Facile Synthesis of Poly(methyl methacrylate) Silica Nanocomposite Monolith by In Situ Free Radical Polymerization of Methyl Methacrylate in the Presence of Functionalized Silica Nanoparticles.

Novel porous poly(methyl methacrylate) (PMMA) silica nanocomposites have been produced by utilization of polymerization-induced phase separation in a simple one-pot approach. A facile free radical polymerization of MMA in the presence of surface methacrylate-functionalized silica nanoparticles was carried out in ethanol-based solvents, successfully producing novel, morphologically designable porous nanocomposite monoliths. Differing from standard free radical polymerization in solution, a mixture of good and poor solvents (ethanol/,-dimethylformamide ratio) for the resulting polymer was used to trigger spinodal phase separation.

Amplified Chirality Transfer to Aromatic Molecules through Non-specific Inclusion by Amorphous, Hyperbranched Poly(fluorenevinylene) Derivatives.

Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries.

The first space-filling polyhedrons of polymer cubic cells originated from Weaire-Phelan structure created by polymerization induced phase separation.

The Weaire-Phelan structure is a three-dimensional structure composed of two different polyhedra having the same volume, i.e., pyritohedron and truncated hexagonal trapezohedron.

Non-uniform Self-folding of Helical Poly(fluorenevinylene) Derivatives in the Solid State Leading to Amplified Circular Dichroism and Circularly Polarized Light Emission.

An unprecedented non-uniform self-folding of artificial polymer chains composed of turn moieties and stretched segments is presented through the design of a set of optically active poly(fluorene-2,7-diylethene-1,2-diyl) (poly(fluorenevinylene)) derivatives bearing a neomenthyl group and a pentyl group attached at the 9-position of fluorene backbone at various ratios. The folded structure is formed and stabilized through inter-chain interactions in the solid state, leading to remarkably enhanced chiroptical properties (chirality amplification) in terms of circular dichroism (CD) and circularly polarized light (CPL) emission. This phenomenon is rationalized by experimental and theoretical CD and CPL spectral analyses.

Ring-Opening Polymerization of Triaziridine Compounds in Water: An Extremely Facile Method to Synthesize a Porous Polymer through Polymerization-Induced Phase Separation.

Dissolution of trifunctional aziridine compounds, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] (3AZ) and tetramethylolmethane-tri-β-aziridinylpropionate (3AZOH), in water initiates a ring-opening polymerization and successful yields the corresponding network polymers via cationic polymerization. The polymerization of 3AZ induced phase separation and produced porous polymers under a wide range of monomer concentrations and polymerization temperatures. The phase separation rate in the 3AZ/water system was estimated by quantifying the turbidity by means of light transmission where transmittance decreased with an increase in the content of phase-separated materials.

Aggregation-induced chirality amplification of optically active fluorescent polyurethane and a cyclic dimer in the ground and excited states.

Optically active linear polyurethane and a cyclic dimer were synthesized from 2,7-diisocyanatofluorene and 2,2'-dihydroxy-1,1'-binaphthyl. The circular dichroism (CD) spectral intensity of the polymer was amplified at a higher concentration through aggregate formation, while circularly polarized light (CPL) emission was not enhanced. The cyclic dimer's CPL emission was largely amplified ( 1.

Optically active covalent organic frameworks and hyperbranched polymers with chirality induced by circularly polarized light.

Axial chirality was induced by circularly polarized light to covalent organic frameworks as well as hyperbranched polymers composed of bezene-1,3,5-triyl core units and oligo(benzene-1,4-diyl) as linker units where variation in induction efficiency was rationally interpreted in terms of internal rotation dynamics studied through CPMAS 13C NMR experiments including CODEX measurements.

Morphology Control and Metallization of Porous Polymers Synthesized by Michael Addition Reactions of a Multi-Functional Acrylamide with a Diamine.

Porous polymers have been synthesized by an aza-Michael addition reaction of a multi-functional acrylamide, ,',″,‴-tetraacryloyltriethylenetetramine (AM4), and hexamethylene diamine (HDA) in HO without catalyst. Reaction conditions, such as monomer concentration and reaction temperature, affected the morphology of the resulting porous structures. Connected spheres, co-continuous monolithic structures and/or isolated holes were observed on the surface of the porous polymers.

Joint-Linker Type Ionic Gels Using Polymerizable Ionic Liquid as a Crosslinker via Thiol-Ene Click Reactions.

In this work, we report the synthesis of ion-conductive gels, or ionic gels, via thiol-ene click reactions. The novel gel systems consist of the multifunctional thiol monomers tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), and dipentaerythritol hexakis(3-mercaptopionate) (DPMP) as joint molecules and bifunctional allyl ionic liquid (IL) as a crosslinker. The thiol-ene reaction was carried out in lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) in a propylene carbonate (PC) (1 M) solvent system via a photopolymerization process.

Synthesis of Network Polymers by Means of Addition Reactions of Multifunctional-Amine and Poly(ethylene glycol) Diglycidyl Ether or Diacrylate Compounds.

Addition reactions of multi-functional amine, polyethylene imine (PEI) or diethylenetriamine (DETA), and poly(ethylene glycol) diglycidyl ether (PEGDE) or poly(ethylene glycol) diacrylate (PEGDA), have been investigated to obtain network polymers in HO, dimethyl sulfoxide (DMSO), and ethanol (EtOH). Ring opening addition reaction of the multi-functional amine and PEGDE in HO at room temperature or in DMSO at 90 °C using triphenylphosphine as a catalyst yielded gels. Aza-Michael addition reaction of the multi-functional amine and PEGDA in DMSO or EtOH at room temperature also yielded corresponding gels.

Synthesis and properties of porous polymers synthesized by Michael addition reactions of multi-functional acrylate, diamine, and dithiol compounds.

Porous polymers have been synthesized by Michael addition reactions of multi-functional acrylate and diamine or dithiol compounds. Aza-Michael addition reaction of multi-functional acrylate, trimethylolpropane propoxylate triacrylate (TPT) and hexamethylene diamine (HDA) in dimethyl sulfoxide (DMSO) successfully yielded the porous polymer. The porous structure was characterized by connected globules or co-continuous structure, and could be controlled by the reaction conditions.

Silk-pectin hydrogel with superior mechanical properties, biodegradability, and biocompatibility.

A new method is developed to prepare silk hydrogels and silk-pectin hydrogels via dialysis against methanol to obtain hydrogels with high concentrations of silk fibroin. The relationship between the mechanical and biological properties and the structure of the silk-pectin hydrogels is subsequently evaluated. The present results suggest that pectin associates with silk molecules when the silk concentration exceeds 15 wt%, suggesting that a silk concentration of over 15 wt% is critical to construct interacting silk-pectin networks.

Biocompatible and biodegradable dual-drug release system based on silk hydrogel containing silk nanoparticles.

We developed a facile and quick ethanol-based method for preparing silk nanoparticles and then fabricated a biodegradable and biocompatible dual-drug release system based on silk nanoparticles and the molecular networks of silk hydrogels. Model drugs incorporated in the silk nanoparticles and silk hydrogels showed fast and constant release, respectively, indicating successful dual-drug release from silk hydrogel containing silk nanoparticles. The release behaviors achieved by this dual-drug release system suggest to be regulated by physical properties (e.