Designing Antioxidant and Antimicrobial Polyethylene Films with Bioactive Compounds/Clay Nanohybrids for Potential Packaging Applications.

In the present work, direct incorporation of bioactive compounds onto the surface and interlayer of nanoclays before their incorporation into the final polymeric film was conducted, based on a green methodology developed by our group that is compatible with food packaging. This will lead to the higher thermal stability and the significant reduction of the loss of activity of the active ingredients during packaging configuration. On this basis, the essential oil (EO) components carvacrol (C), thymol (T) as well as olive leaf extract (OLE), which is used for the first time, were incorporated onto organo-modified montmorillonite (O) or inorganic bentonite (B) through the evaporation/adsorption method. The prepared bioactive nanocarriers were further mixed with low-density polyethylene (LDPE), via melt compounding, in order to prepare films for potential use as fresh fruit and vegetable packaging material. Characterization of the bioactive nanocarriers and films were performed through XRD, TGA, tensile, antimicrobial and antioxidant tests. Films with organically modified montmorillonite loaded with carvacrol (OC), thymol (OT) and olive leaf extract (OOLE) at 5% wt. showed better results in terms of mechanical properties. The films with polyethylene and organically modified montmorillonite loaded with carvacrol or thymol at 20% wt. (PE_OC20 and PE_OT20), as well as with olive leaf extract at 5 or 10 %wt., clay:bioactive substance ratio 1:0.5 and 10% compatibilizer (PE_OOLE5_MA10 and PE_OOLE10_MA10) exhibited the highest antioxidant activity. The resulting films displayed outstanding antimicrobial properties against Gram-negative Escherichia coli (E. coli) with the best results appearing in the films with 10% OC and OT.

Development of Low-Density Polyethylene Films Coated with Phenolic Substances for Prolonged Bioactivity.

The current study proposes an efficient coating methodology for the development of low-density polyethylene (LDPE) films with prolonged bioactivity for food packaging applications. Three natural phenolic-based substances were incorporated at optimized concentrations in methyl-cellulose-based solutions and used as coatings on LDPE films. The amount of surfactant/emulsifier was optimized to control the entrapment of the bioactive substances, minimizing the loss of the substances during processing, and offering prolonged bioactivity. As a result, the growth of Escherichia coli was substantially inhibited after interaction with the coated films, while coated films presented excellent antioxidant activities and maintained their mechanical performance after coating. Considerable bioactivity was observed after up to 7 days of storage in sealed bags in the case of carvacrol- and thymol-coated films. Interestingly, films coated with olive-leaf extract maintained a high level of antimicrobial and antioxidant properties, at least for 40 days of storage.

The Use of Electrochemical Impedance Spectroscopy as a Tool for the In-Situ Monitoring and Characterization of Carbon Nanotube Aqueous Dispersions.

So far, there is no validated technology for characterizing the dispersion and morphology state of carbon nanotubes (CNTs) aqueous dispersions during sonication. Taking advantage of the conductive nature of CNTs, the main hypothesis of the current study is that Electrochemical Impedance Spectroscopy (EIS) is an appropriate technique for the in-situ monitoring and qualification of the dispersion state of CNTs in aqueous media. To confirm our hypothesis, we monitored the Impedance |Z| during the sonication process as a function of type CNTs/admixtures used for the preparation of the aqueous solutions and of crucial process parameters, such as the applied sonication power and duration (i.e., sonication energy). For dispersions above the percolation threshold, a drop of |Z| by approximately seven orders of magnitude was observed, followed by a linear reduction. The dramatic change in |Z| is regarded as an indication of the formation of a conductive path or destruction of an existing one during sonication and can be used to characterize the dispersion and morphology state of CNTs. The results of the EIS provide, straightforwardly and reliably, the required information to create an optimum dispersion protocol for conductive CNT suspensions. The produced dispersions are part of research focusing on the manufacturing of cement-based composite materials with advanced thermoelectric functionalities for energy harvesting. Such dispersions are not only limited to energy harvesting applications but also to applications where functionalities are introduced through the use of conductive-based suspensions.

Development of a Multi-Enzymatic Approach for the Modification of Biopolymers with Ferulic Acid.

