Search

This is the pre-print, accepted version of the published paper Nano Energy, Volume 108, April 2023, 108168.

Physical foaming combined with microwave-induced curing was used in this study to develop an innovative device for bone tissue regeneration. In the first step of the process, a stable physical foaming was induced using a surfactant (i.e. pluronic) as blowing agent of a homogeneous blend of Sodium salt of carboxymethylcellulose (CMCNa) and polyethylene glycol diacrylate (PEGDA700) solution. In the second step, the porous structure of the scaffold was chemically stabilized by radical polymerization induced by a homogeneous rapid heating of the sample in a microwave reactor. In this step 2,2-Azobis[2-(2-imidazolin-2 yl)propane]Dihydrochloride was used as thermoinitiator (TI). CMCNa and PEGDA were mixed with different blends to correlate the properties of final product with the composition. The chemical properties of each sample were evaluated by spectroscopy analysis ATR-IR (before and after curing) in order to maximize reaction yield, and optimize kinetic parameters (i.e. time curing, microwave power). The stability of the materials was evaluated in vitro by degradation test in Phosphate Buffered Saline. Biological analyses were performed to evaluate the effect of scaffold materials on cellular behavior in terms of proliferation and early osteogenic differentiation of human Mesenchymal Stem Cells. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 726-733, 2016.

Simple Summary: The aim of this study was to identify new and innovative strategies to improve the tissue-regeneration process. Concentrated growth factor (CGF) is an autologous biomaterial rich in growth factors and multipotent stem cells. The purpose of our study was to evaluate the osteogenic differentiation of CGF primary cells in the presence of a hydroxyapatite–silicon scaffold, which represents a very interesting material in the field of bone reconstructive surgery. Our findings showed that the hydroxyapatite–silicon scaffold provided support to primary CGF cells by enhancing osteogenic differentiation. These data suggest interesting perspectives in the use of CGF together with scaffolds in the field of regenerative medicine. Abstract: The application of scaffolding materials together with stem cell technologies plays a key role in tissue regeneration. Therefore, in this study, CGF (concentrated growth factor), which represents an autologous and biocompatible blood-derived product rich in growth factors and multipotent stem cells, was used together with a hydroxyapatite and silicon (HA-Si) scaffold, which represents a very interesting material in the field of bone reconstructive surgery. The aim of this work was to evaluate the potential osteogenic differentiation of CGF primary cells induced by HASi scaffolds. The cellular viability of CGF primary cells cultured on HA-Si scaffolds and their structural characterization were performed by MTT assay and SEM analysis, respectively. Moreover, the matrix mineralization of CGF primary cells on the HA-Si scaffold was evaluated through Alizarin red staining. The expression of osteogenic differentiation markers was investigated through mRNA quantification by real-time PCR. We found that the HA-Si scaffold was not cytotoxic for CGF primary cells, allowing their growth and proliferation. Furthermore, the HASi scaffold was able to induce increased levels of osteogenic markers, decreased levels of stemness markers in these cells, and the formation of a mineralized matrix. In conclusion, our results suggest that HA-Si scaffolds can be used as a biomaterial support for CGF application in the field of tissue regeneration.

In this work, a time domain reflectometry (TDR)-based system for continuous and diffused monitoring of soil water content in agriculture is presented. The proposed TDR-based system employs elongate sensing elements (SEs). In practical application, each wire-like SE is buried along the cultivation row to be monitored, and through a single TDR measurement it is possible to retrieve the water content profile of the cultivation along the length of the SE. By connecting the TDR-based monitoring system to the irrigation machines, it would be possible to automatically start/stop irrigation based on the actual water requirement of the cultivations, thus favoring precision agriculture and enhancing irrigation efficiency. To demonstrate the feasibility of the proposed monitoring solution, a dedicated hardware+software platform was developed and the TDR-based system was experimented in open-field cultivations.

