Cross-link Density Of Matrix Research Articles

Synthesis of highly-stretchable graphene – poly(glycerol sebacate) elastomeric nanocomposites piezoresistive sensors for human motion detection applications

Strain sensors capable of monitoring human motion are highly desirable not only to monitor in real time complex body parts movement but also to assess the patients' health condition. In this work, highly stretchable elastomeric nanocomposite strain sensors were developed by synthesis of poly(glycerol sebacate) (PGS) prepolymer, followed by incorporation of the graphene flakes (fG) during the curing procedure of the PGS elastomeric matrix. The PGS had Young's modulus (E) of 69 ± 6 kPa, while the sample with 10 wt% fG had a E of 501 ± 28 kPa, which is as soft as human skin. Moreover, the incorporation of the fG filler led to an increase of the matrix cross-linking density, from 8.0 ± 0.6 mol/m3, up to 35.5 ± 1.4 mol/m3, recorded for the pure matrix and for the sample with 10 wt% fG, respectively. The electromechanical behavior of the nanocomposite samples showed that the resistance changes linearly with the applied strain, until a maximum strain of 50%, and is independent of the stroke speed or applied strain. The nanocomposite sensor sensibility was calculated through the gauge Factor (GF), and a value of ∼2 was obtained for all the processed strain gauges. Furthermore, the developed sensors showed a remarkable capability to monitor the bending movement of the finger. Finally, the performance revealed by the synthetized piezoresistive sensors will contribute to the next generation of highly stretchable smart materials for sensing and control human motion with minimum discomfort.

Processing, characterisation and electromechanical behaviour of elastomeric multiwall carbon nanotubes-poly (glycerol sebacate) nanocomposites for piezoresistive sensors applications

Highly stretchable elastomeric multiwall carbon nanotubes – poly (glycerol sebacate) (MWCNT-PGS) nanocomposites were prepared by mixing conductive multiwall carbon nanotubes (MWCNTs) with PGS prepolymer and curing at 120 °C. The incorporation of conductive filler increases the matrix crosslinking density and mechanical stiffness without loss of the flexibility and elasticity of the polymeric network with low mechanical hysteresis behaviour. The percolation threshold for the electrical conductivity was found to be ∼1 wt% of MWCNTs. The piezoresistive behaviour of the prepared samples shows a negative gauge factor (GF) between −0.5 and −0.8 under uniaxial tensile stress, probably due to geometrical factors, whilst under 3-point bending the calculated GF values were positive and a maximum GF = 42 was achieved for the samples with 2 wt% MWCNTs. Overall, the unique property combination between the MWCNTs and the PGS make them potentially suitable for the development of large deformation piezoresistive sensors, especially for biomedical engineering applications, flexible and wearable devices.

Reloadable Silk-Hydrogel Hybrid Scaffolds for Sustained and Targeted Delivery of Molecules.

Tunable repeated drug administration is often inevitable in a number of pathological cases. Reloadable 3D matrices for sustained drug delivery are predicted as a prospective avenue to realize this objective. This study was directed toward sonication-induced fabrication of novel reloadable Bombyx mori silk fibroin (SF) (4, 6, and 8 wt %) hydrogel, injected within 3D porous (8 wt %) scaffolds. The focus was to develop a dual-barrier reloadable depot system for sustained molecular cargo release. Both the varying SF concentration (4, 6, and 8 wt %) and the sonication time (30, 45, and 60 s) dictated the extent of cross-linking, β-sheet content, and porosity (1-10 μm) influencing the release behavior of model molecules. Release studies of model molecules (trypan blue, TB, 961 Da and bovine serum albumin, BSA, 66 kDa) for 28 days attested that the variations in their molecular weight, the matrix cross-linking density, and the scaffold-hydrogel interactions dictated the release behavior. The Ritger and Peppas equation was further fitted into the release behavior of model molecules from various SF matrices. The hybrid constructs exhibited high compressive strength along with in vitro compatibility using primary porcine chondrocytes and tunable enzymatic degradation as assessed for 28 days. The aptness of the constructs was evinced as a reloadable model molecule (BSA and fluorescein isothiocyanate-inulin, 3.9 kDa) depot system through UV-visible and fluorescence spectroscopic analyses. The novel affordable platform developed using silk scaffold-hydrogel hybrid constructs could serve as a sustained and reloadable drug depot system for administration of multiple and repeated drugs.

