4-Methylbenzylidene camphor microspheres: reconstituted epidermis (Skinethic®) permeation and distribution.

OBJECTIVE: The UV filter 3(4-methylbenzylidene) camphor (4-MBC) is a common ingredient in sunscreen cosmetic products. However, different 'in vitro' and 'in vivo' studies suggest that 4-MBC can cause endocrine disrupting effects. Therefore, there is a need for new systems able to minimize the skin penetration of this UV filter. The aim of this study was to evaluate cutaneous permeation and distribution, through and into EPISKIN reconstituted epidermis (RE) from an O/W emulsion containing 4-MBC free or encapsulated in polymeric substantive microspheres. METHODS: Microspheres containing 4-MBC were prepared using the emulsification-solvent evaporation method and characterized for shape and surface morphology and encapsulation efficiency. O/A emulsions containing sunscreen free or encapsulated in microspheres were undergone to permeation tests through RE using vertical diffusion cells. At the end of the in vitro permeation experiments, the skin was subjected to tape stripping procedure to separate stratum corneum from viable epidermis. Each part was properly treated to extract the sunscreen retained and subject to quantitative analysis. RESULTS: The encapsulation of the sunscreen in the microspheres remarkably reduced the permeation of 4-MBC and increased its retention on the skin surface where its action is more desirable. CONCLUSIONS: The results of this study confirm the validity of substantive microspheres as an ideal formulation candidate to use in sunscreen preparation as they appear minimizing its systemic uptake and the potential associate toxicological risks. Therefore, more of the active sunscreen remains on the surface of the skin where it is intended to act and a higher activity it will explicate.

Thermal mud maturation: organic matter and biological activity.

OBJECTIVE: Many of the therapeutic and cosmetic treatments offered in spas are centred on mud therapy, to moisturize the skin and prevent skin ageing and rheumatic diseases. Thermal mud is a complex matrix composed of organic and inorganic elements which contribute to its functions. It is a natural product derived from the long mixing of clay and thermal water. During its maturation, organic substances are provided by the microalgae, which develop characteristic of the composition of thermal water. METHODS: The aim of this study was to identify methods for introducing objective parameters as a basis for characterizing thermal mud and assessing its efficacy. Samples of thermal mud were collected at the Saturnia spa, where there are several sulphureous pools. The maturation of the mud was evaluated by organic component determination using extractive methods and chromatographic analysis (HPLC, GC-MS, SPME). We also studied the radical scavenging activity of mud samples at different stages of maturation, in a homogeneous phase, using several tests (DPPH, ORAC, ABTS). RESULTS: We identified several classes of compounds: saturated and unsaturated fatty acids, hydroxyl acids, dicarboxylic acids, ketoacids, alcohols and others. SPME analysis showed the presence of various hydrocarbons compounds (C(11) -C(17)) and long-chain alcohols (C(12) -C(16)). Six or seven months seemed appropriate to complete the process of maturation, and the main effect of maturation time was the increase of lipids. Six-month mud showed the highest activity. The hydrophilic extract was more active than the lipophilic extract. CONCLUSION: The results indicate that maturation of thermal mud can be followed on the basis of the changes in its organic composition and antioxidant properties along the time. They also highlight the need to develop reference standards for thermal muds in relation to assess their use for therapeutic and cosmetic purposes.

Polarization insensitive infrared absorbing behaviour of one-dimensional multilayer stack: a fractal approach.

The control and tailoring of infrared absorbance/emittance is a crucial task for all those applications involving thermal radiation management and detection. We theoretically investigated the peculiar absorbing/emitting behaviour of pre-fractal Cantor multilayers, in order to design a polarization-insensitive multilayer stack absorbing over a wide angular lobe in the mid wavelength infrared range (8-10 µm). Using transfer matrix method, we explored the spectral properties arising from both the material and the geometrical dispersion. We considered several combinations of the constituent materials: SiO2 was combined with TiO2 and Si, respectively.

Circular dichroism in the optical second-harmonic emission of curved gold metal nanowires.

