Using supramolecular self-assembled nanocomposite materials made from protein and polysaccharide components is becoming more popular because of their unique properties, such as biodegradability, hierarchical structures, and tunable multifunctionality. However, the fabrication of these materials in a reproducible way remains a challenge. This study presents a new evaporation-induced self-assembly method producing layered hydrogel membranes (LHMs) using tropocollagen grafted by partially deacetylated chitin nanocrystals (CO-g-ChNCs). ChNCs help stabilize tropocollagen's helical conformation and fibrillar structure by forming a hierarchical microstructure through chemical and physical interactions. The LHMs show improved mechanical properties, cytocompatibility, and the ability to control drug release using octenidine dihydrochloride (OCT) as a drug model. Because of the high synergetic performance between CO and ChNCs, the modulus, strength, and toughness increased significantly compared to native CO. The biocompatibility of LHM was tested using the normal human dermal fibroblast (NHDF) and the human osteosarcoma cell line (Saos-2). Cytocompatibility and cell adhesion improved with the introduction of ChNCs. The extracted ChNCs are used as a reinforcing nanofiller to enhance the performance properties of tropocollagen hydrogel membranes and provide new insights into the design of novel LHMs that could be used for various medical applications, such as control of drug release in the skin and bone tissue regeneration.
- MeSH
- biokompatibilní materiály chemie farmakologie MeSH
- buněčná adheze účinky léků MeSH
- chitin chemie MeSH
- fibroblasty účinky léků cytologie MeSH
- hydrogely * chemie farmakologie MeSH
- lidé MeSH
- membrány umělé MeSH
- nádorové buněčné linie MeSH
- nanočástice chemie MeSH
- nanokompozity chemie MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- biokompatibilní materiály MeSH
- chitin MeSH
- hydrogely * MeSH
- membrány umělé MeSH
Recent complications on the use of polypropylene meshes for hernia repair has led to the development of meshes or films, which were based on resorbable polymers such as polycaprolactone (PCL), polylactic acid (PLA) and poly(lactic-co-glycolic acid) (PLGA). These materials are able to create suitable bioactive environment for the growth and development of cells. In this research, we mainly focused on the relations among structure, mechanical performance and biocompatiblity of PCL/PLA and PCL/PLGA and blends prepared by solution casting. The films were characterized regarding the chemical structure, morphology, physicochemical properties, cytotoxicity, biocompatibility and cell growth. All the films showed high tensile strength ranging from 9.5 to 11.8 MPa. SAXS showed that the lamellar stack structure typical for PCL was present even in the blend films while the morphological parameters of the stacks varied slightly with the content of PLGA or PLA in the blends. WAXS indicated preferential orientation of crystallites (and thus, also the lamellar stacks) in the blend films. In vitro studies revealed that PCL/PLGA films displayed better cell adhesion, spreading and proliferation than PCL/PLA and PCL films. Further the effect of blending on the degradation was investigated, to understand the significant variable within the process that could provide further control of cell adhesion. The results showed that the investigated blend films are promising materials for biomedical applications.
- Klíčová slova
- Biocompatibility, Mechanical properties, Nanoscale morphology, Polycaprolactone, Resorbable blends,
- MeSH
- difrakce rentgenového záření MeSH
- glykoly * MeSH
- kopolymer kyseliny glykolové a mléčné MeSH
- maloúhlový rozptyl MeSH
- polyestery MeSH
- vstřebatelné implantáty * MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- glykoly * MeSH
- kopolymer kyseliny glykolové a mléčné MeSH
- poly(lactide) MeSH Prohlížeč
- polycaprolactone MeSH Prohlížeč
- polyestery MeSH
The magnetic properties of nanoscale magnets are greatly influenced by surface anisotropy. So far, its quantification is based on the examination of the blocking temperature shift within a series of nanoparticles of varying sizes. In this scenario, the surface anisotropy is assumed to be a particle size-independent quantity. However, there is no solid experimental proof to support this simplified picture. On the contrary, our work unravels the size-dependent magnetic morphology and surface anisotropy in highly uniform magnetic nanoparticles using small-angle polarized neutron scattering. We observed that the surface anisotropy constant does not depend on the nanoparticle's size in the range of 3-9 nm. Furthermore, our results demonstrate that the surface spins are less prone to polarization with increasing nanoparticle size. Our study thus proves the size dependence of the surface spin disorder and the surface anisotropy constant in fine nanomagnets. These findings open new routes in materials based on a controlled surface spin disorder, which is essential for future applications of nanomagnets in biomedicine and magnonics.
