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Emulsifier molecules, with their amphiphilic character, are ubiquitous in moisturizing creams and primarily serve to disperse the water-insoluble molecules such as emollients, oils, lipids and fats in water. The objective of this study was to investigate the effect of emulsifier molecules on the barrier and biomechanical properties of human stratum corneum (SC) and to compare the efficacy of emulsifier molecules when used in a fully formulated moisturizing cream.We employed methods based on thin-film mechanics to measure the drying stress and intercellular cohesion in the SC. The emulsifier molecules or moisturizing creams formulated with them were applied to a fully hydrated SC adhered to a glass substrate. In-plane stress developed in the SC during drying was then measured by tracking changes in the curvature of the glass substrate. The intercellular cohesion within the SC was measured by means of a double cantilever beam (DCB) set-up, where the treated or untreated SC was sandwiched between two substrates, and the delamination energy calculated by measuring the force required to drive a crack through the SC. Moisturizing cream diffusivity through the stratum corneum was measured by spectroscopic technique and related to internal SC stress and fracture energy.We observe significant differences in the biomechanical behaviour of SC when moisturizing creams with different emulsifier molecules are applied on isolated stratum corneum ex vivo. The reduction in maximum stress varied between 12% and 26% depending on the emulsifier molecules used in the formulation. The intercellular cohesion and the diffusion of molecules in the formulated moisturizing creams through the SC were also found to be strongly dependent on the type of emulsifier molecule used in the formulation.The biomechanical and barrier properties of the human stratum corneum show strong dependence on the emulsifier molecule used in the moisturizing creams, even when the creams included only ~3 weight% emulsifier molecules. Moreover, we found that the reduction in SC peak stress was strongly correlated with the formulation diffusivity into the SC. The moisturizing creams diffusing fastest into the SC had the largest reduction in peak stress and vice versa.Les molécules d’émulsifiant, avec leur caractère amphiphile, sont omniprésents dans les crèmes hydratantes et servent principalement à disperser dans l’eau les molécules hydro insolubles telles que les émollients, les huiles, les lipides et les graisses. L’objectif de cette étude était d’étudier l’effet des molécules d’émulsifiant sur les propriétés barrières et biomécaniques de la couche cornée humaine (stratum corneum, SC), et de comparer l’efficacité des molécules d’émulsifiant lorsqu’elles sont utilisées dans une crème hydratante intégralement formulée. MÉTHODES: Nous avons employé des méthodes basées sur des propriétés mécaniques de couches minces pour mesurer le stress de dessèchement et la cohésion intercellulaire dans le SC. Les molécules d’émulsifiant ou les crèmes hydratantes formulées avec ces molécules ont été appliquées sur un SC entièrement hydraté collé à un substrat de verre. Le stress dans le plan développé dans le SC pendant le dessèchement a été mesuré en suivant les changements de courbure du substrat de verre. La cohésion intercellulaire au sein du SC a été mesurée au moyen d’une configuration de faisceau à double cantilever (DCB), où le SC traité ou non traité a été placé entre deux substrats, et l’énergie de délamination calculée en mesurant la force nécessaire pour entrainer une fissure dans la couche cornée. La diffusivité de la crème hydratante dans la couche cornée a été mesurée par la technique spectroscopique, et était liée à l’énergie interne du stress et de la fracture SC. RÉSULTATS: Nous observons des différences significatives dans le comportement biomécanique du SC lorsque des crèmes hydratantes avec différentes molécules d’émulsifiant sont appliquées sur une couche cornée isolée ex vivo. La réduction du stress maximal variait entre 12 % et 26 % en fonction des molécules d’émulsifiant utilisées dans la formulation. La cohésion intercellulaire ainsi que la diffusion des molécules dans les crèmes hydratantes formulées par le biais du SC se sont également révélées fortement dépendantes du type de molécule d’émulsifiant utilisée dans la formulation.Les propriétés biomécaniques et barrières de la couche cornée humaine montrent une forte dépendance à la molécule d’émulsifiant utilisée dans les crèmes hydratantes, même lorsque ces crèmes contenaient uniquement plus ou moins 3% de molécules d’émulsifiant. De plus, nous avons constaté que la réduction du stress maximal était fortement corrélée à la diffusivité de la formulation dans le SC. Les crèmes hydratantes qui se diffusent le plus rapidement dans le SC avaient la plus grande réduction du stress maximal et vice versa.

