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1.
Polymers (Basel) ; 16(17)2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39274154

RESUMO

This study investigates hydrogels based on 2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) copolymers, incorporating N-hydroxyethyl acrylamide (HEA) and 3-sulfopropyl acrylate potassium salt (SPA). The addition of HEA and SPA is designed to fine-tune the hydrogels' water absorption and mechanical properties, ultimately enhancing their characteristics and expanding their potential for biomedical applications. A copolymer of AMPS, 2-carboxyethyl acrylate (CEA) combined with methacrylic acid (MAA) as poly(AMPS-stat-CEA-stat-MAA, PACM), was preliminarily synthesized. CEA and MAA were modified with allyl glycidyl ether (AGE) through ring-opening, yielding macromers with pendant allyl groups (PACM-AGE). Copolymers poly(AMPS-stat-HEA-stat-CEA-stat-MAA) (PAHCM) and poly(AMPS-stat-SPA-stat-CEA-stat-MAA) (PASCM) were also synthesized and modified with AGE to produce PAHCM-AGE and PASCM-AGE macromers. These copolymers and macromers were characterized by 1H NMR, FT-IR, and GPC, confirming successful synthesis and functionalization. The macromers were then photocrosslinked into hydrogels and evaluated for swelling, water content, and mechanical properties. The results revealed that the PASCM-AGE hydrogels exhibited superior swelling ratios and water retention, achieving equilibrium water content (~92%) within 30 min. While the mechanical properties of HEA and SPA containing hydrogels show significant differences compared to PACM-AGE hydrogel (tensile strength 2.5 MPa, elongation 47%), HEA containing PAHCM-AGE has a higher tensile strength (5.8 MPa) but lower elongation (19%). In contrast, SPA in the PASCM-AGE hydrogels led to both higher tensile strength (3.7 MPa) and greater elongation (92%), allowing for a broader range of hydrogel properties. An initial study on drug delivery behavior was conducted using PACM-AGE hydrogels loaded with photosensitizers, showing effective absorption, release, and antibacterial activity under light exposure. These AMPS-based macromers with HEA and SPA modifications demonstrate enhanced properties, making them promising for wound management and drug delivery applications.

2.
Int J Biol Macromol ; 262(Pt 1): 129967, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38316324

RESUMO

MXenes, synthesized from their precursor MAX phases, have been extensively researched as additives to enhance the drug delivery performance of polymer matrices, whereas there is a limited number of previous reports on the use of MAX phases themselves for such applications. The use of MAX phases can exclude the complicated synthesis procedure and lessen resultant production and environmental costs required to convert MAX phases to MXenes. Herein, electrospun membranes of poly(lactic acid) (PLA) and a MAX phase (Ti3AlC2) have been fabricated for curcumin delivery. The composite membrane exhibits significantly higher toughness (8.82 MJ m-3) than the plasticized PLA membrane (0.63 MJ m-3) with low cytotoxicity, supporting proliferation of mouse fibroblast L929 cells. The curcumin-loaded composite membrane exhibits high water vapor transmission (∼7350 g m-2 day-1), porosity (∼85 %), water wettability, and antibacterial properties against E. coli and S. aureus. Seven-day curcumin release is enhanced from 45 % (PLA) to 67 % (composite) due to curcumin diffusion from the polymer fibers and MAX phase surface that contributes to overall increased curcumin adsorption and release sites. This work demonstrates the potential of the MAX phase to enhance both properties and curcumin delivery, promising for other eco-friendly systems for sustainable drug delivery applications.


Assuntos
Curcumina , Animais , Camundongos , Curcumina/farmacologia , Staphylococcus aureus , Escherichia coli , Titânio , Poliésteres , Antibacterianos/farmacologia , Polímeros
3.
Artif Cells Nanomed Biotechnol ; 51(1): 192-204, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37052886

