Current views on non-invasive in vivo determination of physiological parameters of the stratum corneum using confocal Raman microspectroscopy

Confocal Raman microspectroscopy is widely used in dermatology and cosmetology for analysis of the concentration of skin components (lipids, natural moisturizing factor molecules, water) and the penetration depth of cosmetic/medical formulations in the human stratum corneum (SC) in vivo. In recent years, it was shown that confocal Raman microspectroscopy can also be used for non-invasive in vivo depth-dependent determination of the physiological parameters of the SC, such as lamellar and lateral organization of intercellular lipids, folding properties of keratin, water mobility and hydrogen bonding states. The results showed that the strongest skin barrier function, which is primarily manifested by the orthorhombic organization of intercellular lipids, is provided at ≈20–40% SC depth, which is related to the maximal bonding state of water with surrounding components in the SC. The secondary and tertiary structures of keratin determine water binding in the SC, which is depth-dependent. This paper shows the technical possibility and advantage of confocal Raman microspectroscopy in non-invasive investigation of the skin and summarizes recent results on in vivo investigation of the human SC.

Confocal Raman Spectroscopic Imaging for Evaluation of Distribution of Nano-Formulated Hydrophobic Active Cosmetic Ingredients in Hydrophilic Films

Film-forming systems are highly relevant to the topical administration of active ingredients (AI) to the body. Enhanced contact with the skin can increase the efficacy of delivery and penetration during prolonged exposure. However, after the evaporation of volatile solvents to form a thin film, the distribution of the ingredient should remain homogenous in order to ensure the effectiveness of the formula. This is especially critical for the use of hydrophobic molecules that have poor solubility in hydrophilic films. In order to address this concern, hydroxyphenethyl esters (PHE) of Punica granatum seed oil were prepared as a nanosuspension stabilised by poloxamers (NanoPHE). NanoPHE was then added to a formulation containing polyvinyl alcohol (PVA) as a film forming agent, Glycerol as a plasticiser and an antimicrobial agent, SepicideTM HB. Despite their reliability, reference methods such as high-performance liquid chromatography are increasingly challenged due to the need for consumables and solvents, which is contrary to current concerns about green industry in the cosmetics field. Moreover, such methods fail to provide spatially resolved chemical information. In order to investigate the distribution of ingredients in the dried film, Confocal Raman imaging (CRI) coupled to Non-negatively Constrained Least Squares (NCLS) analysis was used. The reconstructed heat maps from a range of films containing systematically varying PHE concentrations highlighted the changes in spectral contribution from each of the ingredients. First, using NCLS scores it was demonstrated that the distributions of PVA, Glycerol, SepicideTM HB and PHE were homogenous, with respective relative standard deviations (RSD) of 3.33%, 2.48%, 2.72% and 6.27%. Second, the respective relationships between ingredient concentrations in the films and their Raman responses, and the spectral abundance were established. Finally, a model for absolute quantification for PHE was be constructed using the percentage of spectral abundance. The prepared %w/w concentrations regressed against predicted %w/w concentrations, displaying high correlation (R2 = 0.995), while the Root Mean Squared Error (0.0869% w/w PHE) confirmed the precision of the analysis. The mean percent relative error of 3.75% indicates the accuracy to which the concentration in dried films could be determined, further supporting the suitability of CRI for analysis of composite solid film matrix. Ultimately, it was demonstrated that nanoformulation of hydrophobic PHE provides homogenous distribution in PVA based film-forming systems independent of the concentration of NanoPHE used in the formula.

Enhancing Thermal and Mechanical Properties of Ramie Fiber via Impregnation by Lignin-Based Polyurethane Resin

In this study, lignin isolated and fractionated from black liquor was used as a pre-polymer to prepare bio-polyurethane (Bio-PU) resin, and the resin was impregnated into ramie fiber (Boehmeria nivea (L.) Gaudich) to improve its thermal and mechanical properties. The isolated lignin was fractionated by one-step fractionation using two different solvents, i.e., methanol (MeOH) and acetone (Ac). Each fractionated lignin was dissolved in NaOH and then reacted with a polymeric 4,4-methane diphenyl diisocyanate (pMDI) polymer at an NCO/OH mole ratio of 0.3. The resulting Bio-PU was then used in the impregnation of ramie fiber. The characterization of lignin, Bio-PU, and ramie fiber was carried out using several techniques, i.e., Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), pyrolysis-gas-chromatography-mass-spectroscopy (Py-GCMS), Micro Confocal Raman spectroscopy, and an evaluation of fiber mechanical properties (modulus of elasticity and tensile strength). Impregnation of Bio-PU into ramie fiber resulted in weight gain ranging from 6% to 15%, and the values increased when extending the impregnation time. The reaction between the NCO group on Bio-PU and the OH group on ramie fiber forms a C=O group of urethane as confirmed by FTIR and Micro Confocal Raman spectroscopies at a wavenumber of 1600 cm−1. Based on the TGA analysis, ramie fiber with lignin-based Bio-PU had better thermal properties than ramie fiber before impregnation with a greater weight residue of 21.7%. The mechanical properties of ramie fiber also increased after impregnation with lignin-based Bio-PU, resulting in a modulus of elasticity of 31 GPa for ramie-L-isolated and a tensile strength of 577 MPa for ramie-L-Ac. The enhanced thermal and mechanical properties of impregnated ramie fiber with lignin-based Bio-PU resins could increase the added value of ramie fiber and enhance its more comprehensive industrial application as a functional material.