Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part 4: Growth of rat bone marrow stromal cells in three-dimensional hydrogels with positive and negative surface charges and in polyelectrolyte complexes

The growth of bone marrow stromal cells was assessed in vitro in macroporous hydrogels based on 2-hydro- xyethyl methacrylate (HEMA) copolymers with different electric charges. Copolymers of HEMA with sodium methacrylate (MA⁻) carried a negative electric charge, copolymers of HEMA with [2-(methacryloyloxy)ethyl] trimethylammonium chloride (MOETA⁻) carried a positive electric charge and terpolymers of HEMA, MA⁻ and MOETA⁺ carried both, positive and negative electric charges. The charges in the polyelectrolyte complexes were shielded by counter-ions. The hydrogels had similar porosities, based on a comparison of their diffusion parameters for small cations as measured by the real-time tetramethylammonium iontophoretic method of diffusion analysis. The cell growth was studied in the peripheral and central regions of the hydrogels at 2 hours and 2, 7, 14 and 28 days after cell seeding. Image analysis revealed the highest cellular density in the HEMA-MOETA⁺ copolymers; most of the cells were present in the peripheral region of the hydrogels. A lower density of cells but no difference between the peripheral and central regions was observed in the HEMA-MA⁻ copolymers and in polyelectrolyte complexes. This study showed that positively charged functional groups promote the adhesion of cells.     

Macroporous hydrogels based on 2-hydroxyethyl methacrylate

Four series of macroporous hydrogels based on crosslinked copolymers of 2-hydroxyethyl methacrylate (HEMA)-sodium methacrylate (MANa), copolymer HEMA-[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MOETACl), terpolymer HEMA-MANa-MOETACl and on a polyelectrolyte complex were used as carriers for immobilization of proteins, chicken egg white albumin and avidin. The adsorption capacity of the hydrogels for the two proteins, kinetics and pH dependence of albumin adsorption and desorption were studied. The morphology of the hydrogels with and without immobilized albumin was studied by low-vacuum scanning electron microscopy.     

Macroporous hydrogels based on 2-hydroxyethyl methacrylate

Crosslinked macroporous hydrogels based on 2-hydroxyethyl methacrylate (HEMA)—[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MOETACl) copolymer, HEMA-MOETACl—methacrylic acid (MA) terpolymer, and on a polyelectrolyte complex of HEMA—MA copolymer with poly(MOETACl) were prepared. All the hydrogels were prepared in the presence of fractionated sodium chloride particles. The hydrogels were characterized by the number of pores and the total volume of all pores in unit volume, the average volume and the average diameter of single pore. Morphology of the hydrogels was investigated by confocal and scanning electron microscopy. The hydrogels based on polyelectrolyte complexes were also characterized by chemical composition. Homogeneous (non-porous) hydrogels with the same composition as macroporous hydrogels were prepared and characterized by their biocompatibility.     

Macroporous hydrogels based on 2-hydroxyethyl methacrylate. Part 5: Hydrolytically degradable materials

Macroporous hydrogels based on 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate and N-(2-hydroxypropyl)methacrylamide, methacrylic acid and [2-(methacryloyloxy)ethyl]trimethylammonium chloride crosslinked with N,O-dimethacryloylhydroxylamine were prepared. Hydrogels were degraded in a buffer of pH 7.4. Completely water-soluble polymers were obtained over time periods ranging from 2 to 40 days. The process of degradation was followed gravimetrically and by optical and electron microscopy. In vivo biological tests with hydrogels based on copolymers of 2-ethoxyethyl methacrylate/N-(2-hydroxypropyl)methacrylamide were performed.     

Surface modification of hydrogels based on poly(2-hydroxyethyl methacrylate) with extracellular matrix proteins

Infrared attenuated total reflection spectroscopy was used for in situ observation of the deposition of collagen I on poly(2-hydroxyethyl methacrylate-co-methacrylic acid, 2.9%) hydrogels and subsequent attachment of laminin or fibronectin on the collagen surface. While there was no adsorption of collagen dissolved in an acid solution on the hydrogel surface, it deposited on the surface at pH 6.5. The collagen layers with attached laminin or fibronectin were stable on hydrogel surface in physiological solution. The modification with collagen and particularly with collagen and laminin or fibronectin allowed the adhesion and growth of mesenchymal stromal cells and astrocytes on the hydrogel surface.     