RESUMO

Bee propolis has been used in alternative medicine to treat various diseases. Due to its limited water solubility, it is often used in combination with alcohol solvents, causing skin irritation and immune response. To solve this, the new drug delivery system, based on the lipid nanodiscs of 1,2-dimyristoyl-sn-glycero-3-phosphochline (DMPC) and poly(styrene-alt-maleic acid) (PSMA), were created in an aqueous media. At the excess polymer concentrations, the PSMA/DMPC complexation produced the very fine nanoparticles (18 nm). With the increased molar ratio of styrene to maleic acid (St/MA) in the copolymer structure, the lipid nanodisc showed the improved encapsulation efficiency (EE%), comparing to their corresponding aqueous formulations. The maximum value had reached to around 20% when using the 2:1 PSMA precursor. Based on the cytotoxicity test, these nanoparticles were considered to be non-toxic over the low dose administration region (<78 µg/mL). Instead, they possessed the ability to promote the Vero cell growth. The new PSMA/DMPC nanovesicles could thus be used to improve aqueous solubility and therapeutic effects of poorly water-soluble drugs, thus extending their use in modern therapies.


New biomimetic approach for propolis encapsulation was developed with no use of organic solvent.Propolis antioxidants were recovered directly into water-soluble formats.The very fine lipid nanodiscs showed impressive shelf-life stability and tuneable drug-loading capacity.


Assuntos
Própole , Própole/farmacologia , Dimiristoilfosfatidilcolina/química , Poliestirenos/química , Maleatos/química , Polímeros/química , Água
4.
Polymers (Basel) ; 15(2)2023 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-36679184

RESUMO

Ternary-blended, melt-blown films of polylactide (PLA), polycaprolactone (PCL) and cellulose acetate butyrate (CAB) were prepared from preliminary miscibility data using a rapid screening method and optical ternary phase diagram (presented as clear, translucent, and opaque regions) as a guide for the composition selection. The compositions that provided optically clear regions were selected for melt blending. The ternary (PLA/PCL/CAB) blends were first melt-extruded and then melt-blown to form films and characterized for their tensile properties, tensile fractured-surface morphology, miscibility, crystallinity, molecular weight and chemical structure. The results showed that the tensile elongation at the break (%elongation) of the ternary-blended, melt-blown films (85/5/10, 75/10/15, 60/15/25 of PLA/PCL/CAB) was substantially higher (>350%) than pure PLA (ca. 20%). The range of compositions in which a significant increase in %elongation was observed at 55−85% w/w PLA, 5−20% w/w PCL and 10−25% w/w CAB. Films with high %elongation all showed good interfacial interactions between the dispersed phase (PCL and CAB) and matrix (PLA) in FE-SEM and showed improvements in miscibility (higher intermolecular interaction and mixing) and a decrease in the glass transition temperature, when compared to the low %elongation films. The decrease in Mw and Mn and the formation of the new NMR peaks (1H NMR at 3.68−3.73 ppm and 13C NMR at 58.54 ppm) were observed in only the high %elongation films. These are expected to be in situ compatibilizers that are generated during the melt processing, mostly by chain scission. In addition, mathematical modelling was used to study the optimal ratio and cost-effectiveness of blends with optimised mechanical properties. These ternary-blended, melt-blown films have the potential for use in both packaging and medical devices with excellent mechanical performance as well as inherent economic and environmental capabilities.

