Biomedical Promise of Sustainable Microwave-Engineered Symmetric Curcumin Derivatives.

Curcumin is a polyphenol of the Curcuma longa plant, which can be used for various medicinal purposes, such as inflammation and cancer treatment. In this context, two symmetric curcumin derivatives (D1-(1E,6E)-1,7-bis(4-acetamidophenyl)hepta-1,6-diene-3,5-dione and D2-p,p-dihydroxy di-cinnamoyl methane) were obtained by the microwave-based method and evaluated for their antitumoral effect on human cervix cancer in comparison with toxicity on non-tumoral cells, taking into account that they were predicted to act as apoptosis agonists or anti-inflammatory agents. The HeLa cell line was incubated for 24 and 72 h with a concentration of 50 µg/mL of derivatives that killed almost half of the cells compared to the control. In contrast, these compounds did not alter the viability of MRC-5 non-tumoral lung fibroblasts until 72 h of incubation. The nitric oxide level released by HeLa cells was higher compared to MRC-5 fibroblasts after the incubation with 100 µg/mL. Both derivatives induced the decrease of catalase activity and glutathione levels in cancer cells without targeting the same effect in non-tumoral cells. Furthermore, the Western blot showed an increased protein expression of HSP70 and a decreased expression of HSP60 and MCM2 in cells incubated with D2 compared to control cells. We noticed differences regarding the intensity of cell death between the tested derivatives, suggesting that the modified structure after synthesis can modulate their function, the most prominent effect being observed for sample D2. In conclusion, the outcomes of our in vitro study revealed that these microwave-engineered curcumin derivatives targeted tumor cells, much more specifically, inducing their death.

Ag0-Ginger Nanocomposites Integrated into Natural Hydrogelated Matrices Used as Antimicrobial Delivery Systems Deposited on Cellulose Fabrics.

In the textile, medical, and food industries, many of the applications have targeted the use of textile fabrics with antimicrobial properties. Obtaining eco-friendly coatings is of wide interest, especially for applications related to wound dressing or to food packaging. In order to obtain coatings with antimicrobial properties through environmentally friendly methods, a series of experiments were carried out on the use of natural polymers loaded with silver nanoparticles. In this study, coatings with antimicrobial properties were obtained by depositing natural composites based on rice flour, carob flour, or alginate on cotton fabrics. These antimicrobial coatings were multicomponent systems, in which the host matrix was generated via hydration of natural polymers. The nanocomposite obtained from the phytosynthesis of silver particles in ginger extract was embedded in hydrogel matrices. The multicomponent gels obtained by embedding silver nanoparticles in natural polymer matrices were deposited on cotton fabric and were studied in relation to nanoparticles and the type of host matrix, and the antimicrobial activity was evaluated. Fabrics coated with such systems provide a hydrophilic surface with antimicrobial properties and can therefore be used in various areas where textiles provide antibacterial protection.

Cellulose Fabrics Functionalized with Sol-Gel Photocatalytic Coatings Based on Iron (III) Phthalocyanine Tetracarboxylic Acids-TiO2-Silica Hybrids.

Photocatalytic coatings are difficult to obtain on textile materials because of the sometimes contradictory properties that must be achieved. In order to obtain a high efficiency of a photocatalytic effect, the metal-oxide semiconductor must be found in the vicinity of the coating-air interface in order to come into direct contact with the contaminant species and allow light radiation access to its surface. Another necessary condition is related to the properties of the covering textile material as well as to the stability of the xerogel films to light and wet treatments. In this sense, we proposed a solution based on hybrid silica films generated by sol-gel processes, coatings that contain as a photocatalyst TiO2 sensitized with tetracarboxylic acid of iron (III) phthalocyanine (FeTCPc). The coatings were made by the pad-dry-cure process, using in the composition a bifunctional anchoring agent (3-glycidoxipropyltrimethoxysilane, GLYMO), a crosslinking agent (sodium tetraborate, BORAX), and a catalyst (N-methylimidazole, MIM) for the polymerization of epoxy groups. The photodegradation experiments performed on methylene blue (MB), utilized as a model contaminant, using LED or xenon arc as light sources, showed that the treatment with BORAX improves the resistance of the coatings to wet treatments but worsens their photocatalytic performances.

Properties of Composites Based on Recycled Polypropylene and Silico-Aluminous Industrial Waste.

There is an ever-growing interest in recovering and recycling waste materials due to their hazardous nature to the environment and human health. Recently, especially since the beginning of the COVID-19 pandemic, disposable medical face masks have been a major source of pollution, hence the rise in studies being conducted on how to recover and recycle this waste. At the same time, fly ash, an aluminosilicate waste, is being repurposed in various studies. The general approach to recycling these materials is to process and transform them into novel composites with potential applications in various industries. This work aims to investigate the properties of composites based on silico-aluminous industrial waste (ashes) and recycled polypropylene from disposable medical face masks and to create usefulness for these materials. Polypropylene/ash composites were prepared through melt processing methods, and samples were analyzed to get a general overview of the properties of these composites. Results showed that the polypropylene recycled from face masks used together with silico-aluminous ash can be processed through industrial melt processing methods and that the addition of only 5 wt% ash with a particle size of less than 90 µm, increases the thermal stability and the stiffness of the polypropylene matrix while maintaining its mechanical strength. Further investigations are needed to find specific applications in some industrial fields.

Sponges from Plasma Treated Cellulose Nanofibers Grafted with Poly(ethylene glycol)methyl Ether Methacrylate.

