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1.
Phys Chem Chem Phys ; 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38647047

RESUMO

Anodic aluminum oxide (AAO) membranes were used as templates to control orientation of an ion-channel forming columnar mesophase obtained by self assembly of a wedge-shaped sulfonate molecule. Inside the AAO structure, the director vector of the mesophase is oriented parallel to the pore axis due to the confinement effect. The molecular arrangement induced by the spatial confinement within the pores is extended over several microns into the remnant film on the AAO surface. The homeotropic alignment of the channels promotes unidimensional ion conduction through the film plane, which is manifested by a considerable increase in conductivity relative to isotropic samples.

2.
Int J Mol Sci ; 25(1)2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-38203772

RESUMO

Fluorinated proton-exchange membranes (PEMs) based on graft copolymers of dehydrofluorinated polyvinylidene fluoride (D-PVDF), 3-sulfopropyl acrylate (SPA), and 1H, 1H, 2H-perfluoro-1-hexene (PFH) were prepared via free radical copolymerization and characterized for fuel cell application. The membrane morphology and physical properties were studied via small-(SAXS) and wide-angle X-ray scattering (WAXS), SEM, and DSC. It was found that the crystallinity degree is 17% for PEM-RCF (co-polymer with SPA) and 16% for PEM-RCF-2 (copolymer with SPA and PFH). The designed membranes possess crystallite grains of 5-6 nm in diameter. SEM images reveal a structure with open pores on the surface of diameters from 20 to 140 nm. Their transport and electrochemical characterization shows that the lowest membrane area resistance (0.9 Ωcm2) is comparable to perfluorosulfonic acid PEMs (such as Nafion®) and polyvinylidene fluoride (PVDF) based CJMC cation-exchange membranes (ChemJoy Polymer Materials, China). Key transport and physicochemical properties of new and commercial membranes were compared. The PEM-RCF permeability to NaCl diffusion is rather high, which is due to a relatively low concentration of fixed sulfonate groups. Voltammetry confers that the electrochemical behavior of new PEM correlates to that of commercial cation-exchange membranes, while the ionic conductivity reveals an impact of the extended pores, as in track-etched membranes.


Assuntos
Alcenos , Polímeros de Fluorcarboneto , Polímeros , Polivinil , Prótons , Porosidade , Espalhamento a Baixo Ângulo , Difração de Raios X , Acrilatos
3.
Polymers (Basel) ; 16(2)2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38276704

RESUMO

Bottlebrush (BB) elastomers with water-soluble side chains and tissue-mimetic mechanical properties are promising for biomedical applications like tissue implants and drug depots. This work investigates the microstructure and phase transitions of BB elastomers with crystallizable polyethylene oxide (PEO) side chains by real-time synchrotron X-ray scattering. In the melt, the elastomers exhibit the characteristic BB peak corresponding to the backbone-to-backbone correlation. This peak is a distinct feature of BB systems and is observable in small- or medium-angle X-ray scattering curves. In the systems studied, the position of the BB peak ranges from 3.6 to 4.8 nm in BB elastomers. This variation is associated with the degree of polymerization of the polyethylene oxide (PEO) side chains, which ranges from 19 to 40. Upon crystallization of the side chains, the intensity of the peak decays linearly with crystallinity and eventually vanishes due to BB packing disordering within intercrystalline amorphous gaps. This behavior of the bottlebrush peak differs from an earlier study of BBs with poly(ε-caprolactone) side chains, explained by stronger backbone confinement in the case of PEO, a high-crystallinity polymer. Microstructural models based on 1D SAXS correlation function analysis suggest crystalline lamellae of PEO side chains separated by amorphous gaps of monolayer-like BB backbones.

