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      Toward Milder Personal Care Cleansing Products: Fast ex vivo Screening of Irritating Effects of Surfactants on Skin Using Raman Microscopy Translated title: Zu milderen Körperpflegeprodukten: Schnelles Ex-vivo-Screening auf Reizwirkungen von Tensiden auf der Haut mithilfe der Raman-Mikroskopie

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          Abstract

          We report a novel Raman technique that allows fast and reliable ex vivo assessment of the irritability of personal care cleansing products to the skin in terms of the molecular-level effects such as retention of water by corneocytes, change in the packing order and content of intercellular lipids, and the structure of keratin. We test this technique for the single surfactants (dodecyl glucoside, sodium dodecyl sulfate, sodium cocoyl glycinate, lauramidopropyl betaine) that are typically used in personal care, as well as on three types of commercial soap bars (“superfat”, “syndet”, and “combar”). We find that soaking of the skin for prolonged time in pure water can cause unfolding of keratin, which is commonly considered as a signature of “harshness” when dealing with the surfactant formulations. Moreover, molecular-level signatures of irritability of the test surfactants and soaps at brief (10 min) exposure times do not follow the trend expected from their critical micelle concentrations (CMC) and collagen swelling. In particular, dodecyl glucoside has positive impact on the barrier properties of the stratum corneum (SC) and apparent detergency properties (solubilizes lipids without affecting their packing order). We also find that two qualitatively different soap bars (“superfat” and “syndet”) are similarly mild under the conditions studied, while the “combar” soap has detergency properties. These results demonstrate that to improve methodology of predicting irritability of a surfactant-based formulation, we need to study more systematically the molecular-level responses of the SC to exposure.

          Kurzfassung

          Wir berichten über eine neuartige Raman-Technik, die eine schnelle und zuverlässige Ex-vivo-Beurteilung der Hautreizung durch Reinigungsprodukte für Körperpflege erlaubt, insbesondere im Hinblick auf die Auswirkungen auf molekularer Ebene wie Wassereinlagerungen durch Korneozyten, Änderungen der Packungsordnung und des Gehalt an interzellularen Lipiden und die Struktur des Keratins. Wir untersuchen diese Technik sowohl für die einzelnen Tenside (Dodecylglucosid, Natriumdodecylsulfat, Natriumcocoylglycinat, Lauramidopropylbetain), die typischerweise in der Körperpflege verwendet werden, als auch für drei Typen handelsüblicher Seifen („superfat“-, „syndet“- und „combar“-Seife). Wir stellen fest, dass das Einweichen der Haut über einen längeren Zeitraum in reinem Wasser zur Entfaltung des Keratins führen kann, was häufig beim Umgang mit Tensidformulierungen als Rauigkeitszeichen angesehen wird. Darüber hinaus folgen bei kurzen Einwirkungszeiten (10 Minuten) die Reizfähigkeit der Testtenside und Seifen auf der molekularen Ebene nicht dem Trend, der aufgrund ihrer kritischen Mizellenbildungskonzentration (CMC) und Kollagenquellung erwartet wird. Insbesondere hat Dodecylglucosid einen positiven Einfluss auf die Barriereeigenschaften des Stratum Corneum (SC) und die offensichtlichen Detergenzeigenschaften (Es löst Lipide auf, ohne ihre Packungsordnung zu beeinflussen). Wir stellen auch fest, dass zwei qualitativ unterschiedliche Seifenstücke („Superfett“ und „Syndet“) unter den untersuchten Bedingungen ähnlich mild sind, während die „Combar“-Seife waschaktive Eigenschaften aufweist. Diese Ergebnisse zeigen, dass wir die molekularen Antworten des SC auf die Exposition systematischer untersuchen müssen, um die Methodik zur Vorhersage der Reizfähigkeit von tensid-basierten Formulierungen zu verbessern.

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          Most cited references 28

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          Structure of water, proteins, and lipids in intact human skin, hair, and nail.

          Raman spectroscopy is a nondestructive analytical method for determining the structure and conformation of molecular compounds. It does not require sample preparation or pretreatment. Recently, near-infrared Fourier transform Raman spectroscopy has emerged as being specially suited for investigations of biologic material. In this study, we obtained near-infrared Fourier transform Raman spectra of intact human skin, hair, nail, and stratum corneum. We disclosed major spectral differences in conformational behavior of lipids and proteins between normal skin, hair, and nail. The amide I and III band location indicated that the majority of proteins in all samples have the same secondary alpha-helix structure. Positions of (S-S) stretching bands of proteins revealed a higher stability of the disulfide bonds in the hair and the nail. Analysis of vibrations of protein -CH groups showed that in the hair and the nail the proteins are apparently highly folded, interacting with the surroundings only to a small degree. The position of lipid specific peaks in spectra of hair, nail, and stratum corneum suggested a highly ordered, lamellar crystalline lipid structure. A greater lipid fluidity was found in whole skin. Assessment of the structure of water clusters revealed that mainly bound water is present in the human skin, stratum corneum, and nail. In conclusion, structural changes of water, proteins, and lipids in intact skin and skin appendages may be analyzed by Raman spectroscopy. This technique may be used in the future in a noninvasive analysis of structural changes in molecular compounds in the skin, hair, and nail associated with different dermatologic diseases.
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            Cleansing without compromise: the impact of cleansers on the skin barrier and the technology of mild cleansing

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              Effects of atmospheric relative humidity on Stratum Corneum structure at the molecular level: ex vivo Raman spectroscopy analysis.