Since the abrupt outburst of Bitcoin, there has been a meteoric rise in the popularity of blockchain which has been scaled to various domains. Its features have changed the outlook of solutions for many problems and can be applied in various sectors, one being grievance redressal system. In this system, the grievant will submit a grievance which will pass through different levels of hierarchical authoritative screening. Each screening level will have the authority to debar, resolve, revert and forward the grievance to the higher level. Since data integrity is a built-in feature of this system, it eradicates any chances of misuse/abuse of power by the authorities. The dynamic time threshold is an additional feature that automatically transfers the grievance to the higher authority in the hierarchy, thus eliminating any chances of ignorance. Thus, the anomalies and shortcomings of the current grievance system can prevail over.

We report on a sustainable route to protective nanocomposite coatings, where one of the components, nanocellulose fibrils, is derived from trees and the glass matrix is an inexpensive sol-gel organic-inorganic hybrid of zirconium alkoxide and an epoxy-functionalized silane. The hydrophilic nature of the colloidal nanocellulose fibrils is exploited to obtain a homogeneous one-pot suspension of the nanocellulose in the aqueous sol-gel matrix precursors solution. The mixture is then sprayed to form nanocomposite coatings of a well-dispersed, random in-plane nanocellulose fibril network in a continuous organic-inorganic glass matrix phase. The nanocellulose incorporation in the sol-gel matrix resulted in nanostructured composites with marked effects on salient coating properties including optical transmittance, hardness, fracture energy, and water contact angle. The particular role of the nanocellulose fibrils on coating fracture properties, important for coating reliability, was analyzed and discussed in terms of fibril morphology, molecular matrix, and nanocellulose/matrix interactions.

Cellulose nanocomposites can be considered for semistructural load-bearing applications where modulus and strength requirements exceed 10 GPa and 100 MPa, respectively. Such properties are higher than for most neat polymers but typical for molded short glass fiber composites. The research challenge for polymer matrix biocomposites is to develop processing concepts that allow high cellulose nanofibril (CNF) content, nanostructural control in the form of well-dispersed CNF, the use of suitable polymer matrices, as well as molecular scale interface tailoring to address moisture effects. From a practical point of view, the processing concept needs to be scalable so that large-scale industrial processing is feasible. The vast majority of cellulose nanocomposite studies elaborate on materials with low nanocellulose content. An important reason is the challenge to prevent CNF agglomeration at high CNF content. Research activities are therefore needed on concepts with the potential for rapid processing with controlled nanostructure, including well-dispersed fibrils at high CNF content so that favorable properties are obtained. This perspective discusses processing strategies, agglomeration problems, opportunities, and effects from interface tailoring. Specifically, preformed CNF mats can be used to design nanostructured biocomposites with high CNF content. Because very few composite materials combine functional and structural properties, CNF materials are an exception in this sense. The suggested processing concept could include functional components (inorganic clays, carbon nanotubes, magnetic nanoparticles, among others). In functional three-phase systems, CNF networks are combined with functional components (nanoparticles or fibril coatings) together with a ductile polymer matrix. Such materials can have functional properties (optical, magnetic, electric, etc.) in combination with mechanical performance, and the comparably low cost of nanocellulose may facilitate the use of large nanocomposite structures in industrial applications.

Mechanistic behavior and flow properties of cellulose nanofibers (CNFs) in aqueous systems can be described by the crowding factor and the concept of contact points, which are functions of the aspect ratio and concentration of CNF in the suspension. In this study, CNFs with a range of aspect ratio and surface charge density (380–1360 μmol/g) were used to demonstrate this methodology. It was shown that the critical networking point of the CNF suspension, determined by rheological measurements, was consistent with the gel crowding factor, which was 16. Correlated to the crowding factor, both viscosity and modulus of the systems were found to decrease by increasing the charge density of CNF, which also affected the flocculation behavior. Interestingly, an anomalous rheological behavior was observed near the overlap concentration (0.05 wt %) of CNF, at which the crowding factor was below the gel crowding factor, and the storage modulus (G′) decreased dramatically at a given frequency threshold. This behavior ...