4.
Arch Biochem Biophys ; 752: 109843, 2024 02.
Artigo em Inglês | MEDLINE | ID: mdl-38072298

RESUMO

Self-assembling nanoparticles (saNP) and nanofibers were found in the recombinant coronavirus SARS-CoV-2 S1, S2, RBD and N proteins purified by affinity chromatography using Ni Sepharose. Scanning electron (SEM), atomic force (AFM) microscopy on mica or graphite surface and in liquid as well as dynamic light scattering (DLS) revealed nanostructures of various sizes. AFM in liquid cell without drying on the surface showed mean height of S1 saNP 80.03 nm, polydispersity index (PDI) 0.006; for S2 saNP mean height 93.32 nm, PDI = 0.008; for N saNP mean height 16.71 nm, PDI = 0.99; for RBD saNP mean height 16.25 nm, PDI = 0.55. Ratios between the height and radius of each saNP in the range 0.1-0.5 suggested solid protein NP but not vesicles with internal empty spaces. The solid but not empty structures of the protein saNP were also confirmed by STEM after treatment of saNP with the standard contrasting agent uranyl acetate. The saNP remained stable after multiple freeze-thaw cycles in water and hyperosmotic solutions for 2 years at -20 °C. Receptor-mediated penetration of the SARS-CoV-2 S1 and RBD saNP in the African green mokey kidney Vero cells with the specific receptors for ß-coronavirus reproduction was more efficient compared to unspecific endocytosis into MDCK cells without the specific receptors. Amyloid-like structures were revealed in the SARS-CoV-2 S1, S2, RBD and N saNP by means of their interaction with Thioflavin T and Congo Red dyes. Taken together, spontaneous formation of the amyloid-like self-assembling nanostructures due to the internal affinity of the SARS-CoV-2 virion proteins might induce proteinopathy in patients, including conformational neurodegenerative diseases, change stability of vaccines and diagnostic systems.


Assuntos
COVID-19 , Nanoestruturas , Animais , Humanos , Chlorocebus aethiops , SARS-CoV-2 , Células Vero , Proteínas Recombinantes , Amiloide , Proteínas Amiloidogênicas
5.
Molecules ; 28(24)2023 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-38138492

RESUMO

This work presents the synthesis and self-organization of the calamitic fluorinated mesogen, 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-4-iodobutoxy)ethanesulfonic acid, a potential model for perfluorosulfonic acid membranes (PFSA). The compound is derived in three steps from 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride, achieving a 78% overall yield. The resulting compound exhibits intricate thermal behavior. At 150 °C, a crystal-to-crystal transition is observed due to the partial disordering of calamitic molecules, which is followed by isotropization at 218 °C. Upon cooling, sample ordering occurs through the formation of large smectic liquid crystalline phase domains. This thermotropic state transforms into a layered crystal phase at lower temperatures, characterized by alternating hydrophilic and hydrophobic layers. Using X-ray diffraction, crystalline unit cell models at both room temperature and 170 °C were proposed. Computer simulations of the molecule across varying temperatures support the idea that thermal transitions correlate with a loss of molecular orientation. Importantly, the study underscores the pivotal role of precursor self-organization in aligning channels during membrane fabrication, ensuring controlled and oriented positioning.

6.
Polymers (Basel) ; 15(21)2023 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-37959907

RESUMO

In this study, the use of anionic polymerization for the synthesis of living poly(dimethylsiloxane) or PDMS-Li+, as well as poly(2-vinylpyridine) or P2VP-Li+ homopolymers, and the subsequent use of chlorosilane chemistry in order for the two blocks to be covalently joined leading to PDMS-b-P2VP copolymers is proposed. High vacuum manipulations enabled the synthesis of well-defined materials with different molecular weights (Μ¯n, from 9.8 to 36.0 kg/mol) and volume fraction ratios (φ, from 0.15 to 0.67). The Μ¯n values, dispersity indices, and composition were determined through membrane/vapor pressure osmometry (MO/VPO), size exclusion chromatography (SEC), and proton nuclear magnetic resonance spectroscopy (1H NMR), respectively, while the thermal transitions were determined via differential scanning calorimetry (DSC). The morphological characterization results suggested that for common composition ratios, lamellar, cylindrical, and spherical phases with domain periodicities ranging from approximately 15 to 39 nm are formed. A post-polymerization chemical modification reaction to quaternize the nitrogen atom in some of the P2VP monomeric units in the copolymer with the highest P2VP content, and the additional characterizations through 1H NMR, infrared spectroscopy, DSC, and contact angle are reported. The synthesis, characterization, and quaternization of the copolymer structure are important findings toward the preparation of functional materials with enhanced properties suitable for various nanotechnology applications.