Synthesis and characterization of hydrogels based on poly(2-hydroxyethyl methacrylate) for drug delivery under UV irradiation

The present study aims to create a controlled release system through the preparation and characterization of hydrogels based on 2-hydroxyl ethyl methacrylate (HEMA). In order to investigate the influence of photo-initiators on the drug release behavior of the resulting hydrogels, three different photo-initiators [2,2-dimethoxy-2-phenyl-acetophenone] (Irgacure 651), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) and 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959) were used. In addition, hydroxyapatite (HAp) was employed to modify HEMA hydrogels. The synthesis of hydrogels was confirmed by characterization through Fourier transform infrared spectroscopy, nuclear magnetic resonance (¹³C NMR) spectroscopy and digital microscope. The responsive behaviors were investigated by recording swelling ratios under different conditions. In vitro drug release studies were performed for donepezil hydrochloride-loaded hydrogels at pH 1.2, 6.8 and 7.4. The results indicated that hydrogels synthesized using Irgacure 2959 released the maximum amount of donepezil hydrochloride. Moreover, the release rate decreased in the presence of HAp.     

Hydrophilic sponges based on 2-hydroxyethyl methacrylate Part VII: Modulation of sponge characteristics by changes in reactivity and hydrophilicity of crosslinking agents

Despite previous unsuccessful attempts to use hydrated poly(2-hydroxyethyl methacrylate) sponges as implantable biomaterials, recently these materials became important as peripheral components in an artificial cornea of the core-and-skirt design. The low mechanical strength of sponges prompted this study on possible improvement of tensile properties by the use of a variety of crosslinking agents. Three vinylic (dimethacrylates) and two allylic compounds were used at different concentrations (0.1 to 2% (mol)) as crosslinking agents in the production of sponges. Their influence on the mechanical properties, porous morphology and swelling behavior of resulting sponges was evaluated. The onset of phase separation during polymerization was also measured by visible spectrophotometry. The results suggested an inherent heterogeneity of sponges, i.e. pores of non-uniform size and structural inhomogeneities. While the effects of changes in the nature and concentration of crosslinking agents on the equilibrium water content of sponges were ambiguous, some of the mechanical properties, such as toughness and elasticity, were improved by crosslinking with allylic agents. Scanning electron microscopic examination suggested that the mechanical effect is related to the variation of size of the polymer particles constituting the sponge structure, which was proved to be dependent upon the onset of phase separation during polymerization. ©2000 Kluwer Academic Publishers     

Automatic metric 3D surface mesh generation using subdivision surface geometrical model. Part 2: Mesh generation algorithm and examples

In this paper, a new metric advancing front surface mesh generation scheme is suggested. This new surface mesh generator is based on a new geometrical model employing the interpolating subdivision surface concept. The target surfaces to be meshed are represented implicitly by interpolating subdivision surfaces which allow the presence of various sharp and discontinuous features in the underlying geometrical model. While the main generation steps of the new generator are based on a robust metric surface triangulation kernel developed previously, a number of specially designed algorithms are developed in order to combine the existing metric advancing front algorithm with the new geometrical model. As a result, the application areas of the new mesh generator are largely extended and can be used to handle problems involving extensive changes in domain geometry. Numerical experience indicates that, by using the proposed mesh generation scheme, high quality surface meshes with rapid varying element size and anisotropic characteristics can be generated in a short time by using a low‐end PC. Finally, by using the pseudo‐curvature element‐size controlling metric to impose the curvature element‐size requirement in an implicit manner, the new mesh generation procedure can also generate finite element meshes with high fidelity to approximate the target surfaces accurately. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis,surface group modification of 3D MnV2O6 nanostructures and adsorption effect on Rhodamine B

Highly uniform 3D MnV₂O₆ nanostructures modified by oxygen functional groups (COO) were successfully prepared in large quantities by an approach involving preparation of vanadyl ethylene glycolate as the precursor. The growth and self-assembly of MnV₂O₆ nanobelts and nanorods could be readily tuned by additive species and quantities, which brought different morphologies and sizes to the final products. With a focus on the regulation of structure, the formation process of 3D architectures of MnV₂O₆ by self-assembly of nanobelts was followed by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The consecutive processes of vanadyl ethylene glycolate and benzoyl peroxide assisted formation of layered structure Mn_0.5V₂O₅·nH₂O, growth of aligned MnV₂O₆ nanobelts, and oriented assembly were proposed for the growth mechanism. The band gap vs. different morphology was also studied. Optical characterization of these MnV₂O₆ with different morphologies showed direct bandgap energies at 1.8–1.95 eV. The adsorption properties of 3D MnV₂O₆ nanostructures synthesized under different conditions were investigated through the removal test of Rhodamine B in aqueous water, and the 3D nanostructures synthesized with 30 g L^?1 benzoyl peroxide showed good adsorption capability of Rhodamine B.     