5.
Biomacromolecules ; 23(11): 4532-4546, 2022 11 14.
Artigo em Inglês | MEDLINE | ID: mdl-36169096

RESUMO

The efficiency of nerve guide conduits (NGCs) in repairing peripheral nerve injury is not high enough yet to be a substitute for autografts and is still insufficient for clinical use. To improve this efficiency, 3D electrospun scaffolds (3D/E) of poly(l-lactide-co-ε-caprolactone) (PLCL) and poly(l-lactide-co-glycolide) (PLGA) were designed and fabricated by the combination of 3D printing and electrospinning techniques, resulting in an ideal porous architecture for NGCs. Polypyrrole (PPy) was deposited on PLCL and PLGA scaffolds to enhance biocompatibility for nerve recovery. The designed pore architecture of these "PLCL-3D/E" and "PLGA-3D/E" scaffolds exhibited a combination of nano- and microscale structures. The mean pore size of PLCL-3D/E and PLGA-3D/E scaffolds were 289 ± 79 and 287 ± 95 nm, respectively, which meets the required pore size for NGCs. Furthermore, the addition of PPy on the surfaces of both PLCL-3D/E (PLCL-3D/E/PPy) and PLGA-3D/E (PLGA-3D/E/PPy) led to an increase in their hydrophilicity, conductivity, and noncytotoxicity compared to noncoated PPy scaffolds. Both PLCL-3D/E/PPy and PLGA-3D/E/PPy showed conductivity maintained at 12.40 ± 0.12 and 10.50 ± 0.08 Scm-1 for up to 15 and 9 weeks, respectively, which are adequate for the electroconduction of neuron cells. Notably, the PLGA-3D/E/PPy scaffold showed superior cytocompatibility when compared with PLCL-3D/E/PPy, as evident via the viability assay, proliferation, and attachment of L929 and SC cells. Furthermore, analysis of cell health through membrane leakage and apoptotic indices showed that the 3D/E/PPy scaffolds displayed significant decreases in membrane leakage and reductions in necrotic tissue. Our finding suggests that these 3D/E/PPy scaffolds have a favorable design architecture and biocompatibility with potential for use in peripheral nerve regeneration applications.


Assuntos
Polímeros , Pirróis , Engenharia Tecidual/métodos , Poliésteres , Impressão Tridimensional , Alicerces Teciduais
6.
Soft Matter ; 17(45): 10286-10293, 2021 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-34151919

RESUMO

We determine how low frequency vibrational modes control the elastic shear modulus of Mikado networks, a minimal mechanical model for semi-flexible fiber networks. From prior work it is known that when the fiber bending modulus is sufficiently small, (i) the shear modulus of 2D Mikado networks scales as a power law in the fiber line density, G ∼ ρα+1, and (ii) the networks also possess an anomalous abundance of soft (low-frequency) vibrational modes with a characteristic frequency ωκ ∼ ρß/2. While it has been suggested that α and ß are identical, the preponderance of evidence indicates that α is larger than theoretical predictions for ß. We resolve this inconsistency by measuring the vibrational density of states in Mikado networks for the first time. Supported by these results, we then demonstrate analytically that α = ß + 1. In so doing, we uncover new insights into the coupling between soft modes and shear, as well as the origin of the crossover from bending- to stretching-dominated response.

7.
Biomed Phys Eng Express ; 7(4)2021 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-33930887

RESUMO

The potential of naturally occurring substances as a source of biomedical materials is well-recognised and is being increasingly exploited. Silk fibroin membranes derived fromBombyx morisilk cocoons exemplify this, for example as substrata for the growth of ocular cells with the aim of generating biomaterial-cell constructs for tissue engineering. This study investigated the transport properties of selected silk fibroin membranes under conditions that allowed equilibrium hydration of the membranes to be maintained. The behaviour of natural fibroin membranes was compared with fibroin membranes that have been chemically modified with poly(ethylene glycol). The permeation of the smaller hydrated sodium ion was higher than that of the hydrated calcium ion for all three ethanol treated membranes investigated. The PEG and HRP-modified C membrane, which had the highest water content at 59.6 ± 1.5% exhibited the highest permeation of the three membranes at 95.7 ± 2.8 × 10-8cm2s-1compared with 17.9 ± 0.9 × 10-8cm2s-1and 8.7 ± 1.7 × 10-8cm2s-1for membranes A and B respectively for the NaCl permeant. Poly(ethylene glycol) was used to increase permeability while exploiting the crosslinking capabilities of horseradish peroxidase to increase the compressive strength of the membrane. Importantly, we have established that the permeation behaviour of water-soluble permeants with hydrated radii in the sub-nanometer range is analogous to that of conventional hydrogel polymers.


