New fluorescence method for the determination of the critical micelle concentration by photosensitive monoazacryptand derivatives

A novel fluorescence method for the determination of the critical micelle concentration (cmc) is reported. The cmc values of nonionic and anionic surfactants were evaluated utilizing a photosensitive monoazacryptand-Ba2+ complex, whose fluorescence intensity is sensitively changed by environmental conditions based on the photoinduced electron transfer (PET) mechanism as a fluorescent probe (PET method). Based on a comparison of the cmc values obtained by the PET method versus those obtained by conventional fluorescence-based methods as well as the values reported in the literature, one can conclude that the PET method is useful for the cmc determination. In particular, the PET method was more effective for the cmc determination of nonionic surfactants with very low cmc values (< 10(-5) M) than any other fluorescence-based method. In the cases of anionic surfactants, the PET method revealed the formation of the premicellar aggregates comprised of surfactant molecules and fluorescent probes below the cmc. Moreover, the hydrophobicity around the monoazacryptand-Ba2+ complex incorporated into various nonionic surfactant micelles was evaluated by this PET method.     

Short synthesis of skeleton-modified cyclodextrin derivatives with unique inclusion ability

[reaction: see text] Skeleton-modified cyclodextrin (CD) derivatives, in which an alpha-(1,4)-glucosidic bond is converted into a beta-(1,4)-glucosidic bond, were conveniently synthesized by cleavage of a single glucosidic bond in permethylated and 2,6-di-O-methylated alpha- and beta-CDs and subsequent recyclization via the trichloroacetoimidate intermediates. The selective cleavage of an alpha-(1,4)-glucosidic bond of permethylated alpha- and beta-CDs was accomplished by stirring in 30% aq HClO(4) at 25 degrees C to give the corresponding maltohexaose and maltoheptaose derivatives, respectively. The cleavage of a glucosidic bond of hexakis(3-O-benzyl-2,6-di-O-methyl)-alpha-CD was successfully carried out in a mixed 60% aq HClO(4) and 1,4-dioxane solution (1:20). In the case of heptakis(3-O-benzyl-2,6-di-O-methyl)-beta-CD, the solvent-free reaction with p-toluenesulfonic acid was found to be effective for selective cleavage of one glucosidic bond. The permethylated beta-CD derivative with a beta-(1,4)-glucosidic bond (4b) exhibited higher inclusion ability toward sodium m-nitrobenzoate than the parent permethylated beta-CD, while these hosts showed the same inclusion ability toward sodium p-nitrobenzoate. On the other hand, the beta-(1,4)-type permethylated alpha-CD derivative 4a exhibited lower inclusion ability toward sodium p- and m-nitrobenzoates than the parent permethylated alpha-CD. Interestingly, host molecules 4a and 4b showed inclusion selectivity for sodium m-nitrobenzoate as compared with the corresponding para-isomer, in contrast to permethylated CDs which possessed para-isomer selectivity. On the other hand, host molecules 4a and 4b showed para-isomer selectivity toward sodium nitrophenoxide guests, indicating that the inclusion selectivity was remarkably influenced by the guest hydrophilic groups. (1)H NMR studies on complexes of those beta-(1,4)-type CD derivatives with p- and m-nitrobenzoates and p- and m-nitrophenolates were carried out to estimate their structures.     

Effect of alcohols on the gamma-radiation-induced polymerization of ethylene

Gamma-radiation-induced polymerization of ethylene in alcohols such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl alcohols was carried out under a pressure of 400 kg./cm.²at 30°C. at a dose rate of 1.4 × 10⁵ rad/hr. in a batch reactor of 100 ml. capacity. The yield and molecular weight of polymer formed in the alcohols (except tert-butyl alcohol) were much lower than those of the bulk polymerization under the same conditions, whereas the addition of tert-butyl alcohol increased the yield and reduced the molecular weight. From the infrared spectra of the polymers and those of the bromination products it was concluded that only primary OH exists in the polymer formed in methyl alcohol and that both primary and secondary OH are in the polymer formed in other primary alcohols. Both secondary and tertiary OH were observed in the polymer when the secondary alcohols were used, and only tertiary OH in the case of tert-butyl alcohol. These polymers were found to contain small amounts of vinylidene unsaturation and methyl group. On the basis of these results the roles of the alcohols in the polymerization are discussed.     

