Thermoporometry measurements of human hair via differential scanning calorimetry.

OBJECTIVE: Hair fibres possess an inherently porous structure, which is affected by physical and chemical agents from the environment, as well as those from cosmetic treatments. The present work aims to investigate the potential of a calorimetric method for evaluating the changes of hair porosity, in terms of pore size and size distribution. METHODS: The temperature of the phase transition from solid to liquid is known to be depressed if the liquid is confined within a pore. This shift in temperature can be measured by a calorimetric method like differential scanning calorimetry, DSC. This method is termed thermoporometry and it is the tool used for investigating hair porosity in this work. RESULTS: Virgin and bleached hair fibres are measured by DSC and, by using the equations developed for water behaviour confined in pores of a solid, the size and size distribution of the hair pores are evaluated, and the influence of the cosmetic treatment on the pores is discussed. CONCLUSION: Thermoporometry measurements of hair produced results in good agreement with those obtained by other methods for measuring hair porosity. The analysis of the data suggests that the fibre pores are mostly of a radius of 4 nm, and that the bleaching process increases the total volume of pores through the addition of smaller pores. A prolonged bleaching process appears to reduce the amount of fine pores produced by the first short process, resulting in fewer, but larger, cavities, most likely through a process of pore-merging.

OBJECTIF: Les fibres capillaires possèdent une structure intrinsèquement poreuse, qui est affectée par les agents physiques et chimiques de l'environnement, ainsi que par ceux des traitements cosmétiques. Le présent travail vise à étudier le potentiel d'une méthode calorimétrique pour évaluer les changements de porosité des fibres, en termes de taille et de distribution des pores. MÉTHODES: On sait que la température de la transition de phase entre le solide et le liquide est abaissée si le liquide est confiné dans un pore. Ce changement de température peut être mesuré par une méthode calorimétrique telle que la calorimétrie différentielle à balayage (DSC). Cette méthode est appelée thermoporométrie et c'est l'outil utilisé pour étudier la porosité des fibres capillaires dans ce travail. RÉSULTATS: Les fibres capillaires vierges et blanchies sont mesurées par DSC et, en utilisant les équations développées pour le comportement de l'eau confinée dans les pores d'un solide, la taille et la distribution des pores des fibres sont évaluées, et l'influence du traitement cosmétique sur les pores est discutée. CONCLUSION: Les mesures de thermoporométrie sur les fibres capillaires ont donné des résultats en bon accord avec ceux obtenus par d'autres méthodes de mesure de la porosité des cheveux. L'analyse des données suggère que les pores de la fibre ont pour la plupart un rayon de 4 nm et que le processus de blanchiment augmente le volume total des pores par l'ajout de pores plus petits. Un processus de blanchiment prolongé semble réduire la quantité de pores fins produits par le premier processus court, ce qui se traduit par des cavités moins nombreuses mais plus grandes, très probablement par un processus de fusion des pores.

Thermodynamics and Viscoelastic Property of Interface Unravel Combined Functions of Cationic Surfactant and Aromatic Alcohol against Gram-Negative Bacteria.

Lipopolysaccharides (LPSs), the major constituents of the outer membranes of Gram-negative bacteria, play a key role in protecting bacteria against antibiotics and antibacterial agents. In this study, we investigated how a mixture of cationic surfactants and aromatic alcohols, the base materials of widely used sanitizers, synergistically act on LPSs purified from Escherichia coli using isothermal titration calorimetry (ITC), surface tension measurements, and quartz crystal microbalance with dissipation (QCM-D). ITC data measured in the absence of Ca2+ ions showed the coexistence of exothermic and endothermic processes. The exotherm can be interpreted as the electrostatic binding of the cationic surfactant to the negatively charged LPS membrane surface, whereas the endotherm indicates the hydrophobic interaction between the hydrocarbon chains of the surfactants and LPSs. In the presence of Ca2+ ions, only an exothermic reaction was observed by ITC, and no entropically driven endotherm could be detected. Surface tension experiments further revealed that the co-adsorption of surfactants and LPS was synergistic, while that of surfactants and alcohol was negatively synergistic. Moreover, the QCM-D data indicated that the LPS membrane remained intact when the alcohol alone was added to the system. Intriguingly, the LPS membrane became highly susceptible to the combination of cationic surfactants and aromatic alcohols in the absence of Ca2+ ions. The obtained data provide thermodynamic and mechanical insights into the synergistic function of surfactants and alcohols in sanitation, which will enable the identification of the optimal combination of small molecules for a high hygiene level for the post-pandemic society.