7.
Front Bioeng Biotechnol ; 11: 1254136, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37731767

RESUMO

In biotechnological processes, filamentous microorganisms are known for their broad product spectrum and complex cellular morphology. Product formation and cellular morphology are often closely linked, requiring a well-defined level of mechanical stress to achieve high product concentrations. Macroparticles were added to shake flask cultures of the filamentous actinomycete Lentzea aerocolonigenes to find these optimal cultivation conditions. However, there is currently no model concept for the dependence of the strength and frequency of the bead-induced stress on the process parameters. Therefore, shake flask simulations were performed for combinations of bead size, bead concentration, bead density and shaking frequency. Contact analysis showed that the highest shear stresses were caused by bead-bottom contacts. Based on this, a newly generated characteristic parameter, the stress area ratio (SAR), was defined, which relates the bead wall shear and normal stresses to the total shear area. Comparison of the SAR with previous cultivation results revealed an optimum pattern for product concentration and mean product-to-biomass related yield coefficient. Thus, this model is a suitable tool for future optimization, comparison and scaling up of shear-sensitive microorganism cultivation. Finally, the simulation results were validated using high-speed recordings of the bead motion on the bottom of the shake flask.

8.
Nat Mater ; 22(11): 1394-1400, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37749314

RESUMO

Our lives cannot be imagined without polymer networks, which range widely, from synthetic rubber to biological tissues. Their properties-elasticity, strain-stiffening and stretchability-are controlled by a convolution of chemical composition, strand conformation and network topology. Yet, since the discovery of rubber vulcanization by Charles Goodyear in 1839, the internal organization of networks has remained a sealed 'black box'. While many studies show how network properties respond to topology variation, no method currently exists that would allow the decoding of the network structure from its properties. We address this problem by analysing networks' nonlinear responses to deformation to quantify their crosslink density, strand flexibility and fraction of stress-supporting strands. The decoded structural information enables the quality control of network synthesis, comparison of targeted to actual architecture and network classification according to the effectiveness of stress distribution. The developed forensic approach is a vital step in future implementation of artificial intelligence principles for soft matter design.

9.
ACS Appl Mater Interfaces ; 15(35): 41870-41879, 2023 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-37625250

RESUMO

Hot-melt pressure-sensitive adhesives (HMPSAs) are used in applications from office supplies to biomedical adhesives. The major component in HMPSA formulations is thermoplastic elastomers, such as styrene-based block copolymers, that provide both mechanical integrity and moldability. Since neat polymer networks are unable to establish an adhesive bond, large quantities of plasticizers and tackifiers are added. These additives enhance the adhesive performance but complicate the phase behavior and property stability of the pressure-sensitive adhesive. Herein, we introduce an alternative additive-free approach to HMPSA design based on self-assembly of bottlebrush graft-copolymers, where side chains behave as softness, strength, and viscoelasticity mediators. These systems maintain moldability of conventional thermoplastic elastomers, while architecturally disentangled bottlebrush network strands empower several benefits such as extreme softness for substrate wetting, low melt viscosity for molding and 3D-printing, and a broad frequency range of viscoelastic responses for adhesion regulation within almost four orders of magnitude. The brush graft-copolymers implement five independently controlled architectural parameters to regulate the Rouse time, work of adhesion, and debonding mechanisms.

10.
Chemphyschem ; 24(21): e202300310, 2023 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-37560983

RESUMO

Conjugated small molecules are advanced semiconductor materials with attractive physicochemical and optoelectronic properties enabling the development of next-generation electronic devices. The charge carrier mobility of small molecules strongly influences the efficiency of organic and hybrid electronics based on them. Herein, we report the synthesis of four novel small molecules and their investigation with regard to the impact of molecular structure and thermal treatment of films on charge carriers' mobility. The benzodithiophene-containing compounds (BDT) were shown to be more promising in terms of tuning the morphology upon thermal treatment. Impressive enhancement of hole mobilities by more than 50 times was found for annealed films based on a compound M4 comprising triisopropylsilyl-functionalized BDT core. The results provide a favorable experience and strategy for the rational design of state-of-the-art organic semiconductor materials (OSMs) and for improving their charge-transport characteristics.

11.
Polymers (Basel) ; 15(6)2023 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-36987125

RESUMO

The design of new materials for non-contact temperature sensors is an important task for scientists working in the fields of chemistry, physics, and materials science. In the present paper, a novel cholesteric mixture based on a copolymer doped with a highly luminescent europium complex was prepared and studied. It was found that the spectral position of the selective reflection peak strongly depends on temperature and a shift towards shorter wavelengths is observed upon heating with an amplitude of more than 70 nm, from the red to green spectral range. This shift is associated with the existence and melting of clusters of smectic order, as confirmed by X-ray diffraction investigations. The extreme temperature dependence of the wavelength of selective light reflection provides a high thermosensitivity of the degree of circular polarization of the europium complex emission. The highest values of the dissymmetry factor are observed when the peak of selective light reflection fully overlaps with the emission peak. As a result, the highest sensitivity of 65%/K for luminescent thermometry materials was obtained. In addition, the ability of the prepared mixture to form stable coatings was demonstrated. The obtained experimental results, i.e., the high thermosensitivity of the degree of circular polarization, and the ability to form stable coatings allow us to consider the prepared mixture as a promising material for luminescent thermometry.