A series of polymers, including chitosan (CS), carboxymethylcellulose (CMC) and a chitosan-gelatin (CS-GEL) hybrid polymer, were functionalized with ferulic acid (FA) derived from the enzymatic treatment of arabinoxylan through the synergistic action of two enzymes, namely, xylanase and feruloyl esterase. Subsequently, the ferulic acid served as the substrate for laccase from Agaricus bisporus (AbL) in order to enzymatically functionalize the above-mentioned polymers. The successful grafting of the oxidized ferulic acid products onto the different polymers was confirmed through ultraviolet-visible (UV-Vis) spectroscopy, attenuated total reflectance (ATR) spectroscopy, scanning electron microscopy (SEM) and nuclear magnetic resonance (NMR) spectroscopy. Additionally, an enhancement of the antioxidant properties of the functionalized polymers was observed according to the DDPH and ABTS protocols. Finally, the modified polymers exhibited strong antimicrobial activity against bacterial populations of Escherichia coli BL21DE3 strain, suggesting their potential application in pharmaceutical, cosmeceutical and food industries.

Advanced Glass Fiber Polymer Composite Laminate Operating as a Thermoelectric Generator: A Structural Device for Micropower Generation and Potential Large-Scale Thermal Energy Harvesting.

This study demonstrates for the first time a structural glass fiber-reinforced polymer (GFRP) composite laminate with efficient thermal energy harvesting properties as a thermoelectric generator (TEG). This TEG laminate was fabricated by stacking unidirectional glass fiber (GF) laminae coated with p- and n-type single-wall carbon nanotube (SWCNT) inks via a blade coating technique. According to their thermoelectric (TE) response, the p- and n-type GF-SWCNT fabrics exhibited Seebeck coefficients of +23 and -29 µV/K with 60 and 118 µW/m·K2 power factor values, respectively. The in-series p-n interconnection of the TE-enabled GF-SWCNT fabrics and their subsequent impregnation with epoxy resin effectively generated an electrical power output of 2.2 µW directly from a 16-ply GFRP TEG laminate exposed to a temperature difference (ΔT) of 100 K. Both experimental and modeling work validated the TE performance. The structural integrity of the multifunctional GFRP was tested by three-point bending coupled with online monitoring of the steady-state TE current (Isc) at a ΔΤ of 80 K. Isc was found to closely follow all transitions and discontinuities related to structural damage in the stress/strain curve, thus showing its potential to serve the functions of power generation and damage monitoring.

An Approach toward the Realization of a Through-Thickness Glass Fiber/Epoxy Thermoelectric Generator.

The present study demonstrates, for the first time, the ability of a 10-ply glass fiber-reinforced polymer composite laminate to operate as a structural through-thickness thermoelectric generator. For this purpose, inorganic tellurium nanowires were mixed with single-wall carbon nanotubes in a wet chemical approach, capable of resulting in a flexible p-type thermoelectric material with a power factor value of 58.88 µW/m·K2. This material was used to prepare an aqueous thermoelectric ink, which was then deposited onto a glass fiber substrate via a simple dip-coating process. The coated glass fiber ply was laminated as top lamina with uncoated glass fiber plies underneath to manufacture a thermoelectric composite capable of generating 54.22 nW power output at a through-thickness temperature difference οf 100 K. The mechanical properties of the proposed through-thickness thermoelectric laminate were tested and compared with those of the plain laminates. A minor reduction of approximately 11.5% was displayed in both the flexural modulus and strength after the integration of the thermoelectric ply. Spectroscopic and morphological analyses were also employed to characterize the obtained thermoelectric nanomaterials and the respective coated glass fiber ply.

Effect of Environmental Exposure on the Pore Structure and Transport Properties of Carbon Nanotube-Modified Mortars.

Τhe present study investigates the pore structure and transport properties of carbon nanotube-modified cementitious mortars after exposure to freeze-thaw cycles and immersion to sulfate ion solution (sulfate attack) and compares them to those of un-exposed mortars. The effect of parameters related to carbon nanotube content (within the range of 0.2-0.8 wt.%) and type of dispersant (superplasticizer/surfactant) are investigated. It is found that carbon nanotube inclusion results, overall, in a significant drop of the total porosity before exposure. Results demonstrate that environmental exposure leads to a reduction of the fraction of small diameter pores and a respective increase in capillary porosity for both dispersive agents compared to un-exposed specimens. Diffusion coefficients of nano-modified specimens are lower compared to those of un-modified mortars, both before exposure and after sulfate attack. In the case of freeze-thaw cycling, the diffusion coefficients were found to be higher in carbon nanotube-modified mortars when surfactants were used as dispersants, although with improved gas permeability values.