Here we report the experimental observation of circular dichroism in the second-harmonic field (800-400 nm conversion) generated by self-organized gold nanowire arrays with subwavelength periodicity (160 nm). Such circular dichroism, raised by a nonlinear optical extrinsic chirality, is the evident signature of the sample morphology. It arises from the curvature of the self-assembled wires, producing a lack of symmetry at oblique incidence. The results were compared, both in the optical linear and nonlinear regime, with a reference sample composed of straight wires. Despite the weak extrinsic optical chirality of our samples (not observable by our optical linear measurements), high visibility (more than 50%) was obtained in the second-harmonic generated field.

Adaptive tuning of infrared emission using VO2 thin films.

Phase-transition materials provide exciting opportunities for controlling optical properties of photonic devices dynamically. Here, we systematically investigate the infrared emission from a thin film of vanadium dioxide (VO2). We experimentally demonstrate that such thin films are promising candidates to tune and control the thermal radiation of an underlying hot body with different emissivity features. In particular, we studied two different heat sources with completely different emissivity features, i.e. a black body-like and a mirror-like heated body. The infrared emission characteristics were investigated in the 3.5-5.1 µm spectral range using the infrared thermography technique which included heating the sample, and then cooling back. Experimental results were theoretically analyzed by modelling the VO2 film as a metamaterial for a temperature range close to its critical temperature. Our systematic study reveals that VO2 thin films with just one layer 80 nm thick has the potential to develop completely different dynamic tuning of infrared radiation, enabling both black-body emission suppression and as well as mirror emissivity boosting, in the same single layer device. Understanding the dynamics and effects of thermal tuning on infrared emission will benefit wide range of infrared technologies including thermal emitters, sensors, active IR filters and detectors.

Optical polarization based logic functions (XOR or XNOR) with nonlinear Gallium nitride nanoslab.

We present a scheme of XOR/XNOR logic gate, based on non phase-matched noncollinear second harmonic generation from a medium of suitable crystalline symmetry, Gallium nitride. The polarization of the noncollinear generated beam is a function of the polarization of both pump beams, thus we experimentally investigated all possible polarization combinations, evidencing that only some of them are allowed and that the nonlinear interaction of optical signals behaves as a polarization based XOR. The experimental results show the peculiarity of the nonlinear optical response associated with noncollinear excitation, and are explained using the expression for the effective second order optical nonlinearity in noncollinear scheme.

Preparation and characterization of n-dodecyl-ferulate-loaded solid lipid nanoparticles (SLN).

Solid lipid nanoparticles (SLN) containing a novel potential sunscreen n-dodecyl-ferulate (ester of ferulic acid) were developed. The preparation and stability parameters of n-dodecyl-ferulate-loaded SLN have been investigated concerning particle size, surface electrical charge (zeta potential) and matrix crystallinity. The chemical stability of n-dodecyl-ferulate at high temperatures was also assessed by thermal gravimetry analysis. For the selection of the appropriated lipid matrix, chemically different lipids were melted with 4% (m/m) of active and lipid nanoparticles were prepared by the so-called high pressure homogenization technique. n-Dodecyl-ferulate-loaded SLN prepared with cetyl palmitate showed the lowest mean particle size and polydispersity index, as well as the highest physical stability during storage time of 21 days at 4, 20 and 40 degrees C. These colloidal dispersions containing the sunscreen also exhibited the common melting behaviour of aqueous SLN dispersions.

Coherent control of stimulated emission inside one-dimensional photonic crystals.

In this paper, the quasinormal mode (QNM) theory is applied to discuss the quantum problem of an atom embedded inside a one-dimensional (1D) photonic band gap (PBG) cavity pumped by two counterpropagating laser beams. The e.m. field is quantized in terms of the QNMs in the 1D PBG and the atom modeled as a two-level system is assumed to be weakly coupled to just one of the QNMs. The main result of the paper is that the decay time depends on the position of the dipole inside the cavity, and can be controlled by the phase difference of the two laser beams.

High-performance liquid chromatography determination of direct and temporary dyes in natural hair colourings.

A simple and reliable HPLC method is described for the simultaneous determination of nine direct and temporary hair dyes in hair colourings containing vegetal extracts. Detection was performed by a diode array detector and two different wavelengths, in the visible range (450 and 650 nm), were used for quantitation. The method does not involve any extraction procedure and it is sufficiently rapid and accurate for routine analyses. The method described was successfully applied to the identification of synthetic organic dyes in 13 direct and temporary hair dyeing formulations commercialized as 'natural'.

