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This review deals with the synthesis of various polymers carrying bulky and rigid adamantyl substituents in the side chain. The synthetic methods of those polymers include the typical polymer reaction by introducing adamantyl groups to the present polymers and the polymerization of the monomers bearing the adamantyl pendant groups. A variety of vinyl monomers, such as styrenes, 1,3-butadiene, and (meth)acrylates, are capable of the living anionic polymerization to afford the polymers having predictable molecular weights and narrow molecular weight distributions (Mw/Mn =1.1). The resulting adamantyl-substituted polymers show extremely high glass transition temperatures and high thermal stability derived from the stiff adamantyl substituents compared with the corresponding parent polymers.
Amphiphilic block polymers having nitroxide radicals (TEMPO) self-assemble in water to form nanoparticles. This is a new nanomedicine that avoids the adverse effects of conventional antioxidants, which destroy the intracellular redox environment, and makes it possible to treat various oxidative-stress-related diseases such as cerebral or cardiovascular ischemia-reperfusions, Alzheimer’s disease and cancer. In addition, we have designed a gelation function in these materials and developed them as a material for anti-tissue adhesion agents and periodontal diseases. Additionally, we succeeded in enhancing cultured cell functions using an antioxidant biointerface.
In this focus review, our recent progress on hybrid polymers and supramolecules utilizing silicon and arsenic is overviewed. Novel materials design based on polyhedral oligomeric silsesquioxane (POSS) has been realized by focusing on the symmetry. Practical synthetic methods have opened new avenue to experimental studies on organoarsenic compounds.
Highly sensitive and rapid biosensing on a three-dimensional polymer platform. Increasing sensitivity and decreasing assay time are two of the most crucial goals in the development of biosensing devices. We have developed three-dimensional (3D) nanospherical and microfiber structure for biosensing devices aimed at highly sensitive and rapid immunoassays. The system having polystyrene microfiber of 3D structure paired with vacuum pump pressurization to induce bulk flow enables an efficient and rapid immunoassay. Because it takes advantage of the increased amount of immobilized antibody on 3D structure and of the accelerated propagation of antigens by flowing through the microfiber.
Tg of PMMA was greatly enhanced by introducing ion–dipole interaction between lithium cations and carbonyl groups in PMMA as pseudo crosslinking points.
Noticeable molecular weight and temperature dependency for physisorption behavior of semiflexible, non-charged poly(9,9-n-dioctylfluorene) (PF8) onto cuboidal γ-alumina in toluene were found. MM/MD simulations (CVFF) and quantum mechanical (MP2/6-31G(d,p)) calculations suggested that PF8 swaps interacting toluene for (110) surface of γ-alumina by changing the interaction from CH/π interactions to C-H/O interactions of γ-alumina in toluene. The competition between multiple intermolecular CH/π and C-H/O interactions was crucial whether the spontaneous physisorption of PF8 occurs in place of solvent quantity of toluene. The solution-phase physisorption systems should be the consequence of several weak attractive intermolecular interactions coexisting between polymers, surface, and solvents
An incompletely condensed cage silsesquioxane (IC-POSS)-based AB3-type monomer, tris(dimethylsilyl)-p-vinylhexaisobutyl-IC-POSS (3), was prepared by the corner-cleaved reaction of vinylheptaisobutyl-POSS (1) and subsequent capping reaction with chlorodimethylsilane. The hydrosilylation polymerization of 3 in the presence of Karstedt’s catalyst in toluene provided a soluble polymer. The refractive index of the unmodified polymer film was 1.4376. Post functionalization with isoprenol increased the dispersibility in polar organic solvents and significantly increased the glass-transition temperature. Post functionalization with allylheptaisobutyl-POSS significantly increased the thermal stability. Their refractive index varied from 1.4464 to 1.4573 upon post functionalization.
A perfluorinated oligo (ethylene oxide) monoalkyl ether containing a terminal methyl carbonate has been developed for potential application as quasi-solid-state electrolytes for Li-ion batteries. The fluorinated block-structured molecule self-assembles to form nanosegregated bilayer structures, which can be used for anisotropic Li ion transport when complexed with a Li salt. The complex shows ionic conductivities on the order of 10−6 S cm−1 in the ordered smectic phase formed at ambient temperature.
We prepared a series of ionic complexes, [CnMim][CHP] (n = 6–18), by neutralizing cholesterol hydrogen phthalate (CHP) with 1-alkyl (Cn)-3-methylimidazolium hydroxide ([CnMim][OH]) derived from [CnMim][Br]. The complexes of n ≥ 10 formed a thermotropic mesophase in each individual temperature range and solidified into a mesomorphic glass upon cooling, although two samples of n = 6 and 8 showed no ordered structure. Enthalpy relaxation behavior of the mesomorphic glasses (n = 10, 18) was also examined as a function of the aging temperature and time
Multi-walled carbon nanotube (MWCNT)/dendrimer sheet scaffolds, i.e., dendrimers attached to the surface of MWCNT buckypaper, were fabricated, and a hydroxyapatite (HAp) coating prepared on dendrimer-modified buckypaper using an alternate soaking process (ASP) is described. The amount of the HAp that is retained on the surface of the MWCNT/dendrimer sheet scaffolds depends on the dendrimer contents. Moreover, biomimetic crystallization of calcium phosphate on buckypaper in simulated body fluid (SBF) was carried out. TEM analysis of the resulting MWCNT/dendrimer sheet scaffolds revealed that the MWCNT backbone was covered with scaly crystals.