Colloidal dispersions of cellulose nanofibrils (CNFs) are viable alternatives to cellulose II dissolutions used for filament spinning. The porosity and water vapor affinity of CNF filaments make them suitable for controlled breathability. However, many textile applications also require water repellence. Here, we investigated the effects of postmodification of wet-spun CNF filaments via chemical vapor deposition (CVD). Two organosilanes with different numbers of methyl substituents were considered. Various surface structures were achieved, either as continuous, homogeneous coating layers or as three-dimensional, hairy-like assemblies. Such surface features reduced the surface energy, which significantly affected the interactions with water. Filaments with water contact angles of up to 116° were obtained, and surface energy measurements indicated the possibility of developing amphiphobicity. Dynamic vapor sorption and full immersion experiments were carried out to inquire about the interactions with water, whether in the liquid or gas forms. Mechanical tests revealed that the wet strength of the modified filaments were almost 3 times higher than that of the unmodified precursors. The hydrolytic and mechanical stabilities of the adsorbed layers were also revealed. Overall, our results shed light on the transformation of aqueous dispersions of CNFs into filaments that are suited for controlled interactions with water via concurrent hydrolysis and condensation reactions in CVD, while maintaining the moisture buffering capacity and breathability of related structures.

The nematic structuring of cellulose nanofibers (CNFs) is proposed as a nanostructural engineering tool for exploiting the potential of CNFs in conceptually new "transparent papers". The nematic-structured CNF papers exhibit superior mechanical properties, optical transparency, gas-barrier properties, heat transfer properties and electrical resistivity, compared with conventional randomly-structured CNF papers.

Although the anisotropy of wood fibers is reasonably well established, the anisotropy of injection molded wood fiber composites is not well understood. This work focuses on chemo-thermomechanical pulp (CTMP) reinforced polypropylene (PP) composites. A kinetic mixer (Gelimat) is used for compounding CTMP/PP composites, followed by injection molding. Effects from processing induced orientation on mechanical properties are investigated. For this purpose, a film gate mold was designed to inject composites in the shape of plates so that specimens in different directions to the flow could be evaluated. Observations from tensile tests were complemented by performing flexural tests (in different directions) on discs cut from the injected plates. SEM was used to qualitatively observe the fiber orientation in the composites. At high fiber content, both modulus and tensile strength could differ by as much as 40% along the flow and transverse to the flow. The fiber orientation was strongly increased at the highest fiber content, as concluded from theoretical analysis.

A new type of high reinforcement content clay–cellulose–thermoset nanocomposite is proposed, where epoxy precursors diffuse into a wet porous clay–nanocellulose mat, followed by curing. The processing concept was scaled to >200 μm thickness composites, the mechanical properties were high for nanocomposites, and the materials showed better tensile properties at 90% RH compared with typical nanocellulose materials. The nanostructure and phase distributions were studied using transmission electron microscopy; Young’s modulus, yield strength, ultimate strength, and ductility were determined as well as moisture sorption, fire retardancy, and oxygen barrier properties. Clay and cellulose contents were varied as well as the epoxy content. Epoxy had favorable effects on moisture stability and also improved reinforcement effects at low reinforcement content. A more homogeneous nano- and mesoscale epoxy distribution is still required for further property improvements. The materials constitute a new type of three-ph...

Wide-spread use of cellulose nanofibril (CNF) biocomposites and nanomaterials is limited by CNF moisture sensitivity due to surface hydration. We report on a versatile and scalable interface tailor ...

A critical aspect in materials design of polymer nanocomposites is the nature of the nanoparticle/polymer interface. The present study investigates the effect of manipulation of the interface between cellulose nanofibrils (CNF) and poly(methyl methacrylate) (PMMA) on the optical, thermal, and mechanical properties of the corresponding nanocomposites. The CNF/PMMA interface is altered with a minimum of changes in material composition so that interface effects can be analyzed. The hydroxyl-rich surface of CNF fibrils is exploited to modify the CNF surface via an epoxide-hydroxyl reaction. CNF/PMMA nanocomposites are then prepared with high CNF content (∼38 wt %) using an approach where a porous CNF mat is impregnated with monomer or polymer. The nanocomposite interface is controlled by either providing PMMA grafts from the modified CNF surface or by solvent-assisted diffusion of PMMA into a CNF network (native and modified). The high content of CNF fibrils of ∼6 nm diameter leads to a strong interface and polymer matrix distribution effects. Moisture uptake and mechanical properties are measured at different relative humidity conditions. The nanocomposites with PMMA molecules grafted to cellulose exhibited much higher optical transparency, thermal stability, and hygro-mechanical properties than the control samples. The present modification and preparation strategies are versatile and may be used for cellulose nanocomposites of other compositions, architectures, properties, and functionalities.