Unsaturated hydrocarbons with fruity and floral odors.

Hydrocarbons usually do not exhibit odors of interest or well-defined character. However, certain cyclic alkenes have been associated with typical and pleasant notes, such as fruity, green, and floral. One of the best known examples is represented by the isomeric megastigmatrienes, endowed with a pleasant smell of tropical fruits. From the structures of these odorants, 24 analogues and homologues, most of them cyclic alkenes, but including also some open-chain alkenes, have been synthesized to define structural parameters related to the characteristic odors of these compounds. The number and position of double bonds, the substitution on the ring, and the size of the ring are the variables taken into account. Most of the new compounds present a mainly fruity character, associated in several cases with floral and green notes, producing an overall sensation described as "tropical fruit".

New microencapsulated sunscreens: technology and comparative evaluation.

The aim of this work is to obtain new technologically improved microencapsulated sunscreens characterised by UV-radiation stability, good substantivity, low toxicity, a better tolerability and easiness to formulation. For this purpose we prepared two different systems using semisynthetic Hyaluronic Acid (HA) benzyl ester and a synthetic polymer (patent pending). We obtained these systems using two different methodologies: emulsification/solvent evaporation and emulsification/solvent extraction. The comparison between the two formulated systems was carried out in terms of their chemical-physical and biological properties.

Slowing light in chi2 photonic crystals.

A study of parametric nonlinear frequency down-conversion in photonic crystals reveals that under suitable conditions the probe field can be slowed down to approximately 11 m/s. The effect arises as a result of the simultaneous availability of global phase-matching conditions, field localization, and gain experienced by the probe beam. Together, these effects conspire to yield tunneling velocities previously reported only for coherently resonant interactions, i.e., electromagnetic induced transparency, in Bose-Einstein condensates, hot atomic gases, and doped crystals.

Dynamics of counterpropagating pulses in photonic crystals: enhancement and suppression of stimulated emission processes.

Using numerical methods, we study the propagation of counterpropagating pulses in finite photonic crystals. We show that linear interference and localization effects combine to either enhance or suppress stimulated emission processes, depending on the initial phase difference between the input pulses. We consider the example of second harmonic generation, where we find a maximum contrast of three orders of magnitude in nonlinear conversion efficiency as a function of the input phase difference between incident pulses. We interpret these results by viewing the photonic crystal as an open cavity, with a field-dependent, electromagnetic density of modes sensitive to initial and boundary conditions.

Quasinormal-mode description of waves in one-dimensional photonic crystals.

Quasinormal-mode treatment is extended to the description of scalar field behavior in one-dimensional photonic crystals. A one-dimensional photonic crystal is a particular configuration of an open cavity, where discontinuities of the refractive index give rise to field confinement. This paper presents, for a one-dimensional photonic crystal, a discussion about the completeness of the quasinormal-mode representation and, moreover, a discussion on the complex eigenfrequencies, as well as the corresponding field distribution. The concept of density of modes is also discussed in terms of quasinormal modes.

Group velocity, energy velocity, and superluminal propagation in finite photonic band-gap structures.

We have analyzed the notions of group velocity V(g) and energy velocity V(E) for light pulses propagating inside one-dimensional photonic band gap structures of finite length. We find that the two velocities are related through the transmission coefficient t as V(E)=/t/(2)V(g). It follows that V(E)=V(g) only when the transmittance is unity (/t/(2)=1). This is due to the effective dispersive properties of finite layered structures, and it allows us to better understand a wide range of phenomena, such as superluminal pulse propagation. In fact, placing the requirement that the energy velocity should remain subluminal leads directly to the condition V(g)

Simultaneously phase-matched enhanced second and third harmonic generation.

Second and third harmonic generation via a chi((2)) three-wave mixing process can occur with high conversion efficiency in a one-dimensional photonic band gap structure. We find that it is possible to simultaneously achieve enhancement and exact phase-matching conditions of second harmonic and sum frequency generation, omega+2 omega-->3 omega. It is also remarkable that high conversion efficiencies persist under tuning conditions that correspond to a phase mismatch. While these conditions are quite unusual and cannot be achieved in any known bulk material, we show that they can be easily obtained in finite layered structures by using and balancing an interplay between material dispersion and the geometrical dispersion introduced by the structure.