Hybrid composites based on polyethylene and carbon fibres. Part 6: Tensile and fatigue behaviour

The tensile and fatigue behaviour of unidirectional carbon-high-performance polyethylene/epoxy hybrid composites has been studied, including the effect of hybrid design and surface treatment of the high-performance polyethylene (hp-pe) fibres. Results indicated that the tensile behaviour of carbon-hp-pe hybrids in both monotonic and fatigue testing can be interpreted, adopting the conventional ‘constant strain’ model for hybrid composites. Deviations from this constant strain model, so-called hybrid effects, were observed in monotonic tensile testing for those hybrid systems with the highest degree of fibre dispersion, incorporating either untreated or treated hp-pe fibres, whereas only the latter displayed synergistic fatigue performance. Hybrid effects under tensile loading conditions were in reasonable agreement with calculations accounting for statistical effects and stress concentrations as determined by finite element analyses.     

Protein Bricks: 2D and 3D Bio‐Nanostructures with Shape and Function on Demand

Precise patterning of polymer‐based biomaterials for functional bio‐nanostructures has extensive applications including biosensing, tissue engineering, and regenerative medicine. Remarkable progress is made in both top‐down (based on lithographic methods) and bottom‐up (via self‐assembly) approaches with natural and synthetic biopolymers. However, most methods only yield 2D and pseudo‐3D structures with restricted geometries and functionalities. Here, it is reported that precise nanostructuring on genetically engineered spider silk by accurately directing ion and electron beam interactions with the protein's matrix at the nanoscale to create well‐defined 2D bionanopatterns and further assemble 3D bionanoarchitectures with shape and function on demand, termed “Protein Bricks.” The added control over protein sequence and molecular weight of recombinant spider silk via genetic engineering provides unprecedented lithographic resolution (approaching the molecular limit), sharpness, and biological functions compared to natural proteins. This approach provides a facile method for patterning and immobilizing functional molecules within nanoscopic, hierarchical protein structures, which sheds light on a wide range of biomedical applications such as structure‐enhanced fluorescence and biomimetic microenvironments for controlling cell fate.     

Nonlinear Dynamic Finite Element Analysis of Thick Transversely Flexible Sandwich Panel on Elastic Foundation with Account of Damage Progression in Time. Part 2. 3D Analysis and Time Integration

A plate theory for a thick transversely compressible sandwich plate with composite laminated face sheets is constructed using the simplified assumptions earlier described in Part 1. An algorithm, which takes account of damage progression in dynamic problems, is incorporated into the computational scheme based on the geometrically nonlinear formulation and applied to failure analysis of a sandwich plate under ground impact. __________ Translated from Problemy Prochnosti, No. 4, pp. 95 – 112, July – August, 2005.     

A comparative study of tensile properties of non-crimp 3D orthogonal weave and multi-layer plain weave E-glass composites. Part 2: Comprehensive experimental results

This Part 2 paper presents results of comparative experimental study of progressive damage in 2D and 3D woven glass/epoxy composites under in-plane tensile loading. As Part 1, this Part 2 work is focused on the comparison of in-plane tensile properties of two non-crimp single-ply 3D orthogonal weave E-glass fibre composites on one side and a laminate reinforced with four plies of E-glass plain weave on the other. The damage investigation methodology combines mechanical testing with acoustic emission registration (that provides damage initiation thresholds), progressive cracks observation on transparent samples, full-field surface strain mapping and cracks observation on micrographs, altogether enabling for a thorough characterisation of the local micro- and meso-damage modes of the studied composites. The obtained results demonstrate that the non-crimp 3D orthogonal woven composites have significantly higher in-plane strengths, failure strains and damage initiation thresholds than their 2D woven laminated counterpart. The growth of transverse cracks in the yarns of 3D composites is delayed, and they are less prone to a yarn–matrix interfacial crack formation and propagation. Delaminations developing between the plies of plain weave fabric in the laminate at certain load level never appear in the 3D woven single-ply composites.     

Numerical simulation of plasticity-induced fatigue crack closure with emphasis on the crack growth scheme: 2D and 3D analyses

In this paper a numerical simulation of plasticity-induced fatigue crack closure is performed using the finite element method. Emphasis is placed on the crack growth scheme usually adopted for modelling fatigue crack growth in crack closure problems. The number of load cycles between node releases usually reported in the literature has been, in general, one or two. The present work shows that increasing the number of load cycles between node releases has a strong effect on the opening stresses, particularly, under plane strain conditions and 3D fatigue cracks, in contrast plane stress shows little variation with increasing number of load cycles. This investigation also suggests that ratchetting may take place close to the crack tip in both plane strain and 3D crack problems. The problem of discontinuous crack closure under plane strain conditions, often reported in the literature, is also addressed.     

c‐Type method of unified CAMG and FEA. Part 1: Beam and arch mega‐elements—3D linear and 2D non‐linear