ACS nano 12(7), 6378 - 6388 (2018). doi:10.1021/acsnano.8b01084, Nanoscale building blocks of many materials exhibit extraordinary mechanical properties due to their defect-free molecular structure. Translation of these high mechanical properties to macroscopic materials represents a difficult materials engineering challenge due to the necessity to organize these building blocks into multiscale patterns and mitigate defects emerging at larger scales. Cellulose nanofibrils (CNFs), the most abundant structural element in living systems, has impressively high strength and stiffness, but natural or artificial cellulose composites are 3–15 times weaker than the CNFs. Here, we report the flow-assisted organization of CNFs into macroscale fibers with nearly perfect unidirectional alignment. Efficient stress transfer from macroscale to individual CNF due to cross-linking and high degree of order enables their Young’s modulus to reach up to 86 GPa and a tensile strength of 1.57 GPa, exceeding the mechanical properties of known natural or synthetic biopolymeric materials. The specific strength of our CNF fibers engineered at multiscale also exceeds that of metals, alloys, and glass fibers, enhancing the potential of sustainable lightweight high-performance materials with multiscale self-organization., Published by ACS, Washington, DC

Polyurethane (PU) nanocomposites utilizing cellulose nanocrystals (CNCs) as nanofiller and amorphous PU matrix were synthesized in a novel solvent-free bulk process. A green nanofiller, CNCs, was s ...

Free standing and strong odor-removing composite films of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite adsorbents have been colloidally processed. Thermogravimetric desorption analysis (TGA) and infrared spectroscopy combined with computational simulations showed that commercially available silicalite-1 and ZSM-5 have a high affinity and uptake of volatile odors like ethanethiol and propanethiol, also in the presence of water. The simulations showed that propanethiol has a higher affinity, up to 16%, to the two zeolites compared with ethanethiol. Highly flexible and strong free-standing zeolite-CNF films with an adsorbent loading of 89 w/w% have been produced by Ca-induced gelation and vacuum filtration. The CNF-network controls the strength of the composite films and 100 μm thick zeolite-CNF films with a CNF content of less than 10 vol % displayed a tensile strength approaching 10 MPa. Headspace solid phase microextraction (SPME) coupled to gas chromatography-mass spectroscopy (GC/MS) analysis showed that the CNF-zeolite films can eliminate the volatile thiol-based odors to concentrations below the detection ability of the human olfactory system. Odor removing zeolite-cellulose nanofibril films could enable improved transport and storage of fruits and vegetables rich in odors, for example, onion and the tasty but foul-smelling South-East Asian Durian fruit.

The morphology of polymer/nanofibrillated cellulose (NFC) composite sheets produced using different techniques and its influence on low strain stiffness were assessed by optical and transmission electron microscopy. Solvent processing led to relatively homogeneous NFC dispersions and significant reinforcement of the in-plane Young's modulus. The continuous cellular networks obtained by wet comingling of polylactide powder or latex with NFC also provided efficient and essentially scale independent reinforcement, in spite of the extensive agglomeration of the NFC. However, the irreversible nature of these networks is incompatible with low pressure thermoplastic processing routes such as physical foaming, and while they may be broken up by e.g. extrusion, this led to substantial loss in reinforcement, particularly at temperatures above the glass transition temperature of the matrix, consistent with the observation of isolated low aspect ratio NFC aggregates in the extruded specimens.

Nanocomposites with high volume fractions (15-50 vol%) of nanofibrillated cellulose (NFC) were prepared by impregnation of a wet porous NFC network with acetone/epoxy/amine solution. Infrared spectroscopy studies revealed a significant increase in curing rate of epoxy (EP) in the presence of NFC. The NFC provided extremely efficient reinforcement (at 15 vol%: 3-fold increase in stiffness and strength to 5.9 GPa and 109 MPa, respectively), and ductility was preserved. Besides, the glass transition temperature increased with increasing NFC content (from 68 degrees C in neat epoxy to 86 degrees C in 50 vol% composite). Most interestingly, the moisture sorption values were low and even comparable to neat epoxy for the 15 vol% NFC/EP. This material did not change mechanical properties at increased relative humidity (90% RH). Thus, NFC/EP provides a unique combination of high strength, modulus, ductility, and moisture stability for a cellulose-based biocomposite. Effects from nanostructural and interfacial tailoring are discussed. (C) 2014 The Authors. Published by Elsevier Ltd.