Size, Shape, and Lateral Correlation of Highly Uniform, Mesoscopic, Self-Assembled Domains of Fluorocarbon-Hydrocarbon Diblocks at the Air/Water Interface: A GISAXS Study.

The shape and size of self-assembled mesoscopic surface domains of fluorocarbon-hydrocarbon (FnHm) diblocks and the lateral correlation between these domains were quantitatively determined from grazing incidence small-angle X-ray scattering (GISAXS). The full calculation of structure and form factors unravels the influence of fluorocarbon and hydrocarbon block lengths on the diameter and height of the domains, and provides the inter-domain correlation length. The diameter of the domains, as determined from the form factor analysis, exhibits a monotonic increase in response to the systematic lengthening of each block, which can be attributed to the increase in van der Waals attraction between molecules. The pair correlation function in real space calculated from the structure factor implies that the inter-domain correlation can reach a distance that is over 25 times larger than the domain's size. The full calculation of the GISAXS signals introduced here opens a potential towards the hierarchical design of mesoscale domains of self-assembled small organic molecules, covering several orders of magnitude in space.

Existence of Two-Dimensional Physical Gels even at Zero Surface Pressure at the Air/Water Interface: Rheology of Self-Assembled Domains of Small Molecules.

Films of mesoscopic domains self-assembled from fluorocarbon/hydrocarbon diblock copolymers (FnHm) at the air/water interface were found to display highly elastic behavior. We determined the interfacial viscoelasticity of domain-patterned FnHm Langmuir monolayers by applying periodic shear stresses. Remarkably, we found the formation of two-dimensional gels even at zero surface pressure. These monolayers are predominantly elastic, which is unprecedented for surfactants, exhibiting gelation only at high surface pressures. Systematic variation of the hydrocarbon (n=8; m=14, 16, 18, 20) and fluorocarbon (n=8, 10, 12; m=16) block lengths demonstrated that subtle changes in the block length ratio significantly alter the mechanics of two-dimensional gels across one order of magnitude. These findings open perspectives for the fabrication of two-dimensional gels with tuneable viscoelasticity via self-assembly of mesoscale, low-molecular-weight materials.

Alignment control and softness creation in hair with glycylglycine.

Thick and coarse hair, as typically found among the Japanese population, frequently lacks softness that consumers are acutely aware of. Such poor feeling is accentuated by daily grooming, weathering, and chemical treatments, in particular, which can cause changes in the hair shape and the creation of frizzy or irregularly shaped hair. Existing technologies to improve the soft feel of hair, though effective, usually concentrate on the surface of the fiber and often leave the hair feeling either overconditioned or sometimes even sticky from product buildup. Hair softness is said to be governed by a number of factors, but primarily hair diameter and surface condition. In this study, we have also identified hair alignment as playing a critical role in hair softness. In addition, by studying how Japanese women perceive hair softness when touching their hair, we have identified that the strain on the hair fiber associated with these manipulations is far smaller than previously considered. With these factors in mind, we have studied the mechanisms behind a new softening technology containing glycylglycine (GG). It has been found that treatment with GG can give a tangible feeling of hair softness by dramatically improving alignment in unruly hair and by lowering the modulus of the fiber. Moreover, using the atomic force microscope, it has been revealed that the properties of the cell membrane complex of the hair cortex may be modified after GG treatment; the role of this additive in modifying the internal properties of the hair to create softness will thus be discussed.

Unsaturated fatty acid salts remove biofilms on dentures.

Candidiasis-causing Candida sp. forms biofilms with various oral bacteria in the dentures of the elderly, making it harder to kill and remove the microorganism due to the extracellular polymeric substances. We found that biofilms on dentures can effectively be removed by immersion in an unsaturated fatty acid salt solution. Using optical coherence tomography to observe the progression of biofilm removal by the fatty acid salt solution, we were able to determine that the removal was accompanied by the production of gaps at the interface between the biofilm and denture resin. Furthermore, microstructural electron microscopy observations and time-of-flight secondary ion mass spectrometry elucidated the site of action, revealing that localization of the fatty acid salt at the biofilm/denture-resin interface is an important factor.