- Publikační typ
- časopisecké články MeSH
Morphology, macro-, and micromechanical properties of novel poly(urethane-urea)/silica nanocomposites were analyzed by electron microscopy, dynamic mechanical thermal analysis, and microindentation. The studied nanocomposites were based on a poly(urethane-urea) (PUU) matrix filled by nanosilica, and were prepared from waterborne dispersions of PUU (latex) and SiO2. The loading of nano-SiO2 was varied between 0 (neat matrix) and 40 wt% in the dry nanocomposite. The prepared materials were all formally in the rubbery state at room temperature, but they displayed complex elastoviscoplastic behavior, spanning from stiffer elastomeric type to semi-glassy. Because of the employed rigid and highly uniform spherical nanofiller, the materials are of great interest for model microindentation studies. Additionally, because of the polycarbonate-type elastic chains of the PUU matrix, hydrogen bonding in the studied nanocomposites was expected to be rich and diverse, ranging from very strong to weak. In micro- and macromechanical tests, all the elasticity-related properties correlated very strongly. The relations among the properties that related to energy dissipation were complex, and were highly affected by the existence of hydrogen bonding of broadly varied strength, by the distribution patterns of the fine nanofiller, as well as by the eventual locally endured larger deformations during the tests, and the tendency of the materials to cold flow.
- Klíčová slova
- aqueous polyurethane dispersion, mechanical properties, microindentation, nanocomposites, polyurethanes, silica,
- Publikační typ
- časopisecké články MeSH
This contribution lays the foundation for the European database of explanted UHMWPE liners from total joint replacements. Three EU countries (Czech Republic, Italy and Spain) have joined their datasets containing anonymized patient data (such as age and BMI), manufacturer data (such as information on UHMWPE crosslinking, thermal treatment and sterilization), orthopedic evaluation (such as total duration of the implant in vivo and reasons for its revision) and material characterization (such as oxidative degradation and micromechanical properties). The joined database contains more than 500 entries, exhibiting gradual growth, and it is beginning to show interesting trends, which are discussed in our contribution, including (i) strong correlations between UHMWPE oxidative degradation, degree of crystallinity and microhardness; (ii) statistically significant differences between UHMWPE liners with different types of sterilization; (iii) realistic correlations between the extent of oxidative degradation and the observed reasons for total joint replacement failures. Our final objective and task for the future is to continuously expand the database, involving researchers from other European countries, in order to create a robust tool that will contribute to the better understanding of structure-properties-performance relationships in the field of arthroplasty implants.
- Klíčová slova
- European database, UHMWPE, micromechanical properties, oxidative degradation, retrieval study, total joint replacements, ultrahigh molecular weight polyethylene,
- Publikační typ
- časopisecké články MeSH
We compared the results of various microscale indentation creep (microcreep) measurements with macroscale tensile creep (macrocreep) measurements of three common polymers: high-density polyethylene (PE), polypropylene (PP), and polystyrene (PS). The main objective was to verify if the short-term microcreep experiments could predict long-term macrocreep behavior of the selected polymers, whose properties ranged from very soft and ductile (PE) to very hard and brittle (PS). The second objective was to compare several creep predictive schemes: the empirical power law model (PL) and several types of phenomenological elasto-visco-plastic models (EVP). In order to facilitate this task, we developed a universal program package named MCREEP, which fits PL and EVP models to both tensile and indentation creep data. All experimental results and theoretical predictions documented that: (i) regardless of the creep experiment type, both micro- and macrocreep resistance increased in the following order: PE < PP < PS, (ii) the short-term microcreep experiments could be used to predict qualitatively the long-term macrocreep behavior, and (iii) the simple empirical power law model yielded better predictions of long-term creep behavior than the more sophisticated elasto-visco-plastic models.
- Klíčová slova
- indentation creep, microindentation, polymers, tensile creep, viscoelasticity,
- Publikační typ
- časopisecké články MeSH
Plasmon-catalyzed decarboxylation reactions of Ru(II) bis(2,2'-bipyridine)(4,4'-dicarboxy-bipyridine) denoted as Ru(bpy)2(dcbpy) and Ru(II) tris(4,4'-dicarboxy-bipyridine) denoted as Ru(dcbpy)3 complexes in hydrosol systems with Ag nanoparticles (NPs) conditioned by the presence of Ag(0) adsorption sites on Ag NP surfaces have been revealed by surface-enhanced (resonance) Raman scattering (SERRS and/or SERS) spectral probing and monitoring further supported by factor analysis. Interpretation of the experimental results was based on an identification of specific marker bands of the Ru-dcbpy and of the Ru-bpy units. Furthermore, by a series of specifically targeted SERRS and/or SERS experiments complemented by UV/vis spectral measurements and TEM imaging of deposited Ag NPs, plasmon catalysis by charge carriers, namely hot electrons (e-) and hot holes (h+), has been established as the most probable mechanism of decarboxylation reactions undergone by the carboxylate-chemisorbed Ru-dcbpy units of the complexes. The presence of Ag(0) adsorption sites on Ag NP surfaces as the necessary condition of the reaction progress is in full accord with the charge carrier mechanism of plasmon catalysis. In particular, the neutral Ag(0) sites create the interface required for the transport of hot e- to H+ co-reactants complementing thus the C-C bond breaking and CO2 formation caused by hot h+.