Interlaminar fracture toughness behavior of electron-beam cured carbon-fiber reinforced epoxy-resin composites

The work describes the preparation and physical-mechanical characterization of unidirectional CFRP panels manufactured by an electron beam curing technique. Delamination fracture toughness in Mode I and II is investigated in order to evaluate the influence of fiber–matrix adhesion strength, matrix toughness and matrix crosslinking density as determined by the radiation curing process. A matrix system comprising a DGEBA epoxy monomer and an initiator of cationic polymerization have been used, with one batch of resin mixed with a PES monomer in order to enhance matrix toughness. Curing was achieved with a pulsed 10 MeV Electron Beam accelerator. Thermally cured composite systems have also been manufactured and tested for comparison. Results from double cantilever beam and end notched flexure delamination tests have been analyzed and correlated with results from short beam shear, dynamic mechanical thermal analysis tests and SEM micrographs of delaminated surfaces. POLYM. COMPOS., 35:1529–1542, 2014. © 2013 Society of Plastics Engineers

The effect of carbon nanotubes on epoxy matrix nanocomposites

The paper concerns thermal properties of epoxy/nanotubes composites for aircraft application. In this work, influence of carbon nanotubes on thermal stability, thermal conductivity, and crosslinking density of epoxy matrix was determined. Three kinds of nanotubes were used: non-modified with 1- and 1.5-μm length, and 1-μm length modified with amino groups. Scanning electron microscopy observations were done for examining dispersion of nanotubes in the epoxy matrix. Glass transition temperature (Tg) was readout from differential scanning calorimetry. From dynamic mechanical analysis, crosslinking density was calculated for epoxy and its composites. Also, thermogravimetric analysis was done to determine influence of nanotubes addition on thermal stability and decomposition process of composites. Activation energy was calculated from TGA curves by Flynn–Wall–Ozawa method. Thermal diffusivity was also measured. SEM images proved the uniform dispersion of carbon nanotubes without any agglomerates. It was found that nanotubes modified with amino groups lead to the increase of epoxy matrix crosslinking density. The significant increase in Tg was also observed. On the other hand, addition of carbon nanotubes leads to the decrease of thermal stability of polymer due to the increase of thermal diffusivity.

Hydrogel crosslinking density regulates temporal contractility of human embryonic stem cell-derived cardiomyocytes in 3D cultures

Systematically tunable in vitro platforms are invaluable in gaining insight to stem cell-microenvironment interactions in three-dimensional cultures. Utilizing recombinant protein technology, we independently tune hydrogel properties to systematically isolate the effects of matrix crosslinking density on cardiomyocyte differentiation, maturation, and function. We show that contracting human embryonic stem cell-derived cardiomyocytes (hESC-CMs) remain viable within four engineered elastin-like hydrogels of varying crosslinking densities with elastic moduli ranging from 0.45 to 2.4 kPa. Cardiomyocyte phenotype and function was maintained within hESC embryoid bodies for up to 2 weeks. Interestingly, increased crosslinking density was shown to transiently suspend spontaneous contractility. While encapsulated cells began spontaneous contractions at day 1 in hydrogels of the lowest crosslinking density, onset of contraction was increasingly delayed at higher crosslinking densities up to 6 days. However, once spontaneous contraction was restored, the rate of contraction was similar within all materials (71 ± 8 beats/min). Additionally, all groups successfully responded to electrical pacing at both 1 and 2 Hz. This study demonstrates that encapsulated hESC-CMs respond to 3D matrix crosslinking density within elastin-like hydrogels and stresses the importance of investigating temporal cellular responses in 3D cultures.