Computer‐aided mesh generation (CAMG) dictated solely by the minimal key set of requirements of geometry, material, loading and support condition can produce ‘mega‐sized’, arbitrary‐shaped distorted elements. However, this may result in substantial cost saving and reduced bookkeeping for the subsequent finite element analysis (FEA) and reduced engineering manpower requirement for final quality assurance. A method, denoted as c‐type, has been proposed by constructively defining a finite element space whereby the above hurdles may be overcome with a minimal number of hyper‐sized elements. Bezier (and de Boor) control vectors are used as the generalized displacements and the Bernstein polynomials (and B‐splines) as the elemental basis functions. A concomitant idea of coerced parametry and inter‐element continuity on demand unifies modelling and finite element method. The c‐type method may introduce additional control, namely, an inter‐element continuity condition to the existing h‐type and p‐type methods. Adaptation of the c‐type method to existing commercial and general‐purpose computer programs based on a conventional displacement‐based finite element method is straightforward. The c‐type method with associated subdivision technique can be easily made into a hierarchic adaptive computer method with a suitable a posteriori error analysis. In this context, a summary of a geometrically exact non‐linear formulation for the two‐dimensional curved beams/arches is presented. Several beam problems ranging from truly three‐dimensional tortuous linear curved beams to geometrically extremely non‐linear two‐dimensional arches are solved to establish numerical efficiency of the method. Incremental Lagrangian curvilinear formulation may be extended to overcome rotational singularity in 3D geometric non‐linearity and to treat general material non‐linearity. Copyright © 2003 John Wiley & Sons, Ltd.     

Carbon composites based on multi-axial multi-ply stitched preforms – Part 6. Fatigue behaviour at low loads: Stiffness degradation and damage development

This article studies the fatigue properties of a carbon-fibre cross-ply non-crimp fabric reinforced epoxy composite. Tensile–tensile fatigue cycling was carried out at load levels corresponding to the onset of damage in a static tensile test, in machine, cross and bias direction. Specimens in machine and cross direction did not fail up to 10⁶ cycles; specimens in bias direction had an average fatigue life N_max of 3 × 10⁵ cycles. Stiffness degradation in bias direction samples was found to be more severe than in machine or cross direction. Damage development in the samples was studied by means of X-ray photography and appears to show remarkable resemblance to the development under a static tensile test and can be qualitatively compared to the behaviour of non-stitched UD laminates. Post-fatigue tensile tests were done at various stages of the fatigue life. Small differences in damage onset strain level can be found. Failure strain of bias direction tested samples shows significant decrease upon cycling.     

Triple-scale failure estimation for a composite-reinforced structure based on integrated modeling approaches. Part 2: Meso- and macroscopic scale analysis

In this article, the meso- and macroscopic failure features are discussed considering the identical composite component as in the foregoing article. In the meso-scale failure analysis, the risk of plastic instability of the composite tube was estimated considering the shakedown boundary as a failure criterion. The meso-scale stresses of the composite tube were computed using micromechanical homogenization and compared with the shakedown boundary of the composite obtained from the direct shakedown analysis. The stress states were close to the shakedown boundary indicating no critical danger of plastic failure. In the macro-scale failure analysis, the mechanical influence of the local composite integration was investigated with regard to the brittle failure risk of the neutron-embrittled component. To this end, a probabilistic failure analysis code was applied which was based on the fracture mechanics and the weakest-link failure theory. Various fracture criteria were considered. It was found that the failure risk of the tungsten block was strongly reduced by the composite reinforcement of the tube due to the intensification of compressive stress fields.     

Tungsten-oxide thin films as novel materials with high sensitivity and selectivity to NO2, O3, and H2S. Part II: Application as gas sensors

The electrical response of tungsten-oxide thin films as-deposited by electron-beam deposition and annealed (at 350–800 °C for 1–3 h in O₂) to NO₂, O₃ and H₂S was studied both experimentally and theoretically. In order to interpret the kinetic characteristics of tungsten-oxide thin films on exposure to different gases, a model based on surface adsorption/desorption processes coupled with bulk diffusion was used. A link between the geometrical and chemical heterogeneities of the tungsten-oxide film surfaces and their performance characteristics as gas sensors was established. It was shown that the nature and amount of surface-adsorption sites in the different nonstoichiometric phases (W _n O_3n–2 or W _n O_3n–1) and WO₃ as well as their conduction mechanisms are defined from the phase composition of the film, the crystallographic and electronic structures of the phases, the orientation of the crystallites within the film and the geometrical shape and dimensions of the crystallites. All tungsten-oxide thin films investigated in this work are suitable for detection of very low concentrations of NO₂ (0.05–0.5 ppm in N₂ and synthetic air), ozone (25–90 ppb) and H₂S (3–15 ppm in N₂ and synthetic air) at very low working temperatures (80–160 °C). The films annealed at 400 °C for 1–2 h are very selective to ozone at 120–160 °C; the films annealed at 400 °C for 1–3 h and at 800 °C for 1 h are very sensitive to NO₂ (in N₂).