Interlayer structure and magnetic field-induced orientation of modified nanoclays in polymer aqueous solution.

Structural changes and orientation of organically modified montmorillonite (Mt) were investigated by employing synchrotron small-angle X-ray scattering. Mt was modified with various cationic compound [3-(methacryloylamino)propyl]-trimethyl ammonium chloride (MPTC) contents (1.5, 3, 6, 12, and 18 CEC (cation exchange capacity) per 1 CEC of Mt). There are two types of modified Mt structures, lateral monolayer and paraffin type monolayer, in accordance with the MPTC contents. A paraffin-type monolayer is more dominant than a lateral monolayer for efficient packing of MPTC between Mt layers as the MPTC contents increase. In 10 wt% of the modified Mt series oriented in 1 M of polyacrylamide aqueous solution using a magnetic field (1.2 Tesla), the modified Mt series oriented parallel to the magnetic field within 200 s.

Creating stiffness gradient polyvinyl alcohol hydrogel using a simple gradual freezing-thawing method to investigate stem cell differentiation behaviors.

Polyvinyl alcohol (PVA) cylindrical hydrogel with a stiffness gradient was prepared using a simple liquid nitrogen (LN2)-contacting gradual freezing and thawing method in order to investigate the effects of substrate stiffness on stem cell differentiation into specific cell types. The prepared cylindrical PVA hydrogel showed a gradually increasing stiffness along the longitudinal direction from the top at approximately 1 kPa to the bottom (LN2 contacted side) at approximately 24 kPa. From the in vitro culture of bone marrow stem cells, it was observed that each soft (∼1 kPa) and stiff (∼24 kPa) hydrogel section promotes effective neurogenesis and osteogenesis of the cells, respectively, with the tendency to gradually decrease toward the opposing characteristic's side. The stiffness gradient cylindrical PVA hydrogel fabricated using this simple gradual freezing and thawing method can be a useful tool for basic studies, including the determination of optimum stiffness ranges for a variety of stem cell differentiations, as well as the investigation of cell migration in terms of substrate stiffness.

Carboxymethylation of corn starch and characterization using asymmetrical flow field-flow fractionation coupled with multiangle light scattering.

Asymmetrical flow field-flow fractionation (AsFlFFF) was coupled online with multiangle light scattering (MALS) to study the changes in the molecular weight and the size distribution of the corn starch during carboxymethylation. A corn starch was derivatized with sodium chloroacetate in alcoholic medium under alkaline condition to produce carboxymethyl starches (CMS) having various degrees of substitution (DS). The change in thermal characteristics and granule structure of the native corn starch and CMS were compared using Thermogravimetric analysis and scanning electron microscope. The ionic strength of the carrier liquid (water with 0.02% NaN(3)) was optimized by adding 50mM NaNO(3) to minimize the interactions among the starch molecules and between the starch molecules and the AsFlFFF membrane. A field-programmed AsFlFFF allowed determination of the molecular weight distribution (MWD) of starches within about 25min. It was found that carboxymethylation of starch results in reduction in the molecular weight due to molecular degradation by the alkaline treatment. The weight-average molecular weight (M(w)) was reduced down to about 4.4x10(5) from about 7.2x10(6) when DS was 0.14. It seems AsFlFFF coupled with MALS (AsFlFFF/MALS) is a useful tool for monitoring the changes taking place in the molecular weight and the size of starch during derivatization.

Supramolecular ordering of amide dendrons in lyotropic and thermotropic conditions.

Self-assembled superstructures of amide dendrons, from first to third generation including monodendrons and covalently linked dimers, were extensively examined, and the supramolecular ordering processes in thermotropic and lyotropic conditions were compared. The superstructures as determined by X-ray diffraction and DSC revealed that the first and second generation dendrons showed nearly identical superstructures regardless of the assembly conditions. But, the third generation dendrons showed a more sensitive self-organizing behavior. The structure obtained from the gel state was lamellar with a more extended conformation, while the structure from the melt state revealed the columnar superstructures of contracted branches. The superstructure formed from the gel state also showed a structural change upon raising the temperature and assumed a structure similar to the thermotropically driven one, implying that the structure formed from the gel is thermodynamically unstable. The formation of lamellar- or cylinder-type superstructures from amide dendrons was primarily dependent on the shape of dendrons, which is associated with the branch size (generation) and the surrounding conditions.

Self-organization of amide dendrons and their dendronized macromolecules.

A polymerizable methacryl unit was introduced at the focal moiety of the amide dendrons which have amide branches and alkyl periphery. Their dendronized polymers were also prepared by the radical polymerization of the methacryl units. The self-organization characteristics of dendrons and dendronized polymers were then investigated in both the organic and aqueous phases. The amide dendrons (1M and 2M) in which the focal carboxyl group was blocked with methacryl units did not form gel in organic media such as chloroform or THF, whereas amide dendrons with a free carboxyl group at the focal point form self-organized structures. In the aqueous phase, 1M and 2M formed spherical vesicular assemblies. The dendronized polymers with first and second generation dendrons, 1P and 2P, respectively, exhibited lamellar and columnar organization in toluene. In addition to hydrogen bonding between the dendritic amide branches and van der Waals interactions between the alkyl periphery, steric confinement of dendritic side groups along the polymer backbone played a key role in the packing process of the dendronized polymers. In aqueous phase, 1P and 2P showed spherical vesicular aggregates with persistent stability in the presence of Triton X-100.