Emollient structure and chemical functionality effects on the biomechanical function of human stratum corneum.

OBJECTIVE: Cosmetic emollients are widely used in skincare formulations due to their ability to 'soften' the skin and modulate formulation spreadability. Though emollients are commonly used, little is known about their effects on the biomechanical barrier properties of human stratum corneum (SC), which play a critical role in consumer perception of formulation efficacy. Accordingly, our objective was to provide new insights with a study involving fourteen cosmetic emollient molecules with widely varying structures, molecular weights, SC diffusivities, topological polar surface areas (TPSAs), viscosities and chemical functionalities. METHODS: Mechanical stress in the SC was measured in vitro using a substrate curvature measurement technique. Stress development due to SC drying was measured before and after topical treatment with cosmetic emollients. Emollient diffusivity and alterations to lipid content in SC after treatment were measured via ATR-FTIR spectroscopy. The maximum penetration volume of emollient in SC was characterized to elucidate mechanisms underlying emollient effects on stress. RESULTS: The application of all cosmetic emollients caused a reduction in SC mechanical stress under dehydrating conditions, and a linear correlation was discovered between emollient penetration volume and the degree of stress reduction. These molecules also induced increases in stress equilibration rate, signalling changes to SC transport kinetics. Stress equilibration rate increases linearly correlated with decreasing intensity of the νCH2 band, indicating a previously unknown interaction between cosmetic emollients and SC lipids. Stress and penetration volume results were rationalized in terms of a multi-parameter model including emollient molecular weight, diffusivity, TPSA and viscosity. CONCLUSION: We provide a new rational basis for understanding the effects of cosmetic emollient choice on biomechanical properties affecting SC barrier function and consumer perception. We demonstrate for the first time that emollients very likely reduce SC mechanical stress through their ability to take up volume when penetrating the SC, and how molecular weight, SC diffusivity, TPSA and viscosity are predictive of this ability. As cosmetic formulations continue to evolve to meet the needs of customers, emollient molecules can be selected that not only contribute to formulation texture and/or spreadability but that also leverage this novel connection between emollient penetration and SC biomechanics.

OBJECTIF: Les émollients cosmétiques sont largement utilisés dans les formulations de soins de la peau en raison de leur capacité à «adoucir¼ la peau et à moduler la capacité d'étalement de la formulation. Bien que les émollients soient couramment utilisés, on en sait peu sur leurs effets sur les propriétés de barrière biomécanique de la couche cornée humaine (SC), qui jouent un rôle essentiel dans la perception par les consommateurs de l'efficacité de la formulation. En conséquence, notre objectif était de fournir de nouvelles perspectives avec une étude impliquant quatorze molécules émollientes cosmétiques avec des structures, des poids moléculaires, des diffusivités SC, des surfaces polaires topologiques (TPSA), des viscosités et des fonctionnalités chimiques très variables. MÉTHODES: La contrainte mécanique dans le SC a été mesurée in vitro en utilisant une technique de mesure de la courbure du substrat. Le développement du stress dû au séchage SC a été mesuré avant et après un traitement topique avec des émollients cosmétiques. La diffusivité émolliente et les altérations de la teneur en lipides dans la SC après le traitement ont été mesurées par spectroscopie ATR-FTIR. Le volume de pénétration maximal de l'émollient dans SC a été caractérisé pour élucider les mécanismes sous-jacents aux effets émollients sur le stress. RÉSULTATS: L'application de tous les émollients cosmétiques a entraîné une réduction de la contrainte mécanique SC dans des conditions de déshydratation, et une corrélation linéaire a été découverte entre le volume de pénétration de l'émollient et le degré de réduction de la contrainte. Ces molécules ont également induit des augmentations du taux d'équilibrage des contraintes, signalant des changements dans la cinétique de transport SC. Le taux d'équilibrage des contraintes augmente linéairement en corrélation avec la diminution de l'intensité de la bande νCH2 , indiquant une interaction jusque-là inconnue entre les émollients cosmétiques et les lipides SC. Les résultats du stress et du volume de pénétration ont été rationalisés en termes d'un modèle multi-paramètres comprenant le poids moléculaire émollient, la diffusivité, le TPSA et la viscosité. CONCLUSION: Nous fournissons une nouvelle base rationnelle pour comprendre les effets du choix des émollients cosmétiques sur les propriétés biomécaniques affectant la fonction de barrière SC et la perception du consommateur. Nous démontrons pour la première fois que les émollients réduisent très probablement la contrainte mécanique SC grâce à leur capacité à prendre du volume lors de la pénétration du SC, et comment le poids moléculaire, la diffusivité SC, le TPSA et la viscosité sont prédictifs de cette capacité. Alors que les formulations cosmétiques continuent d'évoluer pour répondre aux besoins des clients, des molécules émollientes peuvent être sélectionnées qui contribuent non seulement à la texture et / ou à l'étalement de la formulation, mais qui exploitent également cette nouvelle connexion entre la pénétration des émollients et la biomécanique SC.

