken by heating at elevated temperatures; (iv) the sidewalls of the armchair (n,n) SWNTs (n = 5-10) are subject to the 1,3-DCs of ozone and azomethine ylides; (v) both the 1,3-DC reactivity and retro-1,3-DC reactivity are moderately dependent on the diameters of SWNTs, implying the feasibility of making use of the heterogeneous 1,3-DC chemistry to purify and separate SWNTs diameter-specifically.
Fenced in: Selective electrochemical desorption of self‐assembled monolayers of HS(CH2)11(OCH2CH2)6OH was carried out on parts of a gold substrate restricted to microfluidic channels. This chemical transformation activates parts of the surface for adhesion of multiple types of cells with well‐controlled geometry.
The pollution arising from oil spills is a matter of great concern due to its damaging impacts on the ecological environment, which has created a tremendous need to find more efficient materials for oil spill cleanup. In this work, we reported a sorbent for oil soak-up from a water surface with a high sorption capacity, good selectivity, and excellent reusability based on the hydrophobic-oleophilic fibrous mats that were fabricated via co-axial electrospinning polystyrene (PS) solution as the shell solution and polyurethane (PU) solution as the core solution. The fine structures of as-prepared fibers were regulated by manipulating the spinning voltages, core solution concentrations, and solvent compositions in shell solutions, which were also characterized by field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption method, and synchrotron radiation small-angle X-ray scattering. The effects of inter-fiber voids and intra-fiber porosity on oil sorption capacities were well studied. A comparison of oil sorption capacity for the single fiber with different porous structures was also investigated with the help of scanning transmission X-ray microscopy. The results showed that the sorption capacities of the as-prepared sorbent with regards to motor oil and sunflower seed oil can be 64.40 and 47.48 g g(-1), respectively, approximately 2-3 times that of conventional polypropylene (PP) fibers for these two same oils. Even after five sorption cycles, a comparable oil sorption capacity with PP fibers was still maintained, exhibiting an excellent reusability. We believe that the composite PS-PU fibrous mats have a great potential application in wastewater treatment, oil accident remediation and environmental protection.
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