We report the preparation and structural and mechanical characterization of a tough supramolecular hydrogel, based exclusively on hydrophobic association. The system consists of a multiblock, ...segmented copolymer of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dimer fatty acid (DFA) building blocks. A series of copolymers containing 2K, 4K, and 8K PEG were prepared. Upon swelling in water, a network is formed by self-assembly of hydrophobic DFA units in micellar domains, which act as stable physical cross-link points. The resulting hydrogels are noneroding and contain 75–92 wt % of water at swelling equilibrium. Small-angle neutron scattering (SANS) measurements showed that the aggregation number of micelles ranges from 2 × 102 to 6 × 102 DFA units, increasing with PEG molecular weight. Mechanical characterization indicated that the hydrogel containing PEG 2000 is mechanically very stable and tough, possessing a tensile toughness of 4.12 MJ/m3. The high toughness, processability, and ease of preparation make these hydrogels very attractive for applications where mechanical stability and load bearing features of soft materials are required.
Hydrogels were prepared with physical cross-links comprising 2-ureido-41H-pyrimidinone (UPy) hydrogen-bonding units within the backbone of segmented amphiphilic macromolecules having hydrophilic ...poly(ethylene glycol) (PEG). The bulk materials adopt nanoscopic physical cross-links composed of UPy–UPy dimers embedded in segregated hydrophobic domains dispersed within the PEG matrix as comfirmed by cryo-electron microscopy. The amphiphilic network was swollen with high weight fractions of water (w H2O ≈ 0.8) owing to the high PEG weight fraction within the pristine polymers (w PEG ≈ 0.9). Two different PEG chain lengths were investigated and illustrate the corresponding consequences of cross-link density on mechanical properties. The resulting hydrogels exhibited high strength and resilience upon deformation, consistent with a microphase separated network, in which the UPy–UPy interactions were adequately shielded within hydrophobic nanoscale pockets that maintain the network despite extensive water content. The cumulative result is a series of tough hydrogels with tunable mechanical properties and tractable synthetic preparation and processing. Furthermore, the melting transition of PEG in the dry polymer was shown to be an effective stimulus for shape memory behavior.
Interactions between surfaces and particles in aqueous suspension are usually limited to distances smaller than 1 μm. However, in a range of studies from different disciplines, repulsion of particles ...has been observed over distances of up to hundreds of micrometers, in the absence of any additional external fields. Although a range of hypotheses have been suggested to account for such behavior, the physical mechanisms responsible for the phenomenon still remain unclear. To identify and isolate these mechanisms, we perform detailed experiments on a well-defined experimental system, using a setup that minimizes the effects of gravity and convection. Our experiments clearly indicate that the observed long-range repulsion is driven by a combination of ion exchange, ion diffusion, and diffusiophoresis. We develop a simple model that accounts for our data; this description is expected to be directly applicable to a wide range of systems exhibiting similar long-range forces.
Glaucoma is a progressive optic neuropathy that is the second leading cause of preventable blindness worldwide, after cataract formation. A rise in the intraocular pressure (IOP) is considered to be ...a major risk factor for glaucoma and is associated with an abnormal increase of resistance to aqueous humour outflow from the anterior chamber. Glaucoma drainage devices have been developed to provide an alternative pathway through which aqueous humour can effectively exit the anterior chamber, thereby reducing IOP. These devices include the traditional aqueous shunts with tube-plate design, as well as more recent implants, such as the trabeculectomy-modifying EX-PRESS
implant and the new minimally invasive glaucoma surgery (MIGS) devices. In this review, we will describe each implant in detail, focusing on their efficacy in reducing IOP and safety profile. Additionally, a critical and evidence-based comparison between these implants will be provided. Finally, we will propose potential developments that may help to improve the performance of current devices.
Physically associated hydrogels based on strong hydrophobic interactions often have attractive mechanical properties that combine processability with elasticity. However, there is a need to study ...such interactions and understand their relation to the macroscopic hydrogel properties. Therefore, we use the surfactant sodium dodecyl sulfate (SDS) and urea as reagents that disrupt hydrophobic interactions. The model hydrogel is based on a segmented copolymer between poly(ethylene glycol) (PEG) and hydrophobic dimer fatty acid (DFA). We show that both agents influence viscoelastic properties, dynamics, and relaxation processes of the model hydrogel. In particular, the relaxation time is significantly reduced by urea, as compared to SDS, whereas the surfactant causes a decrease of the modulus of the hydrogel more efficiently. The reversibility of the effects of SDS and urea can be exploited, for instance, by using an injectable sol that solidifies when the SDS or urea diffuses out of the sample. Surfactant-induced processability may be advantageous in future applications of hydrophobically assembled physical hydrogels.
