Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

Influence of the characteristics of soil and fly ash on the supercritical carbon dioxide extraction of dioxins.

Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples.     

Micro-phase sorbent extraction for trace analysis via in situ sorbent formation: application to the spectrophotometric determination of nitrite in environmental waters.

A micro-phase sorbent in situ formation from an aqueous solution was proposed for the sensitive spectrophotometric determination of nitrite in environmental waters. Nitrite in a 10 mL sample solution was converted into a cationic azo dye by the reaction with 4-trifluoromethylanilinium ion and N-1-naphthylethylenediammonium ion in an acidic medium. Addition of dodecylbenzenesulfonate ion caused the formation of a suspension of ion associate in the solution. Centrifugation of the solution led to the isolation of a liquid organic phase that extracted the azo dye at the bottom of the centrifuge tube. The volume of the new phase was ca. 5 microL. After the aqueous phase was discarded, the organic phase was dissolved with 1 mL of 2-methoxyethanol to measure the absorbance. Nitrogen as NO2- at concentrations from 1.5 to 30 microg L(-1) was determined with sufficient precision. When 0.2 mL of 2-methoxyethanol was applied to dissolve the organic phase, 0.3-4.8 microg NO2--N L(-1) was determined. The recovery tests for nitrite added to some river water and seawater were satisfactory. This method is very simple and rapid. It takes only 30 min from the dye formation to the measurement of the absorbance.     

Synthesis of self‐photosensitizing polyesters containing donor–acceptor norbornadiene moieties and benzophenone groups and their photochemical reactions

The ring‐opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor–acceptor norbornadiene (D‐A NBD) dicarboxylic acid, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid, monoglycidyl ester derivatives with D‐A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self‐photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D‐A NBD moieties in these polymers was higher than that of the D‐A NBD moieties in the polymer having no photosensitizing group. Furthermore, the rate of the photoisomerization of the D‐A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo‐irradiated polymers having QC moieties released thermal energies of 146–180 J/g. The D‐A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15–30% after 50 repeated cycles of interconversion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2978–2988, 2007     

Synthesis of copolymers containing a spiro orthocarbonate moiety and evaluation of the volume change during their cationic crosslinking

Spiro orthocarbonate (SOC) monomers having either an exomethylene group {3,3‐dimethyl‐9‐methylene‐1,5,7,11‐tetraoxaspiro[5.5]undecane (ExoSOC)} or an allyl group {9‐allyl‐3,3‐dimethyl‐1,5,7,11‐tetraoxaspiro[5.5]undecane (AllylSOC)} were radically copolymerized with vinyl monomers at several feed ratios to obtain the corresponding copolymers having SOC moieties in the side chain. The obtained copolymers were crosslinked via the double ring‐opening polymerization of the SOC moieties by a treatment with boron trifluoride etherate. The volume changes during the crosslinking of the copolymers were evaluated by density measurements with a gas pycnometer. As the SOC moiety composition increased, the volume shrinkage during the crosslinking was suppressed, and that finally changed into volume expansion. The volume changes during the crosslinking of the copolymers from AllylSOC were slightly larger than those of the copolymers from ExoSOC. The higher volume expansions in the crosslinking of AllylSOC‐based copolymers were ascribable to the lower steric hindrance around the SOC moieties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7040–7053, 2006     

Temperature-induced crystallization and compactibility of spray dried composite particles composed of amorphous lactose and various types of water-soluble polymer

The purpose of this study was to investigate the temperature-induced crystallization and the compactibility of the composite particles containing amorphous lactose and various types of polymers. The composite particles were prepared by spray-drying an aqueous solution of lactose and various types of gel forming water-soluble polymers at various formulating ratios. The stabilizing effect of hydroxypropylcellulose (HPC) and polyvinyl pyrrolidone (PVP) on amorphous lactose in the composite particles was smaller than that of sodium alginate in comparing at the same formulating ratios. The difference in the stability of amorphous lactose in the composite particles was attributed to the difference in the glass transition temperature (Tg) of the composite particles caused by the polymers formulated. The tensile strength of compacted spray-dried composite particles containing the polymers was higher than commercial lactose for direct tabletting (DCL21). The tensile strength of the composite particles was increased with an increase in water content in the particles. The difference in compactibility of the composite particles containing the different amount of polymer and water could be explained by the difference in Tg of the particles.     

Synthesis,surface accumulation,and micellar properties of amphiphilic block copolymers

Amphiphilic block copolymers, i.e., poly(methyl methacrylate)-b-poly(2-dimethylethylammoniumethyl methacrylate), were synthesized by the reaction between two prepolymers. Carboxyl-terminated poly(methyl methacrylate) and hydroxyl-terminated poly(2-dimethylaminoethyl methacrylate) were prepared by radical polymerization of the corresponding monomers in the presence of thioglycolic acid and 2-mercaptoethanol as a chain transfer agent, respectively. Two condensation methods, i.e., DCC and the acid chloride method, were used for the reactions of these prepolymers. The subsequent quarternization produced the amphiphilic block copolymers. Surface property of poly(methyl methacrylate) films containing this amphiphilic block copolymer was examined by measuring contact angles for water. The addition of only 0.5 wt% of the block copolymer was sufficient to make poly(methyl methacrylate) surfaces hydrophilic. The block copolymer formed a polymeric micelle in acetone–water mixed solvent.     

Formulation design of ointment base suitable for healing of lesions in treatment of bedsores

We intended to develop a desired ointment base suitable for treatment of bedsores including the proliferation of granulation and epidermis. The main bedsore bacteria detected in our hospital were S. aureus in gram-positive coccus and P. aeruginosa in gram-negative bacillus. As the macrogol ointment (MO) was found to have bactericidal effects on these bacteria, MO was adopted as the base for the objective ointment. To improve the properties of the ointment base such as regulating the humidity of the exudation and controlling the release of antibiotics formulated in the ointment, co-formulating effects of various additives to MO were evaluated. The sustained release function of the ointment base was obtained by adding hydrophilic petrolatum (HP) to MO. However, the resultant ointment was found to have a poor humidity regulating property. On the other hand, MO containing 5% of hydroxypropyl cellulose (HPC) showed both the humidity regulating and the controlled drug releasing properties. It was considered that HPC particles dispersed in the ointment could be swelled by absorbing water to form a gel network. The curd tension meter tests for the ointments prepared with the various polymers showed that the MO-HPC base, which showed the highest sustained drug releasing property, was found to have the highest hardness. This result means that HPC formulated into the base forms the most rigid gel structure to resist the erosion of the ointment and to control the drug release.     

Indomethacin sustained-release suppositories containing sugar ester in polyethylene glycol base

Indomethacin (IM) sustained-release suppositories were prepared by the fusion method using sugar ester and polyethylene glycol 4000 (PEG). The suppositories were evaluated by in vitro release testing, X-ray analysis and in vivo absorption testing in rabbits. X-ray analysis showed that IM was amorphous in PEG-base suppositories. In a release test, slow-release was obtained when the sugar ester content of a suppository was 60%. The IM plasma level following the administration of the suppository was well sustained in the absorption test. The main slow-release mechanism is considered to be the release of IM from the matrix composed of sugar ester and PEG, which is represented by the Higuchi equation. A good correlation between the release test and the absorption test was obtained. It is considered that the amorphous state of IM in this type of sustained-release suppository would enhance the release and absorption of IM in the rectum of the rabbit, whose rectal fluid volume is small.