Structural Properties and Damage Detection Capability of Carbon Nanotube Modified Mortars after Freeze-Thaw.

Here we explore the structural properties and damage sensing of cementitious mortars after a freeze-thaw process (F-T) as a function of nano-modification. For this purpose, carbon nanotubes were added at 0.2-0.8 wt.% cement using two different dispersive agents. F-T resulted in reduced fracture energy in nano-modified specimens prepared using superplasticizer as a dispersant while the opposite held true for the surfactant-containing ones. All nano-modified mortars possessed significantly higher fracture energy compared to the plain specimens after F-T (up to 73% improvement). The acoustic emission activity was lower after F-T, while acoustic emission indicators revealed a more tensile mode of fracture in both plain and nano-modified mortars.

Fibro/chondrogenic differentiation of dental stem cells into chitosan/alginate scaffolds towards temporomandibular joint disc regeneration.

Tissue engineering (TE) may provide effective alternative treatment for challenging temporomandibular joint (TMJ) pathologies associated with disc malpositioning or degeneration and leading to severe masticatory dysfunction. Aim of this study was to evaluate the potential of chitosan/alginate (Ch/Alg) scaffolds to promote fibro/chondrogenic differentiation of dental pulp stem cells (DPSCs) and production of fibrocartilage tissue, serving as a replacement of the natural TMJ disc. Ch/Alg scaffolds were fabricated by crosslinking with CaCl2 combined or not with glutaraldehyde, resulting in two scaffold types that were physicochemically characterized, seeded with DPSCs or human nucleus pulposus cells (hNPCs) used as control and evaluated for cell attachment, viability, and proliferation. The DPSCs/scaffold constructs were incubated for up to 8 weeks and assessed for extracellular matrix production by means of histology, immunofluorescence, and thermomechanical analysis. Both Ch/Alg scaffold types with a mass ratio of 1:1 presented a gel-like structure with interconnected pores. Scaffolds supported cell adhesion and long-term viability/proliferation of DPSCs and hNPCs. DPSCs cultured into Ch/Alg scaffolds demonstrated a significant increase of gene expression of fibrocartilaginous markers (COLI, COL X, SOX9, COM, ACAN) after up to 3 weeks in culture. Dynamic thermomechanical analysis revealed that scaffolds loaded with DPSCs significantly increased storage modulus and elastic response compared to cell-free scaffolds, obtaining values similar to those of native TMJ disc. Histological data and immunochemical staining for aggrecan after 4 to 8 weeks indicated that the scaffolds support abundant fibrocartilaginous tissue formation, thus providing a promising strategy for TMJ disc TE-based replacement.

Preparation, characterization, mechanical, barrier and antimicrobial properties of chitosan/PVOH/clay nanocomposites.

In the current study low molecular weight poly(vinylalcohol) (PVOH) was used to prepare chitosan/PVOH blends and chitosan/PVOH/montmorillonite nanocomposites via a reflux - solution - heat pressing method. The effect of PVOH content and montmorillonite type (hydrophylic vs. organically modified) on the morphology, mechanical, thermomechanical, barrier and antimicrobial properties of the obtained polymer blends and nanocomposite films was studied. Higher amounts of PVOH (20 and 30%) resulted in plasticization of the films, with an increase in the elongation at break and decrease of the stiffness and the strength while effective blending between chitosan and PVOH chains was observed based on the XRD and DMA findings. Addition of PVOH was beneficial for water and oxygen barrier properties of the obtained films while it did not influence the antimicrobial activity of films against the growth of Escherichia coli. Intercalated structures were obtained after the addition of hydrophilic and organo-modified clays leading into stiffening of the nano-modified films and enhancement of their barrier and antimicrobial properties.

Preparation, characterization, mechanical and barrier properties investigation of chitosan-clay nanocomposites.