Glaucoma is a group of eye conditions that damage the optic nerve, the health of which is vital for vision. The key risk factor for the development and progression of this disease is increased ...intraocular pressure (IOP). Implantable glaucoma drainage devices have been developed to divert aqueous humor from the glaucomatous eye as a means of reducing IOP. The artificial drainage pathway created by these devices drives the fluid into a filtering bleb. The long-term success of filtration surgery is dictated by the proper functioning of the bleb and overlying Tenon's and conjunctival tissue. To better understand the influence of the health condition of these tissues on IOP, we have developed a mathematical model of fluid production in the eye, its removal from the anterior chamber by a particular glaucoma implant-the PRESERFLO® MicroShunt-, drainage into the bleb and absorption by the subconjunctival vasculature. The mathematical model was numerically solved by commercial FEM package COMSOL. Our numerical results of IOP for different postoperative conditions are consistent with the available evidence on IOP outcomes after the implantation of this device. To obtain insight into the adjustments in the implant's hydrodynamic resistance that are required for IOP control when hypotony or bleb scarring due to tissue fibrosis take place, we have simulated the flow through a microshunt with an adjustable lumen diameter. Our findings show that increasing the hydrodynamic resistance of the microshunt by reducing the lumen diameter, can effectively help to prevent hypotony. However, decreasing the hydrodynamic resistance of the implant will not sufficiently decrease the IOP to acceptable levels when the bleb is encapsulated due to tissue fibrosis. Therefore, to effectively reduce IOP, the adjustable glaucoma implant should be combined with a means of reducing fibrosis. The results reported herein may provide guidelines to support the design of future glaucoma implants with adjustable hydrodynamic resistances.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The mechanical response of cells is a powerful biophysical marker for cell state. Information on a cell's elasticity can, for instance, be used to distinguish between different cell phenotypes, or ...between healthy and diseased cells.
Soft colloids make strong glasses Hu, Zhibing; Weitz, David A; Fernandez-Nieves, Alberto ...
Nature (London),
11/2009, Letnik:
462, Številka:
7269
Journal Article
Recenzirano
Glass formation in colloidal suspensions has many of the hallmarks of glass formation in molecular materials. For hard-sphere colloids, which interact only as a result of excluded volume, phase ...behaviour is controlled by volume fraction, ; an increase in drives the system towards its glassy state, analogously to a decrease in temperature, T, in molecular systems. When increases above * 0.53, the viscosity starts to increase significantly, and the system eventually moves out of equilibrium at the glass transition, g 0.58, where particle crowding greatly restricts structural relaxation. The large particle size makes it possible to study both structure and dynamics with light scattering and imaging; colloidal suspensions have therefore provided considerable insight into the glass transition. However, hard-sphere colloidal suspensions do not exhibit the same diversity of behaviour as molecular glasses. This is highlighted by the wide variation in behaviour observed for the viscosity or structural relaxation time, , when the glassy state is approached in supercooled molecular liquids. This variation is characterized by the unifying concept of fragility, which has spurred the search for a 'universal' description of dynamic arrest in glass-forming liquids. For 'fragile' liquids, is highly sensitive to changes in T, whereas non-fragile, or 'strong', liquids show a much lower T sensitivity. In contrast, hard-sphere colloidal suspensions are restricted to fragile behaviour, as determined by their dependence, ultimately limiting their utility in the study of the glass transition. Here we show that deformable colloidal particles, when studied through their concentration dependence at fixed temperature, do exhibit the same variation in fragility as that observed in the T dependence of molecular liquids at fixed volume. Their fragility is dictated by elastic properties on the scale of individual colloidal particles. Furthermore, we find an equivalent effect in molecular systems, where elasticity directly reflects fragility. Colloidal suspensions may thus provide new insight into glass formation in molecular systems.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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•Developed a new method for creating non-spherical colloidal particles.•Produced oblate ellipsoidal particles of controlled, uniform size and shape.•Optimized method to maintain high ...fluorescence intensity for 3D confocal imaging.•Opens up new possibilities for studying the behavior of non-spherical colloids.
We present a robust and straightforward method for producing colloidal particles of oblate ellipsoidal shape via thermo/mechanical stretching of elastomeric films with embedded spherical particles. Our method produces uniformly sized and shaped colloidal particles. The method can be used for producing biaxially stretched particles of different aspect ratios and volumes; moreover, the method has a higher yield and batch size than previously reported methods for producing non-spherical particles via film stretching. These particles are ideal model systems for studying the self-assembly and gel formation for systems with anisotropic shapes and interactions. We illustrate this by adding of a non-adsorbing polymer to the solvent, thereby inducing directional depletion interactions between the particles.
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