In this work, tunable nonwoven mats based on poly(3-hydroxybutyrate) (PHB) and type I collagen (Coll) were successfully produced by electrospinning. The PHB/Coll weight ratio (fixed at 100/0, 70/30, and 50/50, resp.) was found to control the morphological, thermal, mechanical, and degradation properties of the mats. Increasing collagen amounts led to larger diameters of the fibers (in the approximate range 600–900 nm), while delaying their thermal decomposition (from 245°C to 262°C). Collagen also accelerated the hydrolytic degradation of the mats upon incubation in aqueous medium at 37°C for 23 days (with final weight losses of 1%, 15%, and 23% for 100/0, 70/30, and 50/50 samples, resp.), as a result of increased mat wettability and reduced PHB crystallinity. Interestingly, 70/30 meshes were the ones displaying the lowest stiffness (~116 MPa; p<0.05 versus 100/0 and 50/50 meshes), while 50/50 samples had an elastic modulus comparable to that of 100/0 ones (~250 MPa), likely due to enhanced physical crosslinking of the collagen chains, at least at high protein amounts. All substrates were also found to allow for good viability and proliferation of murine fibroblasts, up to 6 days of culture. Collectively, the results evidenced the potential of as-spun PHB/Coll meshes for tissue engineering applications.

In the last few years there has been a growing interest in the use of bio-based and biodegradable plastics, made of renewable resources. A common biodegradable polymer, microbial-derived, is Poly-3-hydroxybutiric acid (PHB). However, PHB homopolymer exhibits a high crystalline structure, which leads to mechanical properties that are not fully compatible with a number of production processes. An interesting approach is blending PHB with other compounds in order to improve its physical properties and reducing the production costs of the finished products. The olive mill wastewater (OMW) is an organic-rich residual that arises from the production and refinery of olive oil, mainly composed by aromatic and aliphatic compounds, proteins, sugars and lipids. In addition, some of these compounds exhibit a higher biotoxicity, which makes OMW not suitable for those applications in which biodegradability is required. Nevertheless, OMW is an inexpensive and abundant source of fine chemicals such as polyphenols, leading, after their extraction, to OMW matrix residuals (OMWR) rich in lignin-cellulose. In this work, OMWR was used as a natural filler for the production of PHB based films. PHB/OMWR composite samples were characterized by chemical, thermal, morphological and mechanical analyses. Furthermore, the degradation profiles, in different environments, were evaluated with the aim to develop materials suitable for agriculture and food packaging applications.

In this work, a novel composite sorbent material for water remediation from oily contaminants, based on a cellulose three-dimensional fibrous scaffold treated with stearic acid and expanded graphite flakes, is presented.The pristine cellulose foams are inherently omniphilic, absorbing indiscriminately both water and oils. However, after being modified with stearic acid and graphite via drop casting, they become superhydrophobic (still preserving their superoleophilic characteristics). As a result, the foams start exhibiting a highly selective behaviour which permits to absorb different kinds of oils and organic solvents, while repelling water completely.Thermal and chemical characterizations reveal that the modification treatment is successfully performed, while the performed mechanical tests demonstrate a good recovery of elasticity after repeated deformations and confirm that the elasticity of the foam is preserved after the treatment. Although based on natural materials, the fabricated foams exhibit oil absorption rate, saturation time and capacity values comparable to those of some synthetic materials with the same aim, exhibiting a very important added value, as it is based on low cost, green and biodegradable materials, requiring, at the same time, low processing costs and providing excellent reusability properties. Keywords: Biocomposite, Superhydrophobic, Superhydrophilic, Multifunctional material, Environment

The authors have recently developed a time-domain reflectometry (TDR)-based leak-localisation system which, being based on an electromagnetic technique, overcomes the well-known downsides (sensitivity to environmental noise, to pipe material and geometry etc.) of traditional, electro-acoustic leak-localisation techniques. Starting from the positive results obtained so far, in this work, the authors investigate the possibility of implementing an integrated TDR/ground penetrating radar (TDR/GPR) approach. The TDR would allow the preliminary leak localisation, while the GPR technique would be used to have a countercheck for possible false positives. Also, GPR would allow to assess the quantity of the leaked water (thus scheduling a priority order for repair) and to obtain a three-dimensional view of the subsurface soil around the pipes, so as to assess their health status. In this work, the combined TDR/GPR approach is tested on a pipe section in the presence of two leaks. In addition to this, in this study, also a different configuration of the TDR sensing element (SE) is experimented. As described in what follows, this new SE configuration is expected to expedite considerably the implementation and the use of the TDR-based leak detection system.