Fabrication of novel multilayered thin films based on inclusion complex formation between amylose derivatives and guest polymers

Novel types of layer-by-layer (LbL) assembly films were successfully fabricated onto a solid substrate through the inclusion complex formation between partially 2,3- O-methylated amyloses (MAs) and polytetrahydrofuran (PTHF). The formation of the LbL assembly films was confirmed by quartz crystal microbalance (QCM) analysis, atomic force microscopy (AFM) observation, and X-ray diffraction (XRD) measurement. The film formation was significantly affected by the methylation degree of amylose. When MAs with 8 and 20% methylation were used as hosts, the formation of LbL assembly films with PTHF was clearly observed. On the other hand, MAs with more than 33% methylation barely formed LbL assembly films with PTHF.     

Inversion of solar transmitted radiance profiles for the atmospheric optical thickness

In a series of papers (Refs. [1–12]), quasilinearization and invariant imbedding have been successfully applied to an inversion of total spectral radiance profiles remotely sensed from space for determining the atmospheric optical properties and the ground albedo, in a least square sense. In the present paper, with the aid of quasilinearization and invariant imbedding, a statistical estimation of the atmospheric optical thickness is made, using solar noisy transmitted radiance measurements on the ground.     

Anatomic localization of scintillation colour image by means of simultaneous colour polaroid film photographing of emission scintiphoto and transmission scintiphoto

A study has been made of a simple and practical method to add the information of anatomical localization upon the emission scintiphoto of the generally used polaroid film. Our experients were a follows: first, the polaroid film of transmission scintiphoto, according to the Anger method, was made, and then, that of emission scintiphoto was made. Next, by double-exposing these two photos to the same polaroid film with the Mamiya-made duplicator, these photos were made into a composite photo. In that case, in order to distinguish the images of these scintiphotos on this composite photo. In that case, in order to distinguish the images of these scintiphotos on this composite photo, a colour polaroid film was used in the double exposure, and here, when each of the two scintiphotos was given its own colour-filter, it was found that the images could be sharply sorted by colour. This method does not require any highly expensive apparatuses and according to this method a disc source and a polaroid duplicator are enough for the exact anatomical localization of scintiphoto-images by the polaroid film.     

High quality a-Si film produced by horizontal plasma furnace

A series of investigation on the a-Si film quality in a p-i-n junction has been made by employing the separated three chamber system of horizontal plasma mode. A clear improvement of film quality has been experimentally verified in a-Si films prepared by this system as compared with those by the single chamber system. On the basis of these investigation, a-SiC/a-Si/μc-Si heterojunction solar cells having more than 9% conversion efficiency have been developed.     

Effect of the thickness of the Pt film coated on a counter electrode on the performance of a dye-sensitized solar cell

The effects of the thickness and morphology of a Pt film coated on a counter electrode on the performance of a dye-sensitized solar cell (DSC) were investigated. Deposition of a Pt film ranging in thickness from 2 to 415 nm gradually decreases the sheet resistance of the counter electrode. No significant difference in the charge-transfer resistance at the electrolyte|counter electrode interface was observed for a Pt film thickness ranging from 25 to 415 nm. A high energy conversion efficiency of approximately 5% can be obtained for DSCs based on a counter electrode with a very thin Pt film of 2 nm, as well as with a 415-nm thick Pt film. These results are important for reducing production costs by reducing the required amount of expensive platinum.     

Mechanism of initiation in the γ-radiation-induced polymerization of ethylene

The relation between the gaseous products and the reaction conditions such as pressure, temperature, and dose rate in the γ-radiation-induced polymerization of ethylene was studied. The main gaseous products were hydrogen and acetylene, and the amounts of these products increased linearly with reaction time, monomer density, and dose rate, while they were independent of reaction temperature. The ratio of rate of formation of hydrogen to acetylene was about one-half. Further, it was found that the number of moles of polymer chain formed was almost equal to that of acetylene at room temperature. An initiation mechanism in which both hydrogen and acetylene are formed is proposed. The equation which is derived on the basis of the initiation mechanism is shown to be in good accordance with the experimental results.