Assuntos
Fibroínas/química , Materiais Biocompatíveis , Peroxidase do Rábano Silvestre , Membranas , Polietilenoglicóis , Água
8.
J Biomed Mater Res B Appl Biomater ; 109(1): 137-148, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-32710466

RESUMO

The importance of the microstzructure of silicone hydrogels is widely appreciated but is poorly understood and minimally investigated. To ensure comfort and eye health, these materials must simultaneously exhibit both high oxygen and high water permeability. In contrast with most conventional hydrogels, the water content and water structuring within silicone hydrogels cannot be solely used to predict permeability. The materials achieve these opposing requirements based on a composite of nanoscale domains of oxygen-permeable (silicone) and water-permeable hydrophilic components. This study correlated characteristic ion permeation coefficients of a selection of commercially available silicone hydrogel contact lenses with their morphological structure and chemical composition. Differential scanning calorimetry measured the water structuring properties through subdivision of the freezing water component into polymer-associated water (loosely bound to the polymer matrix) and ice-like water (unimpeded with a melting point close to that of pure water). Small-angle x-ray scattering, and environmental scanning electron microscopy techniques were used to investigate the structural morphology of the materials over a range of length scales. Significant, and previously unrecognized, differences in morphology between individual materials at nanometer length scales were determined; this will aid the design and performance of the next generation of ocular biomaterials, capable of maintaining ocular homeostasis.


Assuntos
Materiais Biocompatíveis/química , Hidrogéis/química , Silicones/química , Lentes de Contato Hidrofílicas , Desenho de Equipamento , Humanos , Interações Hidrofóbicas e Hidrofílicas , Teste de Materiais , Oxigênio , Permeabilidade , Água
9.
Phys Rev Lett ; 124(11): 118001, 2020 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-32242697

RESUMO

We numerically investigate stress relaxation in soft athermal disks to reveal critical slowing down when the system approaches the jamming point. The exponents describing the divergence of the relaxation time differ dramatically depending on whether the transition is approached from the jammed or unjammed phase. This contrasts sharply with conventional dynamic critical scaling scenarios, where a single exponent characterizes both sides. We explain this surprising difference in terms of the vibrational density of states, which is a key ingredient of linear viscoelastic theory. The vibrational density of states exhibits an extra slow mode that emerges below jamming, which we utilize to demonstrate the anomalous exponent below jamming.

10.
Biochim Biophys Acta Biomembr ; 1862(7): 183281, 2020 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-32209303

RESUMO

The use of styrene maleic acid co-polymer (SMA) for membrane protein extraction and purification has grown in recent years. SMA inserts in the membrane and assembles into small discs of bilayer encircled by polymer, termed SMA lipid particles (SMALPs). This allows purification of membrane proteins whilst maintaining their lipid bilayer environment. SMALPs offer several improvements over conventional detergent approaches, however there are limitations, most notably a sensitivity to low pH and divalent cations. Recently it was shown that the aliphatic diisobutylene-maleic acid (DIBMA) copolymer, was also able to directly solubilise membranes forming DIBMALPs (DIBMA lipid particles), and that this polymer overcame some of the limitations of SMA. In this study the ability of DIBMA to solubilise and purify functional membrane proteins has been compared to SMA. It was found that DIBMA is able to solubilise several different membrane proteins from different expression systems, however for some proteins it gives a lower yield and lower degree of purity than SMA. DIBMA extracted G protein-coupled receptors retain ligand- and G protein-binding. DIBMALPS are larger than SMALPs and display a decreased sensitivity to magnesium. However the stability of DIBMALPs appears to be lower than SMALPs. The lower purity and lower stability are likely linked to the larger size of the DIBMALP particle. However, this also offers a potentially less rigid lipid environment which may be more amenable to protein dynamics. Therefore the optimal choice of polymer will depend on which features of a protein are to be investigated.


Assuntos
Bicamadas Lipídicas/isolamento & purificação , Maleatos/química , Proteínas de Membrana/isolamento & purificação , Poliestirenos/química , Alcenos/química , Bicamadas Lipídicas/química , Gotículas Lipídicas/química , Proteínas de Membrana/química
11.
Br J Ophthalmol ; 104(7): 1028-1032, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-31079054