Superabsorbent hydrogels are macromolecular networks able to absorb and retain large amounts of water solutions within their fine mesh-like structure. More importantly, they are capable of multiple swelling/shrinking transitions in response to specific environmental cues (e.g., pH, ionic strength, temperature, presence of given electrolytes), thus exhibiting a stimuli-sensitive behavior, which makes them appealing for the design of smart devices in a number of technological fields. In particular, in the last two decades, cellulose-based superabsorbent hydrogels have proven to be an environmentally friendly and cost-effective alternative to acrylamide-based products. This chapter reviews the relationship between the molecular structure of cellulose-based hydrogels and their physicochemical properties. First, the network formation through the use of different cellulose derivatives and chemical or physical crosslinking agents is presented. Successively, the smart swelling capability of the hydrogels as a function of composition and structure is thoroughly discussed. Finally, several approaches to the hydrogel characterization are reviewed, with focus on the assessment of key mechanical, thermal and morphological properties.

Bioactive food-preserving materials are based on the use of a natural antimicrobial compound loaded in a carrier material, which is able to trigger its release when requested and to modulate the rate of release, thus using either toxic or inhibitory properties against pathogens or bacteria due to food decomposition. In this study, the Schiff base formation for chitosan functionalization was achieved by the reaction of chitosan with cinnamaldehyde at different concentrations. Cinnamaldehyde is an aromatic α,β-unsaturated aldehyde, and the major component in essential oils from some cinnamon species. It has been shown to exert antimicrobial action against a large number of microorganisms including bacteria, yeasts, and mould. The formation of the Schiff base is reversible under suitable conditions, and this might allow the release of the active cinnamaldehyde from chitosan, used as the carrier. The reaction kinetics was investigated by means of rheological measurements, while infrared spectroscopy was used to assess the efficacy of the functionalization. The addition of nanometric graphene stacks to the cinnamaldehyde-functionalized chitosan films was evaluated with the aim to increase the mechanical properties of the film. Finally, the films were tested for antifungal properties with bread slices against a selected mould line.

The present work is focused on the design of a bioactive chitosan-based scaffold functionalized with organic and inorganic signals to provide the biochemical cues for promoting stem cell osteogenic commitment. The first approach is based on the use of a sequence of 20 amino acids corresponding to a 68-87 sequence in knuckle epitope of BMP-2 that was coupled covalently to the carboxyl group of chitosan scaffold. Meanwhile, the second approach is based on the biomimetic treatment, which allows the formation of hydroxyapatite nuclei on the scaffold surface. Both scaffolds bioactivated with organic and inorganic signals induce higher expression of an early marker of osteogenic differentiation (ALP) than the neat scaffolds after 3 days of cell culture. However, scaffolds decorated with BMP-mimicking peptide show higher values of ALP than the biomineralized one. Nevertheless, the biomineralized scaffolds showed better cellular behaviour than neat scaffolds, demonstrating the good effect of hydroxyapatite deposits on hMSC osteogenic differentiation. At long incubation time no significant difference among the biomineralized and BMP-activated scaffolds was observed. Furthermore, the highest level of Osteocalcin expression (OCN) was observed for scaffold with BMP2 mimic-peptide at day 21. The overall results showed that the presence of bioactive signals on the scaffold surface allows an osteoinductive effect on hMSC in a basal medium, making the modified chitosan scaffolds a promising candidate for bone tissue regeneration.

The present work deals with the development of a biodegradable superabsorbent hydrogel, based on cellulose derivatives, for the optimization of water resources in agriculture, horticulture and, more in general, for instilling a wiser and savvier approach to water consumption. The sorption capability of the proposed hydrogel was firstly assessed, with specific regard to two variables that might play a key role in the soil environment, that is, ionic strength and pH. Moreover, a preliminary evaluation of the hydrogel potential as water reservoir in agriculture was performed by using the hydrogel in experimental greenhouses, for the cultivation of tomatoes. The soil-water retention curve, in the presence of different hydrogel amounts, was also analysed. The preliminary results showed that the material allowed an efficient storage and sustained release of water to the soil and the plant roots. Although further investigations should be performed to completely characterize the interaction between the hydrogel and the soil, such findings suggest that the envisaged use of the hydrogel on a large scale might have a revolutionary impact on the optimization of water resources management in agriculture.