In the current study the effect of dilution of chitosan acetate solution and of the use of a reflux-solution method on the morphology, the mechanical and water barrier properties of chitosan based nanocomposites is being investigated. Two series of nanocomposite films from two chitosan acetate solutions with 2 w/v% and 1 w/v% in chitosan were prepared, with 3, 5 and 10 wt% Na-montmorillonite (NaMMT) and/or 30 wt% glycerol. Intercalation of NaMMT was more effective in films based on 2 w/v% solutions which presented decreased hydrated crystallinity. Upon NaMMT addition an enhancement was found in stiffness and strength (up to 100%) and a remarkable decrease in the elongation at break (up to 75%) and water vapor permeability (WVP) (up to 65%). This enhancement was less pronounced in 1 w/v% systems. Addition of glycerol had a negative effect on the stiffness, strength and WVP, and a positive effect on the elongation at break and the absorbed water. Compared with the conventional solution cast method, the reflux treatment led to a significant improvement of the tested properties of nanocomposite films.

The shape and the thickness of the anterior cruciate ligament along its length in relation to the posterior cruciate ligament: a cadaveric study.

PURPOSE: The purpose of this study was to evaluate the shape of the native anterior cruciate ligament (ACL) along its length in relation to the posterior cruciate ligament (PCL) and compare it with the size of the 3 commonly used autografts (bone-patellar tendon-bone [BPTB], single-bundle hamstring, and double-bundle hamstring). METHODS: With the knee in extension, we filled the intercondylar notch with paraffin, fixing the cruciate ligaments in their natural position, in 8 cadaveric specimens. The ACL-PCL tissue specimen, embedded in paraffin, was removed en bloc. Gross sections were prepared in the coronal plane and were evaluated histologically. The width, thickness, and cross-sectional area of both the ACL and PCL were determined. The dimensions of the semitendinosus tendon (ST), gracilis tendon (GT), and BPTB grafts were measured and compared with those of the native ACL. RESULTS: The PCL occupies the largest part of the intercondylar area, leaving only a small space for the ACL in knee extension. The ACL midsubstance has a width of 5 mm, resembling a band shape. Only before its tibial insertion does the ACL fan out and take the form of its tibial attachment. The BPTB graft has a thickness of 5.8 mm, whereas the ST and GT grafts have a thickness of 6.25 mm and 4.5 mm, respectively, and are comparable to the midsubstance of the ACL but undersized in the tibial insertion (P = .0016 for BPTB graft, P = .002 for ST graft, and P = .0003 for GT graft). A quadruple-looped ST-GT graft, with a diameter of 8 mm, is oversized in the midsubstance (P = .0002) but fits better in the tibial attachment. CONCLUSIONS: The ACL midsubstance has a width of 5 mm, resembling a band shape. Before its tibial insertion, the ACL fans out like a trumpet, taking the form of its wide tibial attachment. CLINICAL RELEVANCE: The dimensions of the native ACL have to be considered in graft selection for anatomic ACL reconstruction.

Cadaveric study of anterior cruciate ligament failure patterns under uniaxial tension along the ligament.

PURPOSE: The purpose of our study was to clarify the events that take place during anterior cruciate ligament (ACL) failure, focusing on the behavior of the ACL as a composition of multiple fibers, during uniaxial tension along the ligament. METHODS: Ten fresh-frozen human cadaveric knee specimens were fixed in an Instron machine (Instron, Norwood, MA), and load was applied parallel to the ACL axis. Two cameras were used to detect the failure mode of the ACL and its different groups of fibers. The distinct bundles of fibers were marked in each specimen before testing. The macroscopic findings during the experiment were used for comparison with the biomechanical results. RESULTS: The ACL showed a non-monotonic response during testing. The load-elongation curve showed a plateau or a second peak after the initial drop in load. Macroscopically, some fibers were failing initially, whereas the intact fibers had a remaining load potential. In our setting, 3 different failure patterns were recognized, specifically, a midsubstance tear of the anteromedial or the posterolateral bundle with a subsequent failure of the intact bundle or an initial avulsion of the anteromedial attachment. Analysis of the video frames showed a direct connection between the failure patterns in the load-elongation curves and the macroscopic sequence of events during ACL failure. CONCLUSIONS: The ACL ligament acts as a multifiber construction. In our setting, rupture follows 3 specific patterns where a complete or partial tear of the fiber bundles occurs first and the remaining intact fiber bundles have a potential load resistance. CLINICAL RELEVANCE: Our study allows a better understanding of the mechanical properties of the ACL. An update on the biomechanics of ACL failure during uniaxial tension after the "double-bundle revolution" could provide data helpful for ACL reconstruction.