In this study, acetylated rye arabinoxylan (AcAX) films were reinforced with nanofibrillated cellulose from spruce (NFC) ranging from I to 10 wt% of the total composition. Free-standing composite films were casted without the use of any plasticizers. The homogeneous dispersion of NFC in the films was confirmed with scanning electron microscopy. The ultimate strength and the Young's modulus determined by tensile tests increased from 65 MPa and 2190 MPa for neat AcAX films to 93 MPa and 3360 MPa for the 10% composite films, respectively. The elongation to break of the 10% NFC composite film was a remarkable 10.5%. The moisture absorbed was still less than 8 wt% for the films with 10% NFC content at 97% relative humidity at room temperature, which is low for hemicellulose-based films. The addition of NFC decreased the water permeability of the films at low NFC contents, which was studied in diffusion cells using radioactive labeled water. Thus NFC can be used in an unmodified form as reinforcement in AcAX films to prepare films or coatings that are more water and humidity resistant than neat hemicellulose-based films. (C) 2014 Elsevier Ltd. All rights reserved.

The nanocellulose fibril is the major load-bearing component in the wood cell wall. It is readily disintegrated from wood pulp, and of great interest as a component in new materials. It can be used to form 100% cellulose nanofiber (CNF) nanopaper films or polymer matrix nanocomposite films of high cellulose content, where the CNF network controls most physical properties. Here, the uniaxial tensile properties of CNF nanopaper and composite films are discussed, together with the deformation mechanisms. The CNF network and most types of nanocomposite films are prepared by a scalable filtration process akin to paper-making. The effects of intrinsic CNF properties, degree of CNF dispersion, CNF–CNF adhesion, CNF-polymer matrix interaction, CNF orientation, and humidity are also discussed.

Polysaccharides guar galactomannan (guar gum), locust bean galactomannan (locust bean gum) and tamarind galactoxyloglucan were selectively oxidized by galactose oxidase. The degrees of oxidation of the products were 18–28% for guar galactomannan, 10–16% for locust bean galactomannan and 12–14% for tamarind galactoxyloglucan, calculated from the ratio of oxidized galactose units and total carbohydrates. The rheological properties of the unoxidized and oxidized polysaccharide solutions were investigated by determining their viscosities, storage and loss moduli, and temperature dependence of moduli from 20 °C to 90 °C. All the studied oxidized polysaccharides formed hydrogels throughout the entire temperature range. Concentration (0.2–1% w/v) and degree of oxidation had an effect on the gel formation. The oxidized galactomannans formed stable gels already in low concentrations, such as 0.2–0.4% w/v, while oxidized galactoxyloglucan required a concentration of 0.8% w/v to be stable up to 90 °C. The oxidized polysaccharide hydrogels are highly potential materials for food and medical applications requiring thermal stability.

In this work, the problem to disperse cellulose nanocrystals (CNC) in hydrophobic polymer matrices has been addressed through application of an environmentally friendly chemical modification approach inspired by clay chemistry. The objective is to compare the effects of unmodified CNC and modified CNC (modCNC) reinforcement, where degree of CNC dispersion is of interest. Hydrophobic functionalization made it possible to disperse wood-based modCNC in organic solvent and cast well-dispersed nanocomposite films of poly(vinyl acetate) (PVAc) with 1-20 wt % CNC. Composite films were studied by infrared spectroscopy (FT-IR), UV-vis spectroscopy, dynamic mechanical thermal analysis (DMTA), tensile testing, and field-emission scanning electron microscopy (FE-SEM). Strongly increased mechanical properties were observed for modCNC nanocomposites. The reinforcement efficiency was much lower in unmodified CNC composites, and specific mechanisms causing the differences are discussed.

Langerhans’ cell histocytosis (LCH), previously known as “histocytosis X”, is a rare disease of unknown etiology that includes a group of histologically similar but clinically different conditions, including solitary eosinophilic granuloma, Hand-Schuller-Christian disease and LettererSiwe disease. Lung involvement is a well-known complication of multi-system LCH, both in children and in adults. Isolated pulmonary LCH, on the other hand, has been reported in adults, especially cigarette smokers, but very rarely in children. In this report, we present a child with an unusual and rare isolated endobronchial pulmonary LCH. To our knowledge, this is the first case of isolated pulmonary LCH in a child to be reported from the Middle East.

Wandering spleen is a rare clinical condition that presents commonly with splenic infarction secondary to torsion. Intrauterine torsion of a wandering spleen, however, is extremely rare. An unusual case of intrauterine torsion of a wandering spleen presenting as an abdominal mass is reported.