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Series of polyelectrolyte−surfactant complexes, DNA−cationic surfactant complexes (cetyltrimethylammonium, cetylpyridinium, and cetylbenzyldimethylammonium), and their self-assembled bulk film materials were prepared on a large scale. Circular dichroism (CD) analysis indicated that the right-handed double helix structure of DNA was retained in these bulk film materials. TGA analysis suggested that 4 molecules of water were required to retain the B-type conformation of the DNA helix in the self-assembled bulk film materials. In addition, it revealed that DNA and the DNA−surfactant complex film materials were thermostable up to as high as 180 °C. Thermodynamical analysis indicated that these film materials were thermo-extensive over a temperature range from 100 to 148 °C. The DNA conformation in the supramolecular complex films can be reversibly tuned by changing the environmental humidity. Film formation was found to occur by self-assembly and self-organization with evaporation of solvent molecules. Various functional dyes such as laser dye, NLO dye, and photochromic dye could easily be incorporated in the self-assembled supramolecular complex films as adducts. Studies of the induced CD spectra demonstrated that 4[4-(dimethylamino)styryl]-1-dococylpyridinium (DMASDPB) could orient on the chiral nanotemplates of DNA in the self-assembled films. UV−vis analysis indicated that these film materials have high transparency from 300 to about 1000 nm. These self-assembled functional-dye-containing DNA−surfactant complex materials, with good processability for multilayer integration into large-area devices, will have promising applications in molecular optical and molecular optoelectronic fields.

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Complex formation between PDMAAm as a hydrogen-bonding acceptor and PAAc as a hydrogenbonding donor, the temperature dependence of the equilibrium swelling for interpenetrating polymer network (IPN) hydrogels composed of PDMAAm and PAAc, and changes in ketoprofen release of these IPN hydrogels were investigated. Interpolymer complexes between PDMAAm and PAAc were very stable at 70 °C in aqueous solution. Dissociation temperatures of the complex between poly(DMAAm-co-AAm) and PAAc shifted to higher values with increasing DMAAm content. These IPNs composed of poly(DMAAm-co-AAm) and PAAc showed limited swelling ratios between their swelling transition temperatures and lower swelling ratios above these transition temperatures. Transition temperatures shift to higher values with increasing DMAAm content. Reversible and pulsatile solute release, reflecting the "on" state at higher temperatures and the "off" state at lower temperatures, was achieved by fabricating these IPN hydrogels.

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ABSTRACT:Montmorillonite was organically modified with distearyldimethylammonium chloride. This organically modified clay (OMON) and poly( e-caprolactone) (PCL) were solvent-cast blended with chloroform, and the structure and properties of the resulting PCL-clay blends were investigated. From isothermal crystallization experiments, it was found that a small amount of OMON in the blend accelerated the crystallization of PCL, whereas a large amount of the organophilic clay delayed it. From smalland wide-angle X-ray scattering measurements, it was found that the silicate layers forming the clay could not be dispersed individually in the PCL blends. In other words, the clay seemed to exist as the tactoids consisting of some silicate layers. These tactoids formed a remarkable geometric structure; that is, their surface planes lay almost parallel to the blend film surface. Furthermore, the tactoids were stacked with insertion of PCL lamellae in the film-thickness direction. Preferred orientation of the PCL crystallites was induced by the presence of the clay. During the drawing process of the blends, fibrillation took place with formation of planelike voids developed on the plane parallel to the film surface. From dynamic viscoelastic measurements, it was shown that intercalation of PCL chains into the layered silicates did not take place in the blends prepared by the solvent-cast method used in this work.

We have synthesized carboxyl semitelechelic oligo(N-isopropylacrylamide) (OIPAAm) using radical telomerization with 3-mercaptopropionic acid. This telomerization is also effective for the synthesis of carboxyl semitelechelic co-oligomers of IPAAm with butyl methacrylate (BMA) as hydrophobic or N,N-dimethylacrylamide (DMAAm) as hydrophilic comonomers. All co-oligomers are highly water-soluble at lower temperatures and exhibit phase separation with increasing temperature. Pure OIPAAm exhibits a lower critical solution temperature (LCST) at 32 degrees C, and the LCST for co-oligomers can be controlled to increase over 32 degrees C with increasing DMAAm composition and to decrease below 32 degrees C with increasing BMA composition. OIPAAm was grafted to bovine serum albumin (BSA) and bovine plasma fibrinogen (BPF) by activated ester-amine coupling. These OIPAAm-biomolecule conjugates maintain their temperature responses, are soluble in cold water, and precipitate over a range of temperatures related to oligomer content. Conjugates could be selectively precipitated and independently separated from conjugate solution mixtures with increasing temperature. In this case, the number of OIPAAm molecules attached to a conjugate affects the aggregate sizes of precipitated conjugates in mixtures. Both conjugate mixture ratios and solution concentrations influence the contamination of oligo(IPAAm-co-DMAAm)-BSA conjugates in precipitated oligo(IPAAm-co-BMA)-BPF conjugates. Furthermore, precipitated conjugates separated using centrifugation and filtration redissolve in water and maintain their biofunctionality, indicating the potential of strategy in reversible bioreactors and protein separations.

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