[From tonsil capping to tonsillectomy to tonsillotomy]. / Von der Mandelkappung über die Tonsillektomie zur Tonsillotomie.

Medicine has been dealing with palatine tonsil disorders since its beginnings. With the initial aim of eliminating chronic centres of inflammation, over time manifold surgical processes to extract tonsils were developed and tested. Very early on it already became clear that the complete extraction of the tonsil along its connective tissue capsule can lead to serious complications: the risk of bleeding after a tonsillectomy is well-known to currently practising surgeons. In order to reduce this risk and due to not yet existing safe anaesthesia, various techniques were developed aimed at merely reducing the size of the tonsils that is partially removing them within their capsules. Since only smaller intratonsillar blood vessels were affected in this process and bigger peritonsillar feeding arteries and veins remained unharmed, the risk of secondary haemorrhage was reduced considerably. The subtlest instruments for this process were created primarily during the 19 th century. This intracapsular, partial tonsillectomy, also referred to as tonsillotomy or " tonsil capping ", became widespread during that time. Due to its fast and easy application, as well as the low complication rates, it was used especially for children. However, the development of safer anaesthetic techniques at the beginning of the 20 th century meant that the extraction of the entire tonsil, tonsillectomy in toto, eventually became more feasible even in children. Against this background as well as a result of intense discussions on possible secondary scarring of the remaining tonsil tissue accompanied by inflammatory after-eff ects, the technique of tonsillotomy, the partial extraction of the tonsils, was gradually abandoned in favour of that of tonsillectomy and eventually almost completely forgotten during the latter half of the 20 th century. The advances in sleep research and the discovery of general developmental physiological impairment arising from disrupted sleep patterns during infancy led to a rebirth of this surgical application. Tonsillotomy is currently widely accepted as a safe and effective method of treatment for obstructive sleep-related breathing disorders in children. However, due to the history of this procedure, the problem of possible long-term inflammatory complications remains. In the following chapters, fi rst, an abstract of the history of the tonsillotomy is presented. Several historic papers on inflammatory secondary disorders in large patient collectives will be introduced based on a search of the existing literature. Despite the correct diagnostic evaluation as well as the limitation to children unfavourable clinical experiences following a tonsillotomy could not be confirmed even then. The development of tonsillotomy to full tonsillectomy procedures in the 20 th century will be illustrated by means of these historic sources.

Objective emotional assessment of tactile hair properties and their modulation by different product worlds.

Tactile properties of cosmetic products constitute weak stimuli and thus can be expected to be easily modified by mental images. In order to enhance an intended positive-emotion-inducing effect of such a product, its experience can be embedded in a certain 'world' that generates a positive emotional imagination. The present study investigated such an influence in 12 males and 12 females, half of each being laymen and experts in sensory assessment. Two product worlds (emotional and technical) and three different hair samples, two of them treated with different shampoos and an untreated one as control, were presented to each subject in counter-balanced order of all six combinations. An objective emotional assessment using a psychophysiological technique developed in an earlier study was applied and compared with a traditional sensory assessment. Among the physiological measures, peripheral blood volume and facial muscular activity were the most sensitive in revealing effects of and interactions between the product worlds and hair samples. A multivariate evaluation of the physiological data revealed three discriminant functions that explained 78.4% of the total variance and enabled a re-classification considerably better than chance. The first discriminant function clearly separated the treated from the untreated hair samples which was not possible by subjective ratings or traditional sensory assessment. The two other discriminant functions comprised a hedonistic and a product world factor. The emotional product world exerted the largest influence in case of the weakest tactile differences between the hair samples, and its influence was larger on laymen than on experts. Gender effects were most prominent in the subjective domain. In conclusion, multivariate psychophysiological methodology is superior to traditional sensory assessment in revealing subtle differences in the tactile perception of cosmetic products.

Coordination chemistry of verdazyl radicals: group 12 metal (Zn, Cd, Hg) complexes of 1,4,5,6-tetrahydro-2,4-dimethyl-6-(2 pyridiyl)-1,2,4,5-tetrazin -3(2H)-one (pvdH3) and 1,5-dimethyl-3-(2 pyridil)-6-oxoverdazyl (pvd).