12.
ACS Cent Sci ; 9(2): 197-205, 2023 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-36844501

RESUMO

Pressure sensitive adhesives (PSAs) are ubiquitous materials within a spectrum that span from office supplies to biomedical devices. Currently, the ability of PSAs to meet the needs of these diverse applications relies on trial-and-error mixing of assorted chemicals and polymers, which inherently entails property imprecision and variance over time due to component migration and leaching. Herein, we develop a precise additive-free PSA design platform that predictably leverages polymer network architecture to empower comprehensive control over adhesive performance. Utilizing the chemical universality of brush-like elastomers, we encode work of adhesion ranging 5 orders of magnitude with a single polymer chemistry by coordinating brush architectural parameters-side chain length and grafting density. Lessons from this design-by-architecture approach are essential for future implementation of AI machinery in molecular engineering of both cured and thermoplastic PSAs incorporated into everyday use.

13.
Polymers (Basel) ; 15(4)2023 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-36850132

RESUMO

We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB1,2) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies. Furthermore, post-polymerization chemical modification reactions such as hydroboration and oxidation were carried out on the extremely low molecular weight PB1,2 in all three terpolymer samples. To justify the successful incorporation of -OH groups in the polydiene segments and the preparation of polymeric brushes, various molecular, thermal, and surface analysis measurements were carried out. The synthesis and chemical modification reactions on such triblock terpolymers are performed for the first time to the best of our knowledge and constitute a promising route to design polymers for nanotechnology applications.

14.
Materials (Basel) ; 16(2)2023 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-36676555

RESUMO

A series of semi-crystalline multi-block thermoplastic polyurethanes (TPU), containing poly(butylene adipate) (PBA), polycaprolactone (PCL) and their equimolar mixture (PBA/PCL) as a soft segment was synthesized. The changes in the physical-mechanical and thermal properties of the materials observed in the course of a 36-month storage at room temperature were related to the corresponding structural evolution. The latter was monitored using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXS) and mechanical tests (tensile strength test). The effects of the composition of the soft segment on the phase separation and crystallization of the soft segment were analyzed in detail. It was found that the melting temperature of the crystalline phase increases with storage time, which is associated with hindering of the phase separation of the hard and soft segments of the TPU samples as it was detected by FTIR.

15.
Polymers (Basel) ; 14(23)2022 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-36501686

RESUMO

In this study the preparation of hybrid materials based on reduced graphene oxide (rGO) and conjugated copolymers is reported. By tuning the number and arrangement of thiophenes in the main chain (indacenothiophene or indacenothienothiophene) and the nature of the polymer acceptor (difluoro benzothiadiazole or diketopyrrolopyrrole) semiconducting copolymers were synthesized through Stille aromatic coupling and characterized to determine their molecular characteristics. The graphene oxide was synthesized using the Staudenmaier method and was further modified to reduced graphene oxide prior to structural characterization. Various mixtures with different rGO quantities and conjugated copolymers were prepared to determine the optoelectronic, thermal and morphological properties. An increase in the maximum absorbance ranging from 3 to 6 nm for all hybrid materials irrespective of the rGO concentration, when compared to the pristine conjugated copolymers, was estimated through the UV-Vis spectroscopy indicating a differentiation on the optical properties. Through voltammetric experiments the oxidation and reduction potentials were determined and the calculated HOMO and LUMO levels revealed a decrease on the electrochemical energy gap for low rGO concentrations. The study indicates the potential of the hybrid materials consisting of graphene oxide and high band gap conjugated copolymers for applications related to organic solar cells.