Alginate micro beads containing Lactobacillus kefiri (the principal bacteria present in the kefir probiotic drink) were produced by a novel technique based on dual aerosols spaying of alginate based solution and CaCl2 as cross linking agent. Carboxymethylcellulose (CMC) has been also added to the alginate in order to change the physic-chemical properties (viscosity and permeability) of the microbeads. Calcium alginate and CMC are biopolymers that can be used for developing oral drug-delivery systems. These biopolymers have been reported to show a pH-dependent swelling behaviour. Calcium alginate and CMC have also been known to possess an excellent mucoadhesive property. The loaded microbeads have been characterized in terms of morphology, chemical composition and stability in different conditions mimicking the gastric environment. In this study, we demonstrate the feasibility of a continuous fabrication of alginate microbeads in a range of 50–70 μm size, encapsulating L. kefiri as active ingredient. The technique involves the use of a double aerosols of alginate based solution and CaCl2 as crosslinking agent. Moreover, the encapsulation process was proved to be effective and not detrimental to bacteria viability. At the same time, it was verified the protective efficacy of the microcapsules against the gastric environment using both SGF pH 1.2 (fasted state) and pH 2.2 (feed state).

Purpose The aim of this project was to study the proliferation and differentiation of human Mesenchymal Stem Cells (hMSCs) onto a cellulose-based hydrogel for bone tissue engineering. Methods Modified-cellulose hydrogel was prepared via double esterification crosslinking using citric acid. The response of hMSCs in terms of cell proliferation and differentiation into osteoblastic phenotype was evaluated by using Alamar blue™ assay and alkaline phosphatase (ALP) activity. Results The results showed that CMCNa and CMCNa_CA have no negative effect on hMSC, adhesion and proliferation. Moreover, the increase of the ALP expression for CMCNa_CA confirms the ability of the hydrogels to support the osteoblastic differentiation. Conclusions The cellulose-based hydrogels have a potential application as filler in bone tissue regeneration.

Rationale and Objectives The aim of this study was to identify the optimal parameter configuration of a new algorithm for fully automatic segmentation of hepatic vessels, evaluating its accuracy in view of its use in a computer system for three-dimensional (3D) planning of liver surgery. Materials and Methods A phantom reproduction of a human liver with vessels up to the fourth subsegment order, corresponding to a minimum diameter of 0.2 mm, was realized through stereolithography, exploiting a 3D model derived from a real human computed tomographic data set. Algorithm parameter configuration was experimentally optimized, and the maximum achievable segmentation accuracy was quantified for both single two-dimensional slices and 3D reconstruction of the vessel network, through an analytic comparison of the automatic segmentation performed on contrast-enhanced computed tomographic phantom images with actual model features. Results The optimal algorithm configuration resulted in a vessel detection sensitivity of 100% for vessels > 1 mm in diameter, 50% in the range 0.5 to 1 mm, and 14% in the range 0.2 to 0.5 mm. An average area overlap of 94.9% was obtained between automatically and manually segmented vessel sections, with an average difference of 0.06 mm 2 . The average values of corresponding false-positive and false-negative ratios were 7.7% and 2.3%, respectively. Conclusions A robust and accurate algorithm for automatic extraction of the hepatic vessel tree from contrast-enhanced computed tomographic volume images was proposed and experimentally assessed on a liver model, showing unprecedented sensitivity in vessel delineation. This automatic segmentation algorithm is promising for supporting liver surgery planning and for guiding intraoperative resections.

Phantoms are commonly used to perform several tasks within the field of medical imaging and radiation therapy. A novel approach to the manufacture of polymeric phantom for tissue mimicking applications by means of stereolithography (SL) is presented. A water solution of polyethylene glycol diacrylate (PEGDA) and a blend of proprietary photoinitiators were used. An SL device was modified with a custom designed elevator- driven build table with the aim of reducing the material volume during the building process. The second step of this work was addressed to the manufacture of a prototype mimicking a simplified vascular system. The prototype was drawn using a computer- aided-design package and the resulting geometric data were used to drive the SL process leading finally to the fabrication a PEGDA phantom. A preliminary echographic study was also carried out to verify the phantom suitability for in in vitro ultrasound contrast agent characterization.