Photonic band edge effects in finite structures and applications to chi 2 interactions.

Using the concept of an effective medium, we derive coupled mode equations for nonlinear quadratic interactions in photonic band gap structures of finite length. The resulting equations reveal the essential roles played by the density of modes and effective phase matching conditions necessary for the strong enhancement of the nonlinear response. Our predictions find confirmation in an experimental demonstration of significant enhancement of second harmonic generation near the photonic band edge. The measured conversion efficiency is in good agreement with the conversion efficiency predicted by the effective-medium model.

Mapping the nonlinear optical susceptibility by noncollinear second-harmonic generation.

We present a method, based on noncollinear second-harmonic generation, to evaluate the nonzero elements of the nonlinear optical susceptibility. At a fixed incidence angle, the generated signal is investigated by varying the polarization state of both fundamental beams. The resulting polarization charts allows us to verify if Kleinman's symmetry rules can be applied to a given material or to retrieve the absolute value of the nonlinear optical tensor terms, from a reference measurement. Experimental measurements obtained from gallium nitride layers are reported. The proposed method does not require an angular scan and thus is useful when the generated signal is strongly affected by sample rotation.

Substantivity of sunscreens -in vitro evaluation of the transdermal permeation characteristics of some benzophenone derivatives.

Synopsis The in vitro permeation through excised hairless mouse skin of a series of 4-O-(N, N-dimethylaminoalkyl)-benzophenones, non-quaternarized and quaternarized, and of two commercial benzophenone sunscreens, taken as reference compounds, was investigated. The aim of the study was to verify the skin penetration of the highly skin-substantive quaternary ammonium derivatives, in comparison with their parent, non-quaternarized compounds. While the quaternary derivatives proved unable to permeate the skin during the period of observation (45 h), their parent amine hydrochlorides and the reference sunscreens (2-hydroxy-4-methoxy-benzophenone-5-sulphonic acid and 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone 5,5'-sodium disulphonate), showed appreciable transdermal fluxes. These data indicate that the presence of a quaternary ammonium group in a molecule, besides inducing a high affinity for cutaneous keratin, may result in hindered or reduced transdermal (and possibly systemic) absorption. Both features may contribute in improving the safety of a cosmetic sunscreen. Résumé On a analysé la pénétration in vitro au travers de peau excisée de souris sans poils d'une gamme de 4-O-(N, N-dimethylaminoalkyl)benzophenones quaternisés et non quaternisés ainsi que de 2 écrans solaires au benzophénone commercialisés utilisés comme témoins. Cette étude avait pour but de vérifier la pénétration dermique de dérivés d'ammonium quaternaire hautement substantifs sur la peau, par rapport à des composés non quatenaires de la même famille. Tandis que les dérivés quaternaires se sont avérés incapables de pénétrer la peau durant la période d'observation (45 heures), les hydrochlorures d'amine et les écrans solaires témoins (2-hydroxy-4-methoxybenzophenone-5-acide sulfonique et 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone 5,5'-disulphonate de sodium), ont montré des flux transdermiques appréciales. Ces données indiquent que la présence d'un groupe d'ammonium quaternaire dans une molécule, bien que possédant une grande affinité pour la kératine cutanée, peut résulter sur une absorption transcutanée (peut-être même systémique) amoindrie voire annihilée. Chacun de ces facteurs peut contribuer à l'amélioration de la sécurité des écrans solaires cosmétiques.

Synthesis and odour properties of floral smelling compounds.

Synopsis To provide further information on the relationships between chemical structure and floral odour, here we report the synthesis and the odour evaluation of some spirane derivatives, designed as conformational models of our previously described floral odorants. One of the new compounds (5-methyl-benzo[1,3]dioxole-2-spiro-1-cyclohexane), in particular, is endowed with a particularly pleasant odour of white flowers, can be easily prepared from commercial products and is more stable than other odorants of the same class; these characteristics make this odorant suitable for being used as an additive in perfumery and cosmetics.