RESUMO

BACKGROUND: Tear film stability is important for healthy visual function, and yet little is known of the ageing mechanisms. The aim of this study was to investigate parallels between biochemical changes and clinical physical parameters, which occur in the tear film of two subject populations differing in age by over 30 years. METHODS: Two distinct age groups were chosen: 11 'younger' (23.7±2.1 years) and 19 'older' (63.0±4.0 years) subjects. A series of clinical tests were performed to access tear volume, tear film stability and general ocular health. Tear protein analyses from extracted Schirmer strips were conducted with the Agilent 2100 Bioanalyzer. RESULTS: Clinical investigations highlighted significant differences between the age groups. For example: McMonnies scores (p=0.009) and bulbar redness (p=0.038) were higher for the older group, whereas tear meniscus height was larger (p=0.018) in the younger group. Similarly, relative plasma-derived albumin levels were higher (17.1%±12.4%) in the tears of the older, compared with the younger (5.0%±9.6%) group. A protein peak at ∼23 kDa was observed in 53% of the older group samples but in only 36% of the samples of the younger subjects (p=0.122). CONCLUSIONS: Distinct differences in tear film composition between the two age groups were observed. Parallels in terms of clinical symptoms which reflected a biochemical response (and vice versa) were found, but specific correlations between clinical measurements and biomarkers for individual subjects were not observed.


Assuntos
Envelhecimento/fisiologia , Proteínas do Olho/metabolismo , Lágrimas/fisiologia , Idoso , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Concentração Osmolar , Projetos Piloto , Inquéritos e Questionários , Lágrimas/química , Adulto Jovem
12.
Phys Rev Lett ; 122(18): 188001, 2019 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-31144889

RESUMO

We numerically investigate nonlocal effects on inhomogeneous flows of soft athermal disks close to but below their jamming transition. We employ molecular dynamics to simulate Kolmogorov flows, in which a sinusoidal flow profile with fixed wave number is externally imposed, resulting in a spatially inhomogeneous shear rate. We find that the resulting rheology is strongly wave-number-dependent, and that particle migration, while present, is not sufficient to describe the resulting stress profiles within a conventional local model. We show that, instead, stress profiles can be captured with nonlocal constitutive relations that account for gradients to fourth order. Unlike nonlocal flow in yield stress fluids, we find no evidence of a diverging length scale.

13.
Proc Natl Acad Sci U S A ; 116(14): 6560-6568, 2019 04 02.
Artigo em Inglês | MEDLINE | ID: mdl-30894489

RESUMO

We present an approach to understand geometric-incompatibility-induced rigidity in underconstrained materials, including subisostatic 2D spring networks and 2D and 3D vertex models for dense biological tissues. We show that in all these models a geometric criterion, represented by a minimal length [Formula: see text], determines the onset of prestresses and rigidity. This allows us to predict not only the correct scalings for the elastic material properties, but also the precise magnitudes for bulk modulus and shear modulus discontinuities at the rigidity transition as well as the magnitude of the Poynting effect. We also predict from first principles that the ratio of the excess shear modulus to the shear stress should be inversely proportional to the critical strain with a prefactor of 3. We propose that this factor of 3 is a general hallmark of geometrically induced rigidity in underconstrained materials and could be used to distinguish this effect from nonlinear mechanics of single components in experiments. Finally, our results may lay important foundations for ways to estimate [Formula: see text] from measurements of local geometric structure and thus help develop methods to characterize large-scale mechanical properties from imaging data.

14.
J Biomed Mater Res B Appl Biomater ; 107(6): 1997-2005, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-30566286

RESUMO

The health of the cornea is paramount; the aim of this study was to assess the permeation of essential tear electrolytes through a range of commercial contact lenses. Donor/receiver conductivity measurements were recorded using a dual-chamber diffusion system which allowed material permeability profiles and coefficients to be calculated. Water structuring properties of the contact lenses were measured by differential scanning calorimetry. Freezing water was subdivided into "ice-like" water (free, non-bound and has a melting point close to that of pure water) and polymer-associated water (free but loosely bound to the polymer matrix). Each material interacts differently with each of the three salts, for example; lotrafilcon B (34% equilibrium water content [EWC]) shows a higher and larger range of receiver concentrations post KCl, NaCl, CaCl2 permeation (76, 59 and 42 mM, respectively) compared with the lower and tighter range exhibited by lotrafilcon A (22% EWC) (36, 22, and 18 mM, respectively). Additionally, in terms of the relationship between permeation and water structure, balafilcon A (34% EWC) has a high KCl permeation (P60 258 × 10-8 cm2 /s) and ice-like water (14%), but narafilcon A (44% EWC) has a low ion permeation (P60 3.9 × 10-8 cm2 /s) and significantly less ice-like water (4%). The permeation trends for the silicone hydrogel materials could not be fully explained by water content and structuring. Composition and, in particular, the microstructure and morphology of these materials must impart a greater influence on permeation capability. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1997-2005, 2019.