In this work, cellulose nanofibers (CNF) were surface treated by plasma and grafted with poly(ethylene glycol)methyl ether methacrylate (PEGMMA) for increasing mechanical strength and hydrophobicity. The surface characteristics of the sponges were studied by scanning electron microscopy, micro-computed tomography, and Fourier transform infrared spectroscopy, which demonstrated successful surface modification. Plasma treatment applied to CNF suspension led to advanced defibrillation, and the resulting sponges (CNFpl) exhibited smaller wall thickness than CNF. The grafting of PEGMMA led to an increase in the wall thickness of the sponges and the number of larger pores when compared with the non-grafted counterparts. Sponges with increased hydrophobicity demonstrated by an almost 4 times increase in the water contact angle and better mechanical strength proved by 2.5 times increase in specific compression strength were obtained after PEGMMA grafting of plasma treated CNF. Cells cultivated on both neat and PEGMMA-grafted CNF sponges showed high viability (>99%). Remarkably, CNF grafted with PEGMMA showed better cell viability as compared with the untreated CNF sample; this difference is statistically significant (p < 0.05). In addition, the obtained sponges do not trigger an inflammatory response in macrophages, with TNF-α secretion by cells in contact with CNFpl, CNF-PEGMMA, and CNFpl-PEGMMA samples being lower than that observed for the CNF sample. All these results support the great potential of cellulose nanofibers surface treated by plasma and grafted with PEGMMA for biomedical applications.

Nanofibrous scaffolds based on bacterial cellulose crosslinked with oxidized sucrose.

In this work, oxidized sucrose (OS), which is a safe bio-based and non-toxic polyaldehyde, was used as a crosslinker in defibrillated bacterial cellulose (BC) sponges obtained by freeze-drying. For mimicking the proteins' crosslinking, BC was first modified with an aminosilane to partially replace the OH groups on the BC surface with more reactive amino groups. Further, the aminosilane-grafted bacterial cellulose (BCA) was crosslinked with OS in different concentrations and thermally cured. Functionalized bacterial celluloses showed a good thermal stability, comparable to that of unmodified cellulose and much improved mechanical properties. A threefold increase in the compression strength was obtained for the BCA scaffold after crosslinking and curing. This was correlated with the uniform pore structure emphasized by the micro-CT and SEM analyses. The OS-crosslinked BCA scaffolds were not cytotoxic and showed a porosity of around 80 %, which was almost 100 % open porosity. This study shows that the crosslinking of aminated BC scaffolds with OS allows the obtaining of 3D cellulose structures with good mechanical properties and high porosity, suitable for soft tissue engineering. The results recommend this new method as an innovative approach to obtaining biomaterial scaffolds that mimic the natural extracellular matrix.

Microfibrillated Cellulose Grafted with Metacrylic Acid as a Modifier in Poly(3-hydroxybutyrate).

This work proposes a new method for obtaining poly(3-hydroxybutyrate) (PHB)/microfibrillated cellulose (MC) composites with more balanced properties intended for the substitution of petroleum-based polymers in packaging and engineering applications. To achieve this, the MC surface was adjusted by a new chemical route to enhance its compatibility with the PHB matrix: (i) creating active sites on the surface of MC with γ-methacryloxypropyltrimethoxysilane (SIMA) or vinyltriethoxysilane (SIV), followed by (ii) the graft polymerization of methacrylic acid (MA). The high efficiency of the SIMA-MA treatment and the lower efficiency in the case of SIV-MA were proven by the changes observed in the Fourier transform infrared FTIR spectra of celluloses. All modified celluloses and the PHB composites containing them showed good thermal stability close to the processing temperature of PHB. SIMA-modified celluloses acted as nucleating agents in PHB, increasing its crystallinity and favoring the formation of smaller spherulites. A uniform dispersion of SIMA-modified celluloses in PHB as a result of the good compatibility between the two phases was observed by scanning electron microscopy and many agglomerations of fibers in the composite with unmodified MC. The dual role of SIMA-MA treatment, as both compatibilizer and plasticizer, was pointed out by mechanical and rheological measurements. This new method to modify MC and obtain PHB/MC composites with more balanced stiffness-toughness properties could be a solution to the high brittleness and poor processability of PHB-based materials.

The Effect of SEBS/Halloysite Masterbatch Obtained in Different Extrusion Conditions on the Properties of Hybrid Polypropylene/Glass Fiber Composites for Auto Parts.

Masterbatches from a linear poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) and halloysite nanotubes (HNT-QM) were obtained in different conditions of temperature and shear using two co-rotating twin-screw extruders. The influence of screw configuration and melt processing conditions on the morpho-structural, thermal and mechanical properties of masterbatches at macro and nanoscale was studied. A good dispersion of halloysite nanotubes and better thermal stability and tensile and nanomechanical properties were obtained at a lower temperature profile and higher screw speed. The effect of masterbatches, the best and worst alternatives, on the properties of a polypropylene (PP)-glass fiber (GF) composite was also evaluated. Double hardness, tensile strength and modulus and four times higher impact strength were obtained for PP/GF composites containing masterbatches compared to pristine PP. However, the masterbatch with the best properties led further to enhanced mechanical properties of the PP/GF composite. A clear difference between the effects of the two masterbatches was obtained by nanoindentation and nanoscratch tests. These analyses proved to be useful for the design of polymer composites for automotive parts, such as bumpers or door panels. This study demonstrated that setting-up the correct processing conditions is very important to obtain the desired properties for automotive applications.

Effect of calcium stearate as a lubricant and catalyst on the thermal degradation of poly(3-hydroxybutyrate).

Poly(3-hydroxybutyrