Physicochemical Properties of α-Form Hydrated Crystalline Phase of 3-(10-Carboxydecyl)-1,1,1,3,5,5,5-heptamethyl Trisiloxane/Higher alcohol/Polyoxyethylene (5 mol) Glyceryl monostearate/Water System.

The α-form hydrated crystalline phase (often called as an α-gel) is one of the hydrated crystalline phases which can be exhibited by surfactants and lipids. In this study, a novel system of an α-form hydrated crystal was developed, composed of 3-(10-carboxydecyl)-1,1,1,3,5,5,5-heptamethyl trisiloxane (CDTS), polyoxyethylene (5 mol) glyceryl monostearate (GMS-5), higher alcohol. This is the first report to indicate that a silicone surfactant can form an α-form hydrated crystal. The physicochemical properties of this system were characterized by small and wide angle X-ray scattering (SWAXS), differential scanning calorimetry (DSC), and diffusion-ordered NMR spectroscopy (DOSY) experiments. SWAXS and DSC measurements revealed that a plurality of crystalline phases coexist in the CDTS/higher alcohol/water ternary system. By adding GMS-5 to the ternary system, however, a wide region of a single α-form hydrated crystalline phase was obtained. The self-diffusion coefficients (Dsel) from the NMR measurements suggested that all of the CDTS, GMS-5, and higher alcohol molecules were incorporated into the same α-form hydrated crystals.

Inhibitory effect of the extract of rhizome of Curcuma longa L in gelatinase activity and its effect on human skin.

Exposure to UV radiation to human skin up-regulates the synthesis of matrix metalloproteinase (MMP) family. Gelatinases are member of MMPs which have been suggested to play an important role in photoaging such as wrinkle formation. To inhibit gelatinase activity is regarded to be very important to keep healthy skin and to protect wrinkle formation. On the other hand, anti-photoaging agents are expected to be derived from natural resources, especially plants. Plant extracts having gelatinase-inhibitory effect that might be used as safe anti-photoaging ingredient were widely screened. An extract of rhizomes of Curcuma longa L. showed inhibitory effect of gelatinase activity. Curcuminoids and slight amount of compound, 6,11-dihydroxy-3-(4-hydroxy-3-mthoxyphenethyl)-7-[(E)-4-(4-hydroxy-3-methoxyphenyl)-2-oxo-3-butenyl]-10-methoxy-2-oxabicyclo[6.3.1.]dodeca-1(11),8(12),9-trien-5-yl (E)-3-(4-hydroxy-3-methoxyphenyl)-2-propenoate (curcuminoid D) were isolated as the gelatinase-inhibitory components from methanol extract of rhizomes. The structure of curcuminoid D was determined by means of spectral data including 1H- and 13C-NMR, and IR. Curcumin exerted the enhancing effect on deposition of basement membrane component at dermal-epidermal junction in skin equivalent model. Topical application of cream containing turmeric extract significantly improved facial skin elasticity and decreased the number of gelatinase-positive stratum corneum clusters in human facial skins. These results indicated that turmeric is an effective ingredient to improve skin condition and to prevent skin from photoaging by suppressing activation of gelatinase chronically caused by UV.

The corrected structure of depressoside, an antioxidative iridoid glucoside extracted from the flowers of Gentiana urnula Harry Sm.

Three known iridoid glucosides (gentiournoside A, gentiournoside E and depressoside) were isolated from the flowers of Gentiana urnula Harry Sm. through activity-guided fractionations with a 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. All three compounds exhibited excellent DPPH radical scavenging activities (IC50: 10-20 µmol L(-1)) comparable to that of ascorbic acid and Trolox. However, examination of the NMR data revealed that the reported chemical structure of depressoside, previously isolated from the leaves of G. depressa, needed correcting due to incorrect elucidation around C-7 of the iridane skeleton, and was corrected to 6-ß-(2,3-dihydroxyphenyl)-D-glucosyl 7-O-(2,3-dihydroxybenzoyl)-loganate. Depressoside exhibited a much higher scavenging activity against superoxide radicals (IC50: 45.5 µmol L(-1)) than the other two extracted compounds (IC50: more than 900 µmol L(-1)) due to the crucial presence of a pyrogallyl unit.

Development of novel cosmetic base using sterol surfactant. II. Solubilizing of sparingly soluble ultraviolet ray absorbers.

Previous studies have reported that O/W emulsion prepared using a surfactant with phytosterol as the hydrophobic moiety exhibited unique morphology; a lamellar structure was present on the surface of the emulsified particles. It is suggested that such a unique self-organized structure was due to the large and bulky planar structure of the sterol. On the other hand, sparingly soluble compounds including ultraviolet ray absorbers and medicines (e.g., indomethacine and finasteride) have been used after they are dissolved mainly in polar oils. However, it is very difficult to dissolve them in bases that contain small amounts of oil components such as lotions. Moreover, many of these sparingly soluble compounds have planar structures such as aromatic rings and are easy to crystallize in polar oil. In this study, sterol surfactants were considered suitable for solubilizing sparingly soluble compounds, since they have a bulky planar structure in their molecules. On this basis, the solubilization of ultraviolet ray absorbers using sterol surfactants was investigated. Methods to solubilize ultraviolet ray absorbers stably and effectively by using a surfactant that had a phytosterol structure have been clarified. Further, the following features were also suggested: (1) the microemulsion of phytosterol surfactant is different from that of other surfactants and (2) a rigid core that has solubilized compounds between the hydrophobic moieties was considered; further, the core was surrounded by a polyoxyethylene chain that prevented the self-aggregation. Analysis using NMR measurements suggested that (1) the polyoxyethylene/polyoxypropylene random copolymer dimethyl ether squeezed in a narrow gap between the hydrophobic moieties of the surfactant, and (2) this eventually increased the solubilized amount of an ultraviolet ray absorber.

A novel melanin inhibitor: hydroperoxy traxastane-type triterpene from flowers of Arnica montana.

We isolated a novel inhibitor of melanin biosynthesis from the flowers of Arnica montana L. (Compositae), and identified it as a traxastane-type triterpene (3beta,16beta-dihydroxy-21alpha-hydroperoxy-20(30)-taraxastene) [1] by means of 1D or 2D-NMR and liquid chromatography/high-resolution mass spectrometry (LC-HR-MS). Compound [1] at the concentration of 0.53 muM completely inhibited melanin accumulation in cultured B16 melanoma cells. It is one of the most potent among known plant inhibitors of melanin biosynthesis in cultured cells, being 50 times more potent than 4-methoxyphenol, which is used as an anti-pigmentation agent. Its mechanism of action is considered to involve inhibition of transcriptional factor MITF-M (melanocyte-type isoform of microphthalmia-associated transcription factor), which would lead to a decrease of tyrosinase and related genes. We confirmed that compound [1] decreased the protein levels of tyrosinase and its related proteins in B16 melanoma cells. Further study revealed that a similar hydroperoxy triterpene also suppressed the melanin pigment accumulation of B16 melanoma cells. These results indicate that the hydroperoxy group may play an important role in the suppression of the melanin accumulation by compound [1].

Determining water content in human nails with a portable near-infrared spectrometer.

The water content of human nail plates was determined using a portable near-infrared (NIR) spectrometer with an InGaAs photodiode array detector. NIR diffuse reflectance (DR) spectra were collected from 108 cut nail plates with different relative humidity and in vivo from fingernails. Partial least-squares (PLS) regression was applied to the NIR spectra in the 1115-1645 nm region to develop calibration models that determine the water content in the cut nail plates and fingernails. A good correlation was obtained between the NIR spectra and the water content measured by nuclear magnetic resonance (NMR) for the NIR measurement of both cut nail plates and fingernails. The results indicate that the water content in the nails can be determined very rapidly (1 s) by means of the portable NIR spectrometer and PLS regression.