Bioactive food-preserving systems are based on the use of a natural antimicrobial agent loaded in a carrier material, which is able to trigger its release once necessary and to control the rate of release, thereby exerting either lethal or inhibitory effects against food pathogens or spoilage microorganisms. In this study the Schiff base of chitosan was synthesized by the reaction with cinnamaldehyde at different concentrations. Cinnamaldehyde is an aromatic α,s-unsaturated aldehyde, and the major component in essential oils from some cinnamon species. It has been shown to exert antimicrobial activity against a wide range of microorganisms including bacteria, yeasts, and mould. The formation of the Schiff base is reversible under suitable conditions, and this might allow the release of the active cinnamaldehyde from chitosan, used as the carrier. The reaction kinetics was investigated by means of rheological analyses and infrared spectroscopy was used to assess the efficacy of the functionalization. Cinnamaldehyde-functionalized chitosan films were then prepared and tested antifungal properties in vitro. Moreover, the effect of the addition of expanded graphite sonicated stacks was evaluated in term of mechanical properties.

The main aim of this work is the synthesis and characterization of cross-linked chitosan systems. Chitosan hydrogels can be prepared by physical or chemical cross-linking of polymer chains. Chemical cross-linking, leading to the creation of hydrogel networks possessing improved mechanical properties and chemical stability, can be achieved using either synthetic agents or natural-based agents. In this work, the cross-linker Genipin, a naturally derived compound, was selected because of the lower acute toxicity compared to many other commonly used synthetic cross-linking reagents. In particular, the chemical stabilization of chitosan through genipin cross-linking molecules was performed and characterized by calorimetric analyses (differential scanning calorimetry), swelling measurements in different pHs, and ionic strength. The reaction kinetics was carried out by means of rheological measurements, and both the activation energy (Ea) and the reaction order (m) were calculated. The hydrogel analyses were carried out at different concentrations of genipin (GN1 and GN2). The results were used to evaluate the possibility to use the chemical cross-linked chitosan–genipin hydrogel for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42256.

Tissue mimicking phantoms have been widely reported to be an important tool for development, optimisation and performance testing of ultrasound-based diagnostic techniques. In particular, modern applications of tissue mimicking phantoms often include characterisation of the nonlinear behaviour of experimental ultrasound contrast agents. In such cases, the tissue-mimicking materials should be chosen not only based on the values of their density, speed of sound and attenuation coefficient, but also considering their effect on the appearance of "native harmonics" due to nonlinear distortion of ultrasound signal during propagation. In a previous paper it was demonstrated that a cellulose-based hydrogel is suitable to simulate nonlinear acoustical behaviour of liver tissue for thicknesses up to 8 cm. In this paper we present the experimental characterisation of the nonlinear acoustical behaviour of a different polyethylene glycol diacrylate (PEGDA)-based hydrogel, in order to assess whether and how it can improve the performances and overcome some limitations of the cellulose-based hydrogel as liver tissue-mimicking material. Samples of pig liver tissue, cellulose-based hydrogel and PEGDA-based hydrogel were insonified in a through-transmission set-up, employing 2.25-MHz pulses with different mechanical index (MI) values. Second harmonic and first harmonic amplitudes were extracted from the spectra of received signals and their difference was then used to compare sample behaviours. Obtained results show how a new more accurate and combined experimental model of linear and nonlinear acoustical behaviour of liver tissue is feasible. In fact, a further confirmation of the cellulose-based hydrogel effectiveness to precisely simulate the liver tissue for penetration depths up to 8 cm was provided, and it was also shown that the employment of the PEGDA-based hydrogel can extend the range of useful tissue-mimicking material thicknesses up to 11 cm, moreover allowing a considerable improvement of the time stability and behaviour reliability of the corresponding manufactured phantoms.

We sought to characterize the acoustical behavior of the experimental ultrasound contrast agent BR14 by determining the acoustic pressure threshold above which nonlinear oscillation becomes significant and investigating microbubble destruction mechanisms.We used a custom-designed in vitro setup to conduct broadband attenuation measurements at 3.5 MHz varying acoustic pressure (range, 50-190 kPa). We also performed granulometric analyses on contrast agent solutions to accurately measure microbubble size distribution and to evaluate insonification effects.Attenuation did not depend on acoustic pressure less than 100 kPa, indicating this pressure as the threshold for the appearance of microbubble nonlinear behavior. At the lowest excitation amplitude, attenuation increased during insonification, while, at higher excitation levels, the attenuation decreased over time, indicating microbubble destruction. The destruction rate changed with pressure amplitude suggesting different destruction mechanisms, as it was confirmed by granulometric analysis.Microbubbles showed a linear behavior until 100 kPa, whereas beyond this value significant nonlinearities occurred. Observed destruction phenomena seem to be mainly due to gas diffusion and bubble fragmentation mechanisms.