16.
Mater Horiz ; 9(12): 3022-3030, 2022 11 28.
Artigo em Inglês | MEDLINE | ID: mdl-36128881

RESUMO

Polymeric networks are commonly used for various biomedical applications, from reconstructive surgery to wearable electronics. Some materials may be soft, firm, strong, or damping however, implementing all four properties into a single material to replicate the mechanical properties of tissue has been inaccessible. Herein, we present the A-g-B brush-like graft copolymer platform as a framework for fabrication of materials with independently tunable softness and firmness, capable of reaching a strength of ∼10 MPa on par with stress-supporting tissues such as blood vessel, muscle, and skin. These properties are maintained by architectural control, therefore diverse mechanical phenotypes are attainable for a variety of different chemistries. Utilizing this attribute, we demonstrate the capability of the A-g-B platform to enhance specific characteristics such as tackiness, damping, and moldability.


Assuntos
Elastômeros , Polímeros , Eletrônica
17.
ACS Macro Lett ; 11(9): 1085-1090, 2022 09 20.
Artigo em Inglês | MEDLINE | ID: mdl-35998353

RESUMO

Brush-like elastomers with crystallizable side chains hold promise for biomedical applications requiring the presence of two distinct mechanical states below and above body temperature: hard and supersoft. The hard semicrystalline state facilitates piercing of the body whereupon the material softens to match the mechanics of surrounding soft tissue. To understand the transition between the two states, the crystallization process was studied with synchrotron X-ray scattering for a series of brush elastomers with poly(ε-caprolactone) side chains bearing from 7 to 13 repeat units. The so-called bottlebrush correlation peak was used to monitor configuration of bottlebrush backbones in the amorphous regions during the crystallization process. In the course of crystallization, the backbones are expelled into the interlamellar amorphous gaps, which is accompanied by their conformational changes and leads to partitioning to unconfined (melt) and confined (semicrystalline) (conformational) states. The crystallization process starts by consumption of the unconfined macromolecules by the growing crystals followed by reconfiguration of macromolecules within the already grown spherulites.


Assuntos
Elastômeros , Polímeros , Cristalização , Conformação Molecular , Polímeros/química , Temperatura
18.
Phys Chem Chem Phys ; 24(26): 16041-16049, 2022 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-35731226

RESUMO

Crystalline and liquid-crystalline conjugated small molecules represent a promising family of semiconductor materials for organic electronics applications. The control of the morphology and optoelectronic properties of small molecules allows tuning their charge transport characteristics and hence, improving the performance of electronic devices. Here, we designed four pentamers based on alternating thiophene and benzothiadiazole moieties and investigated the effect of their structure on the optoelectronic properties, ordering and charge transport characteristics. It is shown that thermal annealing of conjugated pentamers leads to remarkable changes in the microstructure and domain texture of thin films. As a result, an increase in hole mobility for compound M4 by one order of magnitude was achieved. These findings provide a valuable insight into the structure-property relationships for designed small molecules featuring them as promising semiconductor materials for further developing high-performance organic electronics.

19.
J Crit Care ; 70: 154047, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-35490503

RESUMO

PURPOSE: Low tidal volume ventilation (LTVV) is associated with mortality in patients with acute respiratory distress syndrome. We investigated the association of LTVV with mortality in COVID-19 patients. METHODS: Secondary analysis of a national observational study in COVID-19 patients in the first wave of the pandemic. We compared COVID-19 patients that received LTVV, defined as controlled ventilation with a median tidal volume ≤ 6 mL/kg predicted body weight over the first 4 calendar days of ventilation, with patients that did not receive LTVV. The primary endpoint was 28-day mortality. In addition, we identified factors associated with use of LTVV. RESULTS: Of 903 patients, 294 (32.5%) received LTVV. Disease severity scores and ARDS classification was not different between the two patient groups. The primary endpoint, 28-day mortality, was met in 68 out of 294 patients (23.1%) that received LTVV versus in 193 out of 609 patients (31.7%) that did not receive LTVV (P < 0.001). LTVV was independently associated with 28-day mortality (HR, 0.68 (0.45 to 0.95); P = 0.025). Age, height, the initial tidal volume and continuous muscle paralysis was independently associated with use of LTVV. CONCLUSIONS: In this cohort of invasively ventilated COVID-19 patients, approximately a third of patients received LTVV. Use of LTVV was independently associated with reduced 28-day mortality. The initial tidal volume and continuous muscle paralysis were potentially modifiable factors associated with use of LTVV. These findings are important as they could help clinicians to recognize patients who are at risk of not receiving LTVV.