Assuntos
Lentes de Contato Hidrofílicas , Eletrólitos/química , Humanos , Permeabilidade
15.
J Biomed Mater Res B Appl Biomater ; 107(5): 1645-1653, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30296363

RESUMO

This paper presents three families of semi-interpenetrating polymer network (SIPN) hydrogels based on an ester-based polyurethane (EBPU) and hydrophilic monomers: N,N-dimethylacrylamide (NNDMA), N-vinyl pyrrolidone (NVP) and acryloylmorpholine (AMO) as potential materials for keratoprosthesis, orthokeratology and mini-scleral lens application. Hydrogels sheets were synthesized via free-radical polymerization with methods developed in-house. SIPN hydrogels were characterized for their equilibrium water content, mechanical and surface properties. Three families of optically clear SIPN-based hydrogels have been synthesized in the presence of water with >10% of composition attributable to EBPU. Water contents of SIPN materials ranged from 30% to 70%. SIPNs with ≤15% EBPU of total composition showed little influence to mechanical properties, whereas >15% EBPU contributed significantly to an increase in material stiffness. In the hydrated state, SIPNs with ≤15% EBPU of total composition show little difference in polar component (γp ) of surface free energy, whereas for >15% EBPU there is a decrease in γp . The EBPU SIPN hydrogels display complementary material properties for keratoprosthesis, orthokeratology, and mini-scleral applications. © 2018 The Authors. Journal of Biomedical Materials Research Part B: Applied Biomaterials published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1645-1653, 2019.


Assuntos
Materiais Biocompatíveis/síntese química , Materiais Revestidos Biocompatíveis/síntese química , Hidrogéis/síntese química , Poliuretanos/síntese química , Acrilamidas/química , Resinas Acrílicas/síntese química , Administração Oftálmica , Materiais Biocompatíveis/administração & dosagem , Materiais Revestidos Biocompatíveis/administração & dosagem , Humanos , Hidrogéis/administração & dosagem , Interações Hidrofóbicas e Hidrofílicas , Fenômenos Mecânicos , Estrutura Molecular , Polietilenotereftalatos/química , Poliuretanos/administração & dosagem , Pirrolidinonas/química , Relação Estrutura-Atividade , Propriedades de Superfície , Água
16.
Phys Rev Lett ; 121(18): 188002, 2018 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-30444395

RESUMO

While the large majority of theoretical and numerical studies of the jamming transition consider athermal packings of purely repulsive spheres, real complex fluids and soft solids generically display attraction between particles. By studying the statistics of rigid clusters in simulations of soft particles with an attractive shell, we present evidence for two distinct jamming scenarios. Strongly attractive systems undergo a continuous transition in which rigid clusters grow and ultimately diverge in size at a critical packing fraction. Purely repulsive and weakly attractive systems jam via a first-order transition, with no growing cluster size. We further show that the weakly attractive scenario is a finite size effect, so that for any nonzero attraction strength, a sufficiently large system will fall in the strongly attractive universality class. We therefore expect attractive jamming to be generic in the laboratory and in nature.

17.
Phys Rev E ; 98(1-1): 012607, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30110853

RESUMO

Aqueous foams are an important model system that displays coarsening dynamics. Coarsening in dispersions and foams is well understood in the dilute and dry limits, where the gas fraction tends to zero and one, respectively. However, foams are known to undergo a jamming transition from a fluidlike to a solidlike state at an intermediate gas fraction ϕ_{c}. Much less is known about coarsening dynamics in wet foams near jamming, and the link to mechanical response, if any, remains poorly understood. Here we probe coarsening and mechanical response using numerical simulations of a variant of the Durian bubble model for wet foams. As in other coarsening systems we find a steady state scaling regime with an associated particle size distribution. We relate the time rate of evolution of the coarsening process to the wetness of the foam and identify a characteristic coarsening time that diverges approaching jamming. We further probe mechanical response of the system to strain while undergoing coarsening. There are two competing timescales, namely the coarsening time and the mechanical relaxation time. We relate these to the evolution of the elastic response and the mechanical structure.

