Preparation and Characterization of New Bioplastics Based on Polybutylene Succinate (PBS).

Sea and environmental pollution due to microplastics are global problems that in recent years have attracted particular interest in the scientific community. The increase in the world population and the consequent consumerism of non-reusable materials are amplifying these problems. In this manuscript, we present novel bioplastics, which are completely biodegradable, for their potential use in food packaging, to replace fossil-fuel-derived plastic films and slow food degradation due to oxidative processes or microbial contamination. In this study, thin films based on polybutylene succinate (PBS) were prepared to reduce pollution, and different percentages by weight (1, 2 and 3 wt%) of extra virgin olive oil (EVO) and coconut oil (CO) were included to improve the chemico-physical properties of the polymer and possibly improve the functionality of the films in terms of prolonged food preservation. Attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectroscopy was used to evaluate the interactions between the polymer and the oil. Furthermore, the mechanical properties and thermal behavior of the films were evaluated as a function of the oil content. A scanning electron microscopy (SEM) micrograph showed the surface morphology and the thickness of the materials. Finally, apple and kiwi were selected for a food-contact test, and the wrapped sliced fruit was monitored and evaluated for 12 days to macroscopically evaluate the oxidative process and/or eventually occurring contamination. The films were shown to reduce the browning of sliced fruit due to oxidation, and no molds were evidenced up to 10/12 days of observation with the addition of PBS, with 3 wt% of EVO achieving the best outcomes.

New SiO2/Caffeic Acid Hybrid Materials: Synthesis, Spectroscopic Characterization, and Bioactivity.

The sol-gel route represents a valuable technique to obtain functional materials, in which organic and inorganic members are closely connected. Herein, four hybrid materials, containing caffeic acid entrapped in a silica matrix at 5, 10, 15, and 20 wt.%, were synthesized and characterized through Fourier-Transform Infrared (FT-IR) and Ultraviolet-Visible (UV-Vis) spectroscopy. FT-IR analysis was also performed to evaluate the ability to induce the hydroxyapatite nucleation. Despite some structural changes occurring on the phenol molecular skeleton, hybrid materials showed scavenging properties vs. 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and 2,2'-azinobis-(3-ethylbenzothiazolin-6-sulfonic acid) radical cation (ABTS•+), which was dependent on the tested dose and on the caffeic acid wt.%. The SiO2/caffeic acid materials are proposed as valuable antibacterial agents against Escherichia coli and Enterococcus faecalis.

Chlorogenic acid/PEG-based organic-inorganic hybrids: A versatile sol-gel synthesis route for new bioactive materials.

New organic-inorganic hybrid materials were synthesized by an acid catalysed sol-gel approach, using silicon alkoxide and low molecular weight polyethylene glycol (PEG400) as inorganic and organic precursor, respectively. Chlorogenic acid (CGA), an antioxidant natural phenol compound, enriched further the organic component. Hybrids synthesized, all identical in terms of their starting materials, but differing in terms of their relative proportions, were characterized by means of Fourier Transform InfraRed (FTIR) measurements, UV-Vis spectroscopy, and UHPLC-HRMS analysis. The preservation of the intrinsic chlorogenic acid ability to scavenge, in a dose-dependent manner, radical species was investigated by directly exposing the hybrids to DPPH radical and ABTS radical cation. The relative ratio of both the natural compound and PEG heavily affected the antiradical response, suggesting that chemical interactions in the established network were able, based on components' ratio, to differently mask and/or display the CGA moieties, commonly deemed relevant for antioxidant power exerting. Cell culture MTT assay was used to assess the biocompatibility of hybrid materials towards fibroblast NIH-3 T3 cells and neuroblastoma SH-SY5Y cells. Cells tested appeared differently responsive. In particular, a marked cell viability increase was observed when hybrids with low PEG amount (6%) and high CGA (15%) were directly exposed to fibroblast cells, whose mitochondrial redox activity was negatively affected by hybrid synthesized using the highest organic component rate (both PEG and CGA). Cell viability and morphology of human neuroblastoma SH-SY5Y cells were broadly compromised regardless of organic/inorganic starting materials ratio, suggesting the ability of hybrids to exert pro-oxidant effect towards tumour cells and to selectively interfere with their growth. The hybrids, able to elicit cleverly anti- or proliferative effects, were also shown to be bioactive. In fact, a biologically active hydroxyapatite layer was observed to be formed on the surface of the smart synthesized materials. This feature, which makes them a valuable bonding interface with tissues, opens new scenario aiming at further investigating the employment of natural phenol compounds in versatile sol-gel synthesis routes.