              Skin hydration plays an important role in the optimal physical properties and physiological functions of the skin. Despite the advancements in the last decade, dry skin remains the most common characteristic of human skin disorders. Thus, it is important to understand the effect of hydration on Stratum Corneum (SC) components. In this respect, our interest consists in correlating the variations of unbound and bound water content in the SC with structural and organizational changes in lipids and proteins using a non-invasive technique: Raman spectroscopy. Raman spectra were acquired on human SC at different relative humidity (RH) levels (4-75%). The content of different types of water, bound and free, was measured using the second derivative and curve fitting of the Raman bands in the range of 3100-3700 cm(-1). Changes in lipidic order were evaluated using νC-C and νC-H. To analyze the effect of RH on the protein structure, we examined in the Amide I region, the Fermi doublet of tyrosine, and the νasymCH3 vibration. The contributions of totally bound water were found not to vary with humidity, while partially bound water varied with three different rates. Unbound water increased greatly when all sites for bound water were saturated. Lipid organization as well as protein deployment was found to be optimal at intermediate RH values (around 60%), which correspond to the maximum of SC water binding capacity. This analysis highlights the relationship between bound water, the SC barrier state and the protein structure and elucidates the optimal conditions. Moreover, our results showed that increased content of unbound water in the SC induces disorder in the structures of lipids and proteins.
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                Author and article information

                Journal
                tsd
                Tenside Surfactants Detergents
                Carl Hanser Verlag
                0932-3414
                2195-8564
                16 September 2019
                : 56
                : 5
                : 388-397
                Affiliations
                1 Department of Earth and Environmental Engineering, Columbia University, New York, 10027 NY
                2 Global Technology Center, Colgate-Palmolive Company, Piscataway, NJ 08855
                Author notes
                [] Correspondence address, Dr. Irina V. Chernyshova, Department of Earth and Environmental Engineering, Columbia University, New York, 10027 NY, USA, E-Mail: ic2228@ 123456columbia.edu

                Irina Chernyshova is an Associate Research Scientist in the Department of Earth and Environmental Engineering, Columbia University. Her main area of interests includes the development of green surfactant and polymer formulations for various applications including personal care. She holds PhD in intermolecular interactions and spectroscopy from St. Petersburg State University, Russia. Before Columbia University, she was an Associate Professor in the Department of Medical Physics and Bioengineering, Peter the Great St. Petersburg Polytechnic University, Russia. She has authored a monograph on infrared spectroscopy and more than 50 papers in peer-reviewed journals.

                Brajesh Jha has a Ph.D. in Surfactant Chemistry from the University of Pune in India. At present, he is a Senior Technical Associate at Colgate-Palmolive Global Technology Center (GTC) in Piscataway, New Jersey, USA. His research interests are surfactants, interfacial and colloidal science and their application in personal and home care industries. He is also a recipient of prestigious Shaw Mudge and Des Goddard awards for his contributions to emulsion and colloid science.

                Aixing Fan is a Manager of Technology, Personal Care Early Research, at Colgate-Palmolive Global Technology Center (GTC) in Piscataway, New Jersey, USA. Before joining Colgate-Palmolive, she worked as a Staff Chemist at DuPont. She holds PhD in the field of Colloid and Surface Chemistry from Columbia University in the City of New York and Masters from Peking University.

                Hongwei Shen is a Manager of Technology at Colgate Palmolive Company and leads a group of scientists focusing on the surfactant-based formulation research and innovation. He holds PhD in chemistry from McGill University with a focus on polymer chemistry. He has published numerous scientific papers in peer-reviewed journals and holds multiple patents.

                Derek Kim is a R&D scientist with a demonstrated history of working with surfactants, proteins/enzymes, polymers, particles, colloidal systems and analytical techniques. He is a graduate of Columbia University and the Cooper Union in Earth & Environmental Engineering and Chemical Engineering, respectively, and is currently a R&D Research Scientist at Reckitt Benckiser (RB).

                Ponisseril Somasundaran is the La von Duddleson Krumb Professor at Columbia University and Director of NSF/IUCRC Center for Particulate and Surfactant Systems. His main expertise includes colloid and interface science and surfactants. He is the author/editor of fifteen books and over 700 scientific publications and patents. He is a Fellow of the American Institute of Chemical Engineers and a member of the US National Academy of Engineering and the corresponding academies of China, India, Russia, the Balkans, and the Royal Society of Canada.

                Article
                TS110637
                10.3139/113.110637
                © 2019, Carl Hanser Publisher, Munich
                Page count
                References: 36, Pages: 10
                Product
                Self URI (journal page): https://www.hanser-elibrary.com/loi/tsd
                Categories
                Personal Care/Cleansing

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