Elucidating the Role of Matrix Stiffness in 3D Cell Migration and Remodeling

Reductionist in vitro model systems which mimic specific extracellular matrix functions in a highly controlled manner, termed artificial extracellular matrices (aECM), have increasingly been used to elucidate the role of cell-ECM interactions in regulating cell fate. To better understand the interplay of biophysical and biochemical effectors in controlling three-dimensional cell migration, a poly(ethylene glycol)-based aECM platform was used in this study to explore the influence of matrix cross-linking density, represented here by stiffness, on cell migration in vitro and in vivo. In vitro, the migration behavior of single preosteoblastic cells within hydrogels of varying stiffness and susceptibilities to degradation by matrix metalloproteases was assessed by time-lapse microscopy. Migration behavior was seen to be strongly dependent on matrix stiffness, with two regimes identified: a nonproteolytic migration mode dominating at relatively low matrix stiffness and proteolytic migration at higher stiffness. Subsequent in vivo experiments revealed a similar stiffness dependence of matrix remodeling, albeit less sensitive to the matrix metalloprotease sensitivity. Therefore, our aECM model system is well suited to unveil the role of biophysical and biochemical determinants of physiologically relevant cell migration phenomena.

The influence of ascorbic acid, TGF-β1, and cell-mediated remodeling on the bulk mechanical properties of 3-D PEG–fibrinogen constructs

Two-dimensional cell culture studies have shown that matrix rigidity can influence cell function, but little is known about how matrix physical properties, and their changes with time, influence cell function in 3-D. Biosynthetic hydrogels based on PEGylated fibrinogen permit the initial decoupling of matrix chemical and mechanical properties, and are thus potentially attractive for addressing this question. However, the mechanical stability of these gels due to passive hydrolysis and cell-mediated remodeling has not previously been addressed. Here, we show that the bulk mechanical properties of acellular PEG–fibrinogen hydrogels significantly decrease over time in PBS regardless of matrix cross-linking density in 7 days. To compensate, smooth muscle cells (SMCs) were encapsulated and stimulated to produce their own matrix using ascorbic acid or TGF-β1. Ascorbic acid treatment improved the mechanical properties of the constructs after 14 days in less cross-linked matrices, but TGF-β1 did not. The increase in matrix modulus of the constructs was not due to an increase in type I collagen deposition, which remained low and pericellular regardless of cross-link density or the soluble factor applied. Instead, ascorbic acid, but not TGF-β1, preferentially enhanced the contractile SMC phenotype in the less cross-linked gels. Inhibition of contractility reduced cell spreading and the expression of contractile markers, and eliminated any beneficial increase in matrix modulus induced by cell-generated contraction of the gels. Together, these data show that PEG–fibrinogen hydrogels are susceptible to both hydrolysis and proteolysis, and suggest that some soluble factors may stimulate matrix remodeling by modulating SMC phenotype instead of inducing ECM synthesis in a 3-D matrix.

Effect of cross-link density on modification of epoxy resins by N-phenylmaleimide-styrene copolymers

The effect of cross-link density on the toughening of modified resins was investigated for the modification of epoxy resins with N-phenylmaleimide-styrene alternating copolymers (PMS). The cross-link density of the epoxy matrix was controlled by a combination of two kinds of epoxy resins [diglycidyl ether of bisphenol-A (DGEBA) or triglycidyl aminocresol (TGAC)] and hybrid hardeners composed of p, p′-diaminodiphenyl sulphone (DDS) and p, p′-( N, N′-dimethyl)-diaminodiphenyl sulphone (MDS). The addition of 10 wt% of PMS ( M w 214,000 ) led to 120% increase in the fracture toughness ( K 1C) of the DGEBA resin cured with the hybrid hardener (DDS: MDS, 67:33 mol ratio). On addition of 15 wt% of PMS ( M w 214,000 ), K 1C for the modified resin increased 110% in the TGAC/hybrid hardener (DDS: MDS, 67:33 mol ratio) system. Morphologies of the modified resins depended on PMS molecular weight and concentration, and the cross-link density of the matrix. The toughening of epoxies could be explained by the cocontinuous phase structure in every case.