Kazutami Sakamoto

Stimuli-free auto-modulated material release from mesoporous nanocompartment films

Mesoporous nanocompartment films composed of silica particles and hollow silica capsules were prepared by the layer-by-layer (LbL) technique. The resulting mesoporous nanocompartment films possess special molecular encapsulation and release capabilities so that stimuli-free auto-modulated stepwise release of water or drug molecules was achieved through the mesopore channels of robust silica capsule containers embedded in the film. Stepwise release of water was reproducibly observed that originates in the non-equilibrated rates between evaporation of water from the mesopore channels to the exterior and the capillary penetration of water from container interior to the mesopore channels. It was generalized to evaporation of other substances, fragrances, limonene. Application was also tested in the controlled release of the sunscreen UV-absorber (UV-S1) for circumvention of its rapid dissolution in water and prolongation of its prophylactic effect toward harmful ultraviolet radiation. UV-S1 was successfully entrapped within the mesoporous nanocompartment films and was released in a prolonged stepwise mode. The nanocompartment films developed in this research are promising materials for drug delivery since they allow gradual release of therapeutic agents with likely related improvements in their efficacy.

Interlaboratory validation of the in vitro eye irritation tests for cosmetic ingredients. (1) Overview of the validation study and Draize scores for the evaluation of the tests

A three-step interlaboratory validation of alternative methods to the Draize eye irritation test (Draize test) was conducted by the co-operation of 27 organizations including national research institutes, universities, cosmetic industries, kit suppliers and others. Twelve alternative methods were evaluated using 38 cosmetic ingredients and isotonic sodium chloride solution. Draize tests were conducted according to the OECD guidelines using the same lot of test substances as was evaluated in the alternative tests. Results were as follows. (1) Variation in Draize scores was large near the critical range (maximal average Draize total scores (MAS)=15-50) for the evaluation of cosmetic ingredients. (2) Interlaboratory variation was relatively small for the alternative tests. The mean coefficients of variation (CV%) were less than 50 for all assays except for the hens egg-chorioallantoic membrane test (HET-CAM), chorioallantoic membrane-trypan blue staining test (CAM-TB) and haemoglobin denaturation test (HD). The CV% of these three methods came into the same range as the other tests when non-irritants were excluded from the data analysis. (3) Results for acids (pH of 10% solution <2.5), alkalis (pH of 10% solution >11.5) and alcohols (lower mono-ol) in cytotoxicity tests clearly deviated from the other samples in the comparison of cytotoxicity with Draize results. (4) Pearsons correlation coefficients (r) between results from cytotoxicity tests using serum and MAS were -0.86 to -0.92 for samples excluding acids, alkalis and alcohols. (5) When the samples were divided into liquids and powders, r of CAM-TB increased from 0.71 for all samples to 0.80 and 0.92, respectively. (6) Spearmans rank correlation coefficients between the results of alternative methods and MAS were relatively high (r>0.8) in the case of HET-CAM and CAM-TB. Those for cytotoxicity tests were high if the data for acids, alkalis and alcohols were excluded (SIRC-CVS: r=0.945, SIRC-NRU: r=0.931, HeLa-MTT: r=0.926, CHL-CVS: r=0.880). Exclusion of data for powdered samples also increased the coefficient of HET-CAM and CAM-TB to 0.831 and 0.863, respectively. These results suggest that no single method can constitute an evaluation system applicable to all types of test substances by itself. However, several methods will be useful for the prediction of eye irritation potential of cosmetic ingredients if they are used with clear understanding of the characteristics of those methods.

Interactions between Vitamin E Homologues and Ascorbate Free Radicals in Murine Skin Homogenates Irradiated with Ultraviolet Light