- Publikační typ
- časopisecké články MeSH
We report a reproducible preparation and characterization of highly homogeneous thermoplastic starch/pol(ε-caprolactone) blends (TPS/PCL) with a minimal thermomechanical degradation and co-continuous morphology. These materials would be suitable for biomedical applications, specifically for the local release of antibiotics (ATB) from the TPS phase. The TPS/PCL blends were prepared in the whole concentration range. In agreement with theoretical predictions based on component viscosities, the co-continuous morphology was found for TPS/PCL blends with a composition of 70/30 wt.%. The minimal thermomechanical degradation of the blends was achieved by an optimization of the processing conditions and by keeping processing temperatures as low as possible, because higher temperatures might damage ATB in the final application. The blends' homogeneity was verified by scanning electron microscopy. The co-continuous morphology was confirmed by submicron-computed tomography. The mechanical performance of the blends was characterized in both microscale (by an instrumented microindentation hardness testing; MHI) and macroscale (by dynamic thermomechanical analysis; DMTA). The elastic moduli of TPS increased ca four times in the TPS/PCL (70/30) blend. The correlations between elastic moduli measured by MHI and DMTA were very strong, which implied that, in the future studies, it would be possible to use just micromechanical testing that does not require large specimens.
- Klíčová slova
- microindentation, micromechanical properties, poly(ε-caprolactone), polymer blends, structure–properties relations, thermoplastic starch,
- Publikační typ
- časopisecké články MeSH
We characterized a set of eleven clinically relevant formulations of UHMWPE for total joint replacements. Although their molecular and supermolecular structure were quite similar as evidenced by IR, DSC and SAXS measurements, there were slight differences in their crystallinity (DSC crystallinity ranging from 52 to 61%), which were connected with processing conditions, such as the total radiation dose, thermal treatment and/or addition of biocompatible stabilizers. Mechanical properties were assessed at all length scales, using macroscale compression testing, non-instrumented and instrumented microindentation hardness testing (at loading forces ~500 mN), and nanoindentation hardness testing measured at both higher and lower loading (~4 mN and ~0.6 mN, respectively). In agreement with theoretical predictions, we found linear correlations between UHMWPE crystallinity and its stiffness-related properties (elastic moduli, yield stress, and hardness) at all length scales (macro-, micro- and nanoscale). Detailed statistical evaluation of our dataset showed that the accuracy and precision of the applied methods decreased in the following order: non-instrumented microindentation ≥ instrumented microindentation ≥ macromechanical properties ≥ nanoindentation measured at higher loading forces ≫ nanoindentation measured at lower loading forces. The results confirm that microindentation and nanoindentation at sufficiently high loading forces are reliable methods, suitable for UHMWPE characterization.
- Klíčová slova
- Macro-, Micro- and nanomechanical properties, Microindentation, Nanoindentation, UHMWPE,
- MeSH
- difrakce rentgenového záření MeSH
- maloúhlový rozptyl MeSH
- polyethyleny * MeSH
- testování materiálů MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- polyethyleny * MeSH
- ultra-high molecular weight polyethylene MeSH Prohlížeč
This work is focused on the comparison of macro-, micro- and nanomechanical properties of a series of eleven highly homogeneous and chemically very similar polymer networks, consisting of diglycidyl ether of bisphenol A cured with diamine terminated polypropylene oxide. The main objective was to correlate the mechanical properties at multiple length scales, while using very well-defined polymeric materials. By means of synthesis parameters, the glass transition temperature (Tg) of the polymer networks was deliberately varied in a broad range and, as a result, the samples changed their mechanical behavior from very hard and stiff (elastic moduli 4 GPa), through semi-hard and ductile, to very soft and elastic (elastic moduli 0.006 GPa). The mechanical properties were characterized in macroscale (dynamic mechanical analysis; DMA), microscale (quasi-static microindentation hardness testing; MHI) and nanoscale (quasi-static and dynamic nanoindentation hardness testing; NHI). The stiffness-related properties (i.e., storage moduli, indentation moduli and indentation hardness at all length scales) showed strong and statistically significant mutual correlations (all Pearson's correlation coefficients r > 0.9 and corresponding p-values < 0.001). Moreover, the relations among the stiffness-related properties were approximately linear, in agreement with the theoretical prediction. The viscosity-related properties (i.e., loss moduli, damping factors, indentation creep and elastic work of indentation at all length scales) reflected the stiff-ductile-elastic transitions. The fact that the macro-, micro- and nanomechanical properties exhibited the same trends and similar values indicated that not only dynamic, but also quasi-static indentation can be employed as an alternative to well-established DMA characterization of polymer networks.
- Klíčová slova
- crosslinked polymers, depth-sensing indentation, glass transition temperature, microindentation, nanoindentation, soft elastic rubbers, stiff vitrified networks,
- Publikační typ
- časopisecké články MeSH