Assuntos
COVID-19 , Síndrome do Desconforto Respiratório , COVID-19/terapia , Humanos , Unidades de Terapia Intensiva , Paralisia , Respiração Artificial , Síndrome do Desconforto Respiratório/terapia , Volume de Ventilação Pulmonar/fisiologia
20.
Int J Cosmet Sci ; 44(3): 343-362, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35478184

RESUMO

OBJECTIVE: The cuticle of human hair has been examined, via a range of analytical methods, in order to reveal previously unknown information about its structure and to deepen understanding of its contribution to fibre properties. METHODS: Cross-sections of hair fibre have been examined with X-ray microdiffraction oriented perpendicular to the surface of the cross-sections. AFM investigations were carried out for further investigating and deciphering the structure of the cuticle. Moisture sorption analytics of cuticle separated from fibre and mechanical tests of decuticled fibres against virgin fibres were used for understanding the role of the cuticle in the economy of hair fibre. RESULTS: Previously unknown swelling behaviour of the hair cuticle during moisture sorption has been revealed, as has an increased significance of the cuticle's role in moisture management at higher values of relative humidity. Through AFM investigation, the reaction of hair cuticles with chlorine water has further strengthened the idea that the Allwörden membrane does not exist, and is actually an artefact of the delamination of the A-layer and exocuticle from the underlying endocuticle. Using decuticled fibres for stress-strain tests, and by comparing the results with those of virgin fibres, the effect of the cuticle on the post-yield area of the hair fibre stress-strain diagram has also been demonstrated. Finally, X-ray microdiffraction and AFM investigations suggest that the cuticle possesses a small-scale ordered structure, based on possibly not fully crystalline and irregularly arranged α-helices oriented almost perpendicular to the growth axis of the fibre and enhancing the general description of cuticle as the protective layer of the fibre. CONCLUSION: The role of the cuticle for the hair fibre is more complex than previously thought. The cuticle is demonstrated not only to possess a hidden rod-matrix structure, that supports its protective nature, but also to play specific roles in the fibre's response to moisture, and in fibre mechanical behaviour.


OBJECTIF : la cuticule des cheveux humains a été examinée à l'aide d'un ensemble de méthodes analytiques, afin de révéler des informations jusqu'alors inconnues sur sa structure et d'approfondir la compréhension de son rôle dans les propriétés de la fibre. MÉTHODES : des coupes transversales de fibres capillaires ont été examinées par microdiffraction radiographique orientée perpendiculairement à la surface des coupes. Des expérimentations par AFM ont été réalisées pour approfondir les recherches et découvrir la structure de la cuticule. Des analyses d'absorption de l'humidité de la cuticule séparée de la fibre et des tests mécaniques des fibres décuticulées par rapport aux fibres vierges ont été utilisés pour comprendre le rôle de la cuticule dans la préservation de la fibre capillaire. RÉSULTATS : un comportement de gonflement jusqu'alors inconnu de la cuticule des cheveux durant l'absorption de l'humidité a été révélé, de même qu'une importance accrue du rôle de la cuticule dans la gestion de l'humidité à des valeurs plus élevées d'humidité relative. À l'aide des expérimentations par AFM, la réaction de la cuticule des cheveux avec de l'eau chlorée a à nouveau renforcé l'idée selon laquelle la membrane d'Allwörden n'existe pas et est en réalité un artéfact de délaminage de la couche A et de l'exocuticule provenant de l'endocuticule sous-jacente. L'utilisation de fibres décuticulées pour des tests de contrainte et la comparaison des résultats avec ceux de fibres vierges ont également démontré l'effet de la cuticule sur la zone post-rendement du diagramme de contrainte de la fibre capillaire. Enfin, les expérimentations par microdiffraction radiographique et AFM suggèrent que la cuticule possède une structure ordonnée à petite échelle, basée sur des hélices alpha potentiellement non entièrement cristallines et disposées de manière irrégulière, orientées presque perpendiculairement à l'axe de croissance de la fibre, améliorant la description générale de la cuticule comme couche protectrice de la fibre. CONCLUSION : le rôle de la cuticule pour la fibre capillaire est plus complexe qu'on ne le pensait. Il a été démontré que la cuticule possède non seulement une structure rod-matrix cachée, qui maintient sa nature protectrice, mais joue également des rôles spécifiques dans la réponse de la fibre à l'humidité et dans son comportement mécanique.


Assuntos
Cabelo , Água , Cabelo/química , Humanos
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