The mechanism of oxidation of ascorbic acid in mouse skin homogenates by UV light was investigated by measuring ascorbate free radical formation using electron spin resonance signal formation. Addition of vitamin E (α‐tocopherol or α‐tocotrienol) had no effect, whereas short‐chain homologues (2,5,7,8‐tetramethyl‐6‐hydroxy‐chroman‐2‐carboxylic acid [Trolox] and 2,2,5,7,8‐penta‐methyl‐6‐hydroxychromane [PMC]) accelerated ascorbate oxidation. The similar hydrophilicity of ascorbate, Trolox and PMC increased their interaction, thus rapidly depleting ascorbate. When dihydrolipoic acid was added simultaneously with the vitamin E homologues, the accelerated ascorbate oxidation was prevented. This was due to the regeneration of ascorbate and PMC from their free radicals by a recycling mechanism between ascorbate, vitamin E homologues and dihydrolipoic acid. Potentiation of antioxidant recycling may be protective against UV irradiation‐induced damage. The rate of ascorbate oxidation in the presence of vitamin E homologues was enhanced by a photosensitizer (riboflavin) but was not influenced by reactive oxygen radical quenchers, superoxide dismutase or 5,5‐dimethyl‐l‐pyrroline‐iV‐ox‐ide. These experimental results suggest that the UV irradiation‐induced ascorbate oxidation in murine skin homogenates is caused by photoactivated reactions rather than reactive oxygen radical reactions.

Ferroelectric Liquid Crystal with Extremely Large Spontaneous Polarization

The greatest value ever reported for spontaneous polarization, as high as 4.2×10-8 C/cm2, is observed in DOBA-1-MBC. The relaxation frequency of this material determined from frequency dependence of the dielectric constant is higher than that of DOBAMBC by more than one order of magnitude. DOBA-1-MPC also indicates large spontaneous polarization as high as 1.8×10-8 C/cm2. These characteristics are discussed in terms of molecular structure of these ferroelectric liquid crystals.

Synthesis and ferroelectric properties of new series of ferroelectric liquid crystals

Abstract Four new series of ferroelectric liquid crystals (p-alkoxybenzylidene-p′-amino-1p″-methylbutylcinnamate, p-alkoxybenzylidene-p′-amino-1p″-methylpropyl-cinnamate, o-hydroxy-p-alkoxybenzylidene-p′-amino-2p″-methylbutylcinnamate and o-hydroxy-p-alkoxybenzylidene-p′-amino-1p″-methylpropylcinnamate) have been synthesized. Mesomorphism and dielectric properties of these compounds are studied. Some compounds have extremely high spontaneous polarization.

Wormlike Micelle Formation by Acylglutamic Acid with Alkylamines

Rheological properties of alkyl dicarboxylic acid-alkylamine complex systems have been characterized. The complex materials employed in this study consist of an amino acid-based surfactant (dodecanoylglutamic acid, C12Glu) and a tertiary alkylamine (dodecyldimethylamine, C12DMA) or a secondary alkylamine (dodecylmethylamine, C12MA). (1)H NMR and mass spectroscopic data have suggested that C12Glu forms a stoichiometric 1:1 complex with C12DMA and C12MA. Rheological measurements have suggested that the complex systems yield viscoelastic wormlike micellar solutions and the rheological behavior is strongly dependent on the aqueous solution pH. This pH-dependent behavior results from the structural transformation of the wormlike micelles to occur in the narrow pH range 5.5-6.2 (in the case of C12Glu-C12DMA system); i.e., positive curved aggregates such as spherical or rodlike micelles tend to be formed at high pH values. Our current study offers a unique way to obtain viscoelastic wormlike micellar solutions by means of alkyl dicarboxylic acid-alkylamine complex as gemini-like amphiphiles.

Effect of surfactants on human stratum corneum: electron paramagnetic resonance study.

Electron paramagnetic resonance (EPR) spectra of nitroxide spin probes are useful for studying biological membranes and chemical-membrane interactions. Recently, we established a stripping method to remove stratum corneum (SC) for this purpose. To assess this stripping method with EPR and correlate with standard methods, we quantified the irritant effects of three types of surfactants by measurements of visual score and transepidermal water loss (TEWL), SC hydration and chromametry and studied EPR spectra measurements of surfactant-treated cadaver SC (C-SC) and stripped off SC (S-SC) on patch tested sites. 5-Doxyl stearic acid was the spin label. The order parameter S obtained from the spectra of S-SC correlated with those of C-SC and TEWL values. The results suggest that this method is capable of evaluating the fluidity of SC and correlates with the above bioengineering parameters.

Peptide-based gemini amphiphiles: phase behavior and rheology of wormlike micelles.

Aqueous binary phase behavior of a peptide-based gemini amphiphile with glutamic acid and lysine as spacer group, acylglutamyllysilacylglutamate (m-GLG-m where m = 12, 14, and 16), has been reported over a wide range of concentration and temperature. Lauroylglutamyllysillauroylglutamate, 12-GLG-12, self-assembles into spherical micelles above critical micelle concentration (CMC). The micellar region extends up to 32 wt %, and an ordering of spherical micelles into micellar cubic phase, I(1), takes place at 33 wt % at 25 °C. The phase transition, I(1) - hexagonal liquid crystal, (H(1)) - lamellar liquid crystal, (L(α)) has been observed with further increase in concentration; moreover, mixed phases are also observed between the pure liquid crystal domains. Similar phases were observed with 16-GLG-16 above 50 °C (Krafft temperature). The partial ternary phase behavior shows that the micellar solutions of m-GLG-m can solubilize a large amount of cationic amphiphile, alkyltrimethylammonium bromide, C(n)TAB, (where n = 14 (TTAB) and 16 (CTAB)) at 25 °C. An addition of C(n)TAB to the aqueous solutions of 16-GLG-16 in a dilute region forms a transparent solution of viscoelastic wormlike micelles at very low concentration (0.25 wt %) even at ambient condition. A mixture of oppositely charged amphiphiles, m-GLG-m and C(n)TAB, exhibits synergism as a result the amphiphile layer curvature, becomes less positive, and favors the transition from sphere to rod to transient networks (wormlike micelles). The gemini amphiphile, 16-GLG-16, forms wormlike micelles at relatively low concentrations compared to others reported so far. Viscosity increases by six orders of magnitude compared to that of pure solvent. The hydrophobic chain length of m-GLG-m and coamphiphile affects the rheology; the maximum viscosity achieved with 16-GLG-16/H(2)O/CTAB is higher than that of 14-GLG-14/H(2)O/CTAB, 12-GLG-12/H(2)O/CTAB, and 16-GLG-16/H(2)O/TTAB systems. These temperature-sensitive systems exhibited viscoelastic behavior described by the Maxwell mechanical model with a single stress relaxation mode.

Electron resonance studies on the influence of anionic surfactants on human skin.

BACKGROUND When skin is exposed to chemicals, raw materials interact with the lipid structure of the stratum corneum. At least two types of disorders can be distinguished--that of alkyl chains inside one lipid bilayer and that of lipid layer arrangement. Electron spin resonance (ESR) spectroscopy of a nitroxide spin label is a valuable method in the study of biological membranes. OBJECTIVE These experiments define the effect of anionic surfactants on the lipid bilayer of human stratum corneum. METHODS 5-Doxyl stearic acid (5-DSA) was used as the spin label. Sodium lauryl sulfate (SLS) and sodium lauroyl-L-glutamate (SLG) were the anionic surfactants studied. ESR spectrum measurements of surfactant-treated stratum corneum were performed and order parameters calculated. RESULTS 1% of SLS leads to an obvious change in ESR spectra--from strongly to weakly immobilized spectra. The molecular motion of spin labels (5-DSA) in SLS-treated stratum corneum is different from that of spin labels in the untreated stratum corneum. The ESR spectra suggest that SLS affects the spin label binding to the lipid membrane and causes an increase in the mobility of bilayers. On the other hand, there were minimal changes in ESR spectra of 1% of SLG-treated stratum corneum. An increase in fluidity of skin lipid bilayers suggests a decrease in the skin barrier function. CONCLUSION ESR may provide a facile and robust method to define the subclinical irritancy potential of anionic surfactants and other materials.

Influence of surfactant mixtures on intercellular lipid fluidity and skin barrier function

Background/aims: Surfactant mixtures are used in cosmetic and pharmaceutical formulas in order to establish product efficacy while maintaining mildness and skin lipids. The electron paramagnetic resonance (EPR) technique of the spin labeling method with a nitroxide spin probe is a valuable method in the study of biological membranes. The objective of this study was to define the influence of surfactant mixtures on intercellular lipid fluidity and correlate EPR spectral data with in vivo safety data.