18-MEA and hair appearance.

The effects of the removal of 18-MEA on the dynamic contact angle (advancing contact angle and receding contact angle) and friction force (friction force microscopy (FFM)) were examined in the present study. Chemically untreated hair tresses formed more finely ordered bundles, with the fibers aligned more parallel to each other, in the wet state, and lying flat and aligned parallel to each other in the dry state. Hair tresses in which 18-MEA had been removed by potassium t-butoxide treatment formed coarser tangled bundles and were aligned in a disorderly manner in the wet state, causing the hair to become entangled and disorderly in the dry state. This was because the 18-MEA-removed hair fibers adhered to each other and were not easy to realign in the wet state. The distorted part of the bundle dried faster and the tress shape was eventually fixed in the entangled shape. One role of 18-MEA is to allow hair fibers to lie flat and parallel with respect to each other in the wet state by providing relatively high receding contact angles and low surface friction. Hair alignment in the dry state is directly affected by hair alignment in the wet environment, particularly in the case of damaged hair.

Specific localisation of ions in bacterial membranes unravels physical mechanism of effective bacteria killing by sanitiser.

Antimicrobial resistance is a major threat to public health. Although many commercial sanitisers contain a combination of cationic surfactants and aromatic alcohols, the physical mechanisms where these two substances bind to or how they disturb bacterial membranes are still largely unknown. In this study, we designed a well-defined model of Gram-negative bacteria surfaces based on the monolayer of lipopolysaccharides with uniform saccharide head groups. Since commonly used X-ray reflectivity is sensitive to changes in the thickness, roughness and electron density but is not sensitive to elements, we employed grazing incidence X-ray fluorescence. In the absence of Ca2+, cationic surfactants can penetrate into the membrane core with no extra support by disturbing the layer of K+ coupled to negatively charged saccharide head group at z = 17 Å from the air/chain interface. On the other hand, Ca2+ confined at z = 19 Å crosslink charged saccharides and prevent the incorporation of cationic surfactants. We found that the addition of nonlethal aromatic alcohols facilitate the incorporation of cationic surfactants by the significant roughening of the chain/saccharide interface. Combination of precise localisation of ions and molecular-level structural analysis quantitatively demonstrated the synegtestic interplay of ingredients to achieve a high antibacterial activity.

A role of the anteiso branch of 18-MEA in 18-MEA/SPDA to form a persistent hydrophobicity to alkaline-color-treated weathered hair.

The effect of the anteiso-branch moiety of 18-MEA (18-methyleicosanic acid) to create a persistent hydrophobicity of alkaline-color-treated weathered hair treated with 18-MEA/SPDA (stearoxypropyldimethylamine) was investigated by comparing a straight-chain fatty acid (n-heneicosanoic acid, n-HEA) and an iso-branch fatty acid (19-methyleicosanic acid, 19-MEA) with the anteiso-branch fatty acid (18-MEA), using dynamic contact angle measurements, quantification of 18-MEA by LC/MS, and temperature controlled atomic force microscopy (AFM). The dynamic contact angle measurements indicated that the anteiso-branch moiety of 18-MEA is critical for the creation of a persistent hydrophobicity to alkaline-color-treated weathered hair. The temperature-controlled AFM investigations revealed that the anteiso-branch moiety of 18-MEA in the 18-MEA/SPDA system produces a persistent hydrophobicity to alkaline-color-treated weathered hair by providing higher fluidity to the upper region of the 18-MEA/SPDA layer.

Deposition of 18-MEA onto alkaline-color-treated weathered hair to form a persistent hydrophobicity.