18.
Phys Rev Lett ; 120(14): 148004, 2018 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-29694121

RESUMO

When elastic solids are sheared, a nonlinear effect named after Poynting gives rise to normal stresses or changes in volume. We provide a novel relation between the Poynting effect and the microscopic Grüneisen parameter, which quantifies how stretching shifts vibrational modes. By applying this relation to random spring networks, a minimal model for, e.g., biopolymer gels and solid foams, we find that networks contract or develop tension because they vibrate faster when stretched. The amplitude of the Poynting effect is sensitive to the network's linear elastic moduli, which can be tuned via its preparation protocol and connectivity. Finally, we show that the Poynting effect can be used to predict the finite strain scale where the material stiffens under shear.

19.
J Biomed Mater Res A ; 106(5): 1355-1362, 2018 05.
Artigo em Inglês | MEDLINE | ID: mdl-29330941

RESUMO

Denture adhesives are designed to be moisture-sensitive through the inclusion of a blend of polymer salts with varying degrees of water-sensitivity. This enables the adhesive to mix with saliva in vivo and activate its high tack, through the formation of a mucilaginous layer. We report for the first time, the use of differential scanning calorimetry to study a series of hydrophobic and hydrophilic polymeric systems in order to correlate water-structuring behavior with adhesion strength. Adhesive bonding of the more hydrophobic variants was higher than that of a commercial-based control and a more hydrophilic polymer system in both lap shear and tensile configurations. Water-binding data suggested that increasing the hydrophobicity of the maleic acid copolymer substituents led to decreased levels of freezing water. In comparison, increasing the hydrophilic nature of the polymer backbone gave higher levels of freezing water within the hydrated samples. The results of this study emphasize the importance of varying the levels of hydrophobic and hydrophilic components within denture adhesive formulations, alongside the types of water present within the adhesive systems. This phenomenon has shown the potential to fine-tune the adhesive properties and failure mode against poly(methyl methacrylate), surfaces. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 1355-1362, 2018.


Assuntos
Adesivos/química , Dentaduras , Água/química , Congelamento , Interações Hidrofóbicas e Hidrofílicas , Resistência à Tração
20.
Cont Lens Anterior Eye ; 41(1): 47-53, 2018 02.
Artigo em Inglês | MEDLINE | ID: mdl-28951004

RESUMO

PURPOSE: The use of the Schirmer strips (SS) as a tool in the characterisation of dry eye disease, depends upon the quantitative assessment of tear production and constituents. The aim of this study was to ascertain the extent to which the properties of commercially available SS can vary and the way in which this baseline information may relate to their comparability in clinical use. METHODS: Five SS were analysed: Clement Clarke®, TearFlo®, Bio Schirmer®, Omni Schirmer® and JingMing®. Various aspects of their physical appearance and physicochemical behaviour were measured, including size, weight, and thickness together with surface morphology (assessed by SEM) and aqueous uptake and release behaviour (including the influence of each strip on protein retention and eluent osmolarity). RESULTS: All physical parameters varied between the strips studied for example the Clement Clark was the largest, thickest, and heaviest strip assessed in this study. SEM images showed that each of the SS had unique surface morphologies. Statistically significant differences among the strips were found for uptake (p=0.001) and release volume (p=0.014). Clement Clarke absorbed the highest volume over a fixed time period (23.8±1.6µl) and Omni the lowest (19.3±0.5µl). Clement Clarke showing the highest eluent osmolarity value (5.0±0.0mOsm/L) and TearFlo the lowest (2.8±0.4mOsm/L). CONCLUSION: The five strips investigated in this study indicate that there is no standardisation of commercial strips, despite the fact that the need for standardisation was recognised over fifty years ago. This study provides useful baseline information relating to SS comparability in clinical use.


Assuntos
Síndromes do Olho Seco/metabolismo , Proteínas do Olho/análise , Lágrimas/química , Humanos , Concentração Osmolar , Fitas Reagentes
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