Thermally switchable polyrotaxane as a model of stimuli-responsive supramolecules for nano-scale devices

A polyrotaxane consisting of many β-cyclodextrins (β-CDs) and a triblock copolymer of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) capped with bulky end-groups was synthesized as a model of stimuli-responsive supramolecules for nanoscale devices. The polyrotaxane was reversibly soluble-insoluble in water in response to temperature. This was achieved through the assembled and dispersed states of β-CDs along the block copolymer. It is considered that intermolecular hydrogen bondings of β-CDs, as well as the PEG segment length of the copoloymer, are predominant factors for regulating such thermally switchable behavior of the polyrotaxane.     

Facile Synthesis of Linear and Cyclic Poly(diphenylacetylene)s by Molybdenum and Tungsten Catalysis

Improved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s by polymerization of the corresponding diphenylacetylenes using MoCl₅- and WCl₄-based catalytic systems have been developed. MoCl₅ induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph₄Sn and ArSnⁿBu₃ to produce cis-stereoregular linear poly(diphenylacetyelene)s with high molecular weights (number-average molar mass (M_n)=30,000–3,200,000) in good yields (up to 98 %). On the other hand, WCl₄ induces ring expansion polymerization of diphenylacetylenes in the presence of Ph₄Sn or reducing reagents to produce cis-stereoregular cyclic poly(diphenylacetylene)s with high molecular weights (M_n=20,000–250,000) in moderate to good yields (up to 90 %). Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods using WCl₆-Ph₄Sn and TaCl₅-ⁿBu₄Sn systems.     

Synthesis of porous C/Fe3O4 microspheres by spray pyrolysis with NaNO3 additive for lithium-ion battery applications

In this work, we successfully synthesized porous C/Fe₃O₄ microspheres by spray pyrolysis at 700ºC with a sodium nitrate (NaNO₃) additive in the precursor solution. Furthermore, we studied their electrochemical properties as anode material for Li-ion batteries. The systematic studies by various characterization techniques show that NaNO₃ catalyzes the carbonization of sucrose and enhances the crystallization of Fe₃O₄. Moreover, an aqueous etching can easily remove sodium compounds to produce porous C/Fe₃O₄ microspheres with large surface areas and pore volumes. The porous C/Fe₃O₄ microspheres exhibit a reversible capacity of ~780 mAh g^–1 in the initial cycles and ~520 mAh g^–1 after 30 cycles at a current density of 50 mA g^–1. Moreover, a reversible capacity of ~400 mAh g^–1 is attainable after 200 cycles, even at a high current density of 500 mA g^–1. The wide range of pores produced from the removal of sodium compounds might enable easy electrolyte penetration and facilitate fast Li-ion diffusion, while the N-doping can promote the electronic conductivity of the carbon. These features of porous C/Fe₃O₄ microspheres led to the improved electrochemical properties of this sample.

Graphical Abstract

     

Supramolecular network formation through inclusion complexation of an α‐cyclodextrin‐based molecular tube

The supramolecular network formation through inclusion complexation between α‐cyclodextrin‐based molecular tube (MT) and poly(ethylene oxide) monocetylether‐graft‐dextran (5C₁₆PEO‐g‐Dex40) was demonstrated. From isothermal titration calorimetric (ITC) measurement, it was confirmed that MT formed an inclusion complex with two C₁₆PEO side chains in 5C₁₆PEO‐g‐Dex40. From viscosity measurements, the specific viscosity of the solution containing MT and 5C₁₆PEO‐g‐Dex40 was much larger than that containing 5C₁₆PEO‐g‐Dex40. It is considered that MT participates in the supramolecular network formation of 5C₁₆PEO‐g‐Dex40 through inclusion complexation with two C₁₆PEOs grafted to independent Dex40s.     

Changes in the Hydration State of a Block Copolymer of Poly(N‐isopropylacrylamide) and Poly(ethylene oxide) on Thermosensitive Micellization in Water

A diblock copolymer of poly(N‐isopropylacrylamide) and poly(ethylene oxide) (PiPA‐b‐PEO) has been prepared by radical polymerization with a ceric ion initiation system. Its thermosensitive micellization has been investigated by means of IR and fluorescence spectroscopy. The PiPA segments are critically dehydrated above 33.5°C (5 wt.‐%) and associate through hydrophobic interaction to form the hydrophobic core of the micelle. In contrast, the change in the hydration state of the PEO segments upon micellization is small.