Structure and dynamic properties of liquids confined in MCM-41 mesopores

The microscopic structure and dynamic properties of water, methanol, and acetonitrile confined in mesoporous MCM-41 materials have been investigated under monolayer and capillary-condensation conditions as a function of pore size and temperature by in situ FTIR and X-ray diffraction and quasi-elastic neutron scattering techniques. Both interfacial and confinement effects on the structure and dynamics of the liquids in hydrophilic pores are discussed at the molecular level.     

Polymer scrambling: macromolecular radical crossover reaction between the main chains of alkoxyamine-based dynamic covalent polymers

A novel polymer hybridization method, "polymer scrambling", was developed on the basis of the macromolecular radical crossover reaction between the main chains of dynamic covalent polymers. The macromolecular crossover reaction was successfully monitored by GPC and NMR measurements. The present methodology is innovative for the preparation of novel polymer hybrid materials at the nanometer scale.     

Programmed thermodynamic formation and structure analysis of star-like nanogels with core cross-linked by thermally exchangeable dynamic covalent bonds

Programmed thermodynamic formation of star-like nanogels from designed diblock copolymers with thermally exchangeable dynamic covalent bonds in their side chains and structure analysis of the nanogels were performed. Linear diblock copolymers that consist of poly(methyl methacrylate) block and random copolymer block of methyl methacrylate (MMA) and methacrylic esters with alkoxyamine moiety were prepared by atom transfer radical polymerization (ATRP). By heating the diblock copolymers in anisole, a cross-linking reaction occurred as a result of the radical crossover reaction of alkoxyamine moieties to afford star-like nanogels. Kinetic studies have revealed that the cross-linking behavior reaches equilibrium at a given reaction time, with characteristic reaction behaviors for thermodynamic reactions being observed. The equilibrium structures of the star-like nanogels were controlled by the initial concentrations of diblock copolymers as well as their compositions and molecular weights. Furthermore, by heating the star-like nanogels with excess alkoxyamine, linear polymers were successfully regenerated. The molecular weights and sizes of the nanogels were evaluated by gel permeation chromatography-multiangle laser light scattering (GPC-MALLS) and small-angle X-ray scattering (SAXS) measurements, respectively, and the morphologies of the nanogels were directly observed by scanning force microscopy (SFM).     

Two-dimensional alignment of imogolite on a solid surface

Surface modified imogolite fiber, hydrated aluminium silicate that has the shape of a rigid hollow cylinder, was aligned with consistent nano spacing and was visualized by scanning tunneling microscopy.     

Landmine detection: improved binding of 2,4-dinitrotoluene in a gamma-CD/metal oxide matrix and its sensitive detection via a cyclic surface polarization impedance (cSPI) method

Highly sensitive and selective detection of 2,4-DNT, a representative explosive, was achieved by the synergic effect of molecular imprinting and host (cyclodextrin)-guest interaction in ultrathin layers of TiO(2) and SiO(2) gel; the detection limit using cSPI measurements reached nM concentration.     

Water‐dispersible microgel modified with methacryloyl groups by ionic bonding on the surface and the photopolymer microgel

A novel water‐dispersible reactive microgel, which had a diameter of 40–90 nm, was synthesized for photopolymer materials. The microgels have segments with substituted ammonium groups, to provide water solubility, in their polymer networked structure. It has unsaturated groups connected to the quaternary nitrogens by ionic bonding (I‐type microgel). The I‐type microgel was compared with one that has methacryloyl groups connected with the quaternary nitrogens of the microgel by covalent bonding (C‐type microgel). The I‐type microgels were able to separately control the modified amount of quaternary nitrogen and methacryloyl group. In the presence of 2,4‐diethylthioxantone as a photoinitiator and pentaerthritol triacrylate as a crosslinker, the photopolymer containing the C‐type or I‐type microgels had sensitivity high enough for practical use. Not only the amount of the methacryloyl group of the microgel but the amount of the quaternary nitrogen affected the sensitivity and the rate of polymerization of the water‐dispersible photopolymer containing the I‐type microgels. Copyright © 2000 John Wiley & Sons, Ltd.     

Tetrahydropyranyl-protected poly( p -hydroxystyrene) containing vinyl ether compound for three-component photopolymers

Poly(p-hydroxystyrene)s (PHSs) partially protected by tetrahydropyranyl (THP), PPT-x, containing 2,2′-bis(4-(2-(vinyloxy)ethoxy)phenyl)propane as a crosslinking agent were used as three-component photopolymers in combination with diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) as a photoacid generator. The PPT-x with a higher THP-protecting ratio was deprotected at higher temperatures than the PPT-x with a lower THP-protecting ratio. The conversions of vinyl ether compound in the photopolymer films were not related to the THP-protecting ratios in PPT-x and increased with increasing baking time. Under different THP-protecting ratios and prebaking temperatures, the PPT-x showed varying lithographic behavior between a positive-working mode and a negative-working mode. These three-component photopolymer solutions of PPT-x have good preservation stability. © 1998 John Wiley & Sons, Ltd.     

Novel dual-mode photoresist based on decarboxylation by photogenerated base compound

The copolymers containing a carboxyl group were used as the two-component photopolymers in combination with dimethyl 4-(o-nitrophenyl)-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (NMHP) as a photobase generator. Under irradiation by 365 nm light, NMHP is converted to dimethyl 4-(o-nitrosophenyl)-2,6-dimethyl-3,5-pyridinedicarboxylate (NMP). NMP acts as a base catalyst for the thermal decarboxylation of a carboxyl group in the polymer. The decarboxylation in the polymer provides a negative-working photoresist under the additional flood-exposure of 365 nm light before development. This process is called the photoassisted contrast (PAC) process. NMHP acts as a dissolution inhibitor for the aqueous base development of the polymers containing a carboxyl group but NMP promotes the dissolution of the polymers. This change in the solubility inhibition of NMHP offers a positive-working photoresist without the process of post-exposure baking (PEB) and the PAC process. Therefore, NMP, the photoproduct of NMHP, produces dual-tone-mode photoresists with the copolymers containing a carboxyl group. © 1998 John Wiley & Sons, Ltd.     

Characterization of Novel Biodegradable Segmented Polyurethanes Prepared from Amino-Acid Based Diisocyanate

Segmented polyurethanes (SPUs) which were expected to yield non-toxic degradation products were synthesized from lysine-based diisocyanate (LDI), 1,3-propanediol (PDO), and polycaprolactone diol (PCL). SPUs were synthesized via a standard two-step prepolymer method. The hard segment fraction was changed in order to tune the mechanical properties and the degradability. The aggregation structures of the SPUs were characterized by infrared spectroscopy and differential scanning calorimetry (DSC), temperature dependence of dynamic viscoelasticity, and small-angle X-ray scattering (SAXS). DSC and dynamic viscoelastic measurements revealed that the glass transition temperature (T_g) of the soft segment increased with an increase in the hard segment fraction. SAXS of SPUs revealed the aggregation states of hard and soft segments. Furthermore, the degradation of SPUs was investigated by exposing the polymers to a buffer solution at 310 K (pH=7.6). The degradation rate of SPUs increased with an increase in the soft segment fraction. This is because the soft segment has the hydrolyzable ester linkages and the ester linkages are susceptible to hydrolysis compared with the urethane linkages. Finally, an electrospray deposition method was used to fabricate biodegradable SPU micro-fibers. FE-SEM images showed that higher concentration of solution favored the formation of uniform biodegradable micro-fibers without beads-like structure.