Chlorogenic Acid Entrapped in Hybrid Materials with High PEG Content: A Strategy to Obtain Antioxidant Functionalized Biomaterials?

The formation of pro-oxidant species after implantation of biomaterials could be responsible for the failure of the implant itself, because of oxidative stress-induced damage. In this work, the SiO2/polyethylene glycol (PEG)/chlorogenic acid (CGA) hybrids synthesized by the sol⁻gel method with 50 wt% of the polymer and different amounts of CGA (5, 10, 15 and 20 wt%) were studied. The hybrids soaked in simulated body fluid (SBF) showed the formation of hydroxyapatite layers on their surface, suggesting that the hybrids are bioactive. Their radical scavenging capacity towards DPPH· and ABTS·+ (2,2'-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid), evaluated at three different doses (0.5, 1 and 2 mg), showed probe- and dose-dependent behavior. In addition, the antioxidant properties of CGA were not affected by the presence of high amounts of the polymer. The in vitro biocompatibility in three cell lines (NIH 3T3, HaCaT and SH-SY5Y) was assessed by using the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. Apart from SH-SY5Y, the cell viability-expressed as mitochondrial redox activity percentage of cells directly exposed to powders-and morphology was not affected, suggesting that the hybrids have the ability to interfere and act selectively against tumor cells. The antibacterial properties of the different materials against Escherichia coli and Enterococcus faecalis were affected by different amounts of the natural antioxidant component.

Sol⁻Gel Synthesis of Silica-Based Materials with Different Percentages of PEG or PCL and High Chlorogenic Acid Content.

Implanted biomedical devices can induce adverse responses in the human body, which can cause failure of the implant-referred to as implant failure. Early implant failure is induced numerous factors, most importantly, infection and inflammation. Natural products are, today, one of the main sources of new drug molecules due to the development of pathogenic bacterial strains that possess resistance to more antibiotics used currently in various diseases. The aim of this work is the sol⁻gel synthesis of antibacterial biomedical implants. In the silica matrix, different percentages (6, 12, 24, 50 wt %) of polyethylene glycol (PEG) or poly(ε-caprolactone) (PCL) were embedded. Subsequently, the ethanol solutions with high amounts of chlorogenic acid (CGA 20 wt %) were slowly added to SiO2/PEG and SiO2/PCL sol. The interactions among different organic and inorganic phases in the hybrid materials was studied by Fourier transform infrared (FTIR) spectroscopy. Furthermore, the materials were soaked in simulated body fluid (SBF) for 21 days and the formation of a hydroxyapatite layer on their surface was evaluated by FTIR and XRD analysis. Finally, Escherichia coli and Pseudomonas aeruginosa were incubated with several hybrids, and the diameter of zone of inhibition was observed to assessment the potential antibacterial properties of the hybrids.

Drug Release of Hybrid Materials Containing Fe(II)Citrate Synthesized by Sol-Gel Technique.

The use of oral iron integration is commonly recommended for the treatment of iron deficiency, nevertheless the diagnosis and treatment of this disease could clearly be improved. The aim of this work was the synthesis of therapeutic systems, iron (II) based, by sol-gel method. In an SiO2 matrix, we embedded different weight percentages of polyethylene glycol (PEG6, 12, 24 wt%) and ferrous citrate (Fe(II)C5, 10, 15 wt%) for drug delivery applications. Fourier Transform Infrared (FTIR) spectroscopy was used to study the interactions among different components in the hybrid materials. Release kinetics in a simulated body fluid (SBF) were investigated and the amount of Fe2+ released was detected by Ultraviolet⁻Visible spectroscopy (UV-VIS) after reaction with ortho-phenantroline. Furthermore, the biological characterization was carried out. The bioactivity of the synthesized hybrid materials was evaluated by the formation of a layer of hydroxyapatite on the surface of samples soaked in SBF using FTIR spectroscopy. Finally, also, the potential antibacterial properties of the different materials against two different bacteria, E. coli and P. aeruginosa, were investigated.