Ferricyanide oxidation of 1,4,5,6-tetrahydro-2,4-dimethyl-6-(2'-pyridyl)-1,2,4,5-tetrazin-3(2H)-one (pvdH3) produces the stable chelating free radical 1,5-dimethyl-3-(2'-pyridyl)-6-oxoverdazyl (pvd) as an orange solid. Combination of group 12 metal halides with the ligand pvdH3 in acetonitrile results in precipitation of metal complexes. The mercuric chloride complex crystallizes in the monoclinic space group P2(1/c) with unit cell dimensions a = 8.5768(8) A, b = 19.1718(17) A, c = 8.5956(8) A, beta = 90.405 degrees, and V = 1413.4(2) A3. The mercuric ion is tricoordinate with a distorted trigonal planar geometry. Cadmium iodide and zinc chloride induce ring opening of the tetrazine resulting in pentacoordinate complexes of a hydrazone ligand. The cadmium iodide complex crystallizes in the triclinic space group P1 with cell dimensions a = 7.7184(8) A, b = 8.0240(9) A, c = 13.348(2) A, alpha = 97.876(4) degrees, beta = 95.594(6) degrees, gamma = 107.304(6) degrees, and V = 773.40(21) A3. Oxidation of all three metal complexes produces verdazyl radicals. Metal coordination is indicated by small changes in the EPR spectrum and by changes in the UV-visible spectrum, in particular the changes in the position of bands in the visible region. The metal halide-pvd complexes can also be synthesized by direct combination of metal halides with the free radical.

Evidence for parallel photocycles and implications for the proton pump in bacteriorhodopsin.

In order to account for the large variety of kinetic phenomena in the light-induced reactions of bacteriorhodopsin's retinal chromophore (BR), a scheme of parallel photocycles has been proposed [W. Eisfeld, C. Pusch, R. Diller, R. Lohrmann and M. Stockburger, Biochemistry, 32 (1993) 7196-7215]. In the present study an experimental test for the validity of this model is described which is based on the fact that in the alkaline region the longest-living intermediates M(f), M(S) or N in each of the proposed cycles have significantly different lifetimes. A condition for the existence of parallel cycles would be that the population of M(f), M(S) or N is accompanied by a respective depletion of BR in each individual cycle. Dual-beam laser experiments were performed which showed that this condition is fulfilled. It is concluded that those proton transfer steps which are important for the function as a proton pump are the same for all cycles.

Sensory rhodopsin I photocycle intermediate SRI380 contains 13-cis retinal bound via an unprotonated Schiff base.

Sensory rhodopsin I (SRI), the mutated derivative SRI-D76N and the complex of SRI with its transducer HtrI were overexpressed in Halobacterium salinarium and analyzed by resonance Raman spectroscopy. In the initial state SRI contains all-trans retinal bound via a protonated Schiff base as confirmed by retinal extraction which yields 95 +/- 3% all-trans retinal. The photocycle intermediate absorbing maximally at 380 nm (SRI380) contains a Schiff base linkage between the protein and 13-cis retinal. Extraction of illuminated SRI yields up to 93% 13-cis retinal. Neither the mutation D76N nor HtrI changed the vibrational pattern of the chromophore.

Resonance Raman and optical transient studies on the light-induced proton pump of bacteriorhodopsin reveal parallel photocycles.

The photocycle of bacteriorhodopsin (bR) was studied at ambient temperature in aqueous suspensions of purple membranes using time-resolved resonance Raman (RR) and optical transient spectroscopy (OTS). The samples were photolyzed, and the fractional concentrations of the retinylidene chromophore in its parent state, BR570, and in the intermediate states L550, M412, N560, and O640 were determined in the time domain 20 microseconds-1 s and in the pH range 4-10.5. Two kinetically different L components could be identified. At pH 7 one fraction of L (approximately 65%) decays in 80 microseconds to M (deprotonation of the Schiff base), whereas the residual part is converted in approximately 0.5 ms to N. The RR spectra reveal only minor structural changes of the chromophore in the L-->N transition. These were attributed to a conformational change of the protein backbone [Ormos, P., Chu, K., & Mourant, J. (1992) Biochemistry 31, 6933]. With decreasing pH the L-->N transition is delayed to > 2 ms following a titration-like function with pKa approximately 6.2. The decay of M412 monitored by OTS can be fitted for each pH value by two different amplitudes and time constants (Mf, tau f; Ms, tau s; f = fast, s = slow). Both Mf and Ms consist of subcomponents which can be distinguished by their different reaction pathways (but not by OTS). Mf occurs in the reaction sequences L-->Mf-->N-->BR and L-->Mf-->O-->BR. The population of the first sequence, in which N is formed with the time constant tau f (approximately 2-4 ms, pH 6-10.5), increases with pH. Ms is also found in two different reaction sequences of the form L-->Ms-->BR. The quantitative analysis reveals that each "titration effect" can be related to a certain fraction of bR. It is proposed that each fraction can be identified with a "subspecies" of bR which undergoes an independent and individual cyclic reaction. A complete reaction scheme is set up which represents the manifold of observed phenomena. It is concluded from the pH dependence of the lifetimes of Ms and N that the reconstitution of BR570 in the reaction steps Ms-->BR and N-->BR requires the uptake of a proton from the external phase. It is argued that this proton catalyzes the reisomerization of retinal, whereas the Schiff base is internally reprotonated from Asp-85. A model for proton pumping is proposed in which the proton taken up from the external phase to catalyze the reisomerization of retinal is the one which is pumped through the membrane during the photocycle of bR.