A technology for the deposition of a persistent hydrophobicity to alkaline-color-treated weathered hair surfaces using 18-MEA (18-methyleicosanoic acid) is presented. Two approaches were examined in order to make 18-MEA bind tightly to the alkaline-color-treated weathered hair surface. One was to apply 18-MEA as an acid form and the other was to apply 18-MEA as a salt or complex. It was found that the combination of 18-MEA with specific cationic surfactants [stearoxypropyldimethylamine (SPDA) and docosyldimethylamine (DSDA)] makes the alkaline-color-treated weathered hair surface hydrophobic and that its hydrophobicity is maintained even after shampooing. Characterization of adsorbed layers of 18-MEA/SPDA on a mica surface, as a possible hydrophilic surface model, was performed using atomic force microscopy (AFM) and angle-resolved X-ray photoelectron spectroscopy (AR-XPS). The results revealed that 18-MEA/SPDA formed a layer with high wear resistance, with an alkyl chain, the hydrophobic moiety, oriented at an angle of around 25 degrees to the air interface.

Changes in hair properties by Eucalyptus extract.

A long-term usage investigation of a scalp lotion containing Eucalyptus extract, which increases the amount of ceramide in the skin, was carried out to explore the change in physical properties of the hair fiber. Half-head or whole-head usage studies of a scalp lotion with Eucalyptus extract were carried out for the following groups: Japanese female, Japanese senior female, Japanese male, and Caucasian female panelists. As a result, the improvement in hair luster and bounce in the root part of the hair were recognized by the panelists after the long-term application of the scalp lotion with Eucalyptus extract. Measurement of hair gloss intensity and bending stress at the root suggests that this improvement is based on changes in these physical properties. These results indicate that the recognition of panelists is based on an actual change in the hair fiber properties. The efficacy of Eucalyptus extract is expressed regardless of race, age, or gender, since similar results were confirmed in all panelist groups. In order to investigate the cause of these phenomena, we measured the elasticity (Young's modulus) of the new-growth part of the cortex in Eucalyptus extract-treated hair and placebo hair by the nano-indentation method of atomic force microscopy (AFM). These results suggest that the Young's modulus of the new-growth part of the cortex in Eucalyptus extract treated-hair increases in comparison with placebo hair. The IR spectra of treated samples of hair show changes that appear to confirm a decrease in the alpha-helix structure and an increase in the beta-sheet structure.

Formation of nanostructure on hair surface: its characteristic optical properties and application to hair care products.

Uneven structures on hair fiber surface, such as lift up of cuticle or build up of hair spray ingredients, generally cause a diffuse reflection which results in a dull and unhealthy appearance. However, in the case of finer structure than wavelength of visible light, the optical properties change significantly. An application of the phenomenon to hair care products is reported in this paper. Formation of the fine structure on hair surface was achieved by only a shampoo and rinse-off conditioner system including amino-silicone. Chroma enhancement of hair and light introduction into hair fibers were observed simultaneously with formation of the fine structure on the hair surface. The light introduction phenomenon is understood in terms of "Effective Medium Approximation" (EMA). The simulation study based on EMA indicates that a very low refractive index surface is expected to be realized, which well explains the optical experimental results. When the shampoo and conditioner system developed to form the structure on fiber surface was applied to dyed hair, enhancement and long-lasting of vivid appearance was confirmed in spite of dye elution.

Influence of internal structures of hair fiber on hair appearance. III. Generation of light-scattering factors in hair cuticles and the influence on hair shine.

The effects of thermal treatments on hair fiber induced by blow-drying have been investigated. It was found that the hair shows whitish and powdery appearance after heat drying, especially when dark hair is rapidly dried from a wet condition. For all kinds of hair, the appearance of numerous glittering speckles was confirmed on the cuticle surface by optical microscopic observations. SEM images of hair transverse and longitudinal sections with glittering speckles revealed that the splitting of cuticle layers generated by blow-drying occurred not only at the outermost parts of cuticle cells but also at the inner parts of the cellular interfaces. The release and uptake of moisture through fiber surfaces induces deformation of cuticle cells, probably because of anisotropic swelling or drying of the cells. The cuticles with glittering speckles are found to be fragile and are easily damaged in combination with other mechanical stresses such as combing force. Furthermore, the authors have found an efficient system for both improving hair shine and preventing cuticle damage caused by the blow-drying/combing process.

Direct observation of surfactant aggregate behavior on a mica surface using high-speed atomic force microscopy.

The processes of dynamic aggregate transformations of micelles at a mica surface were observed using high-speed atomic force microscopy. We showed that salt concentration affects not only the equilibrium state adsorbed structure but also the time required to reach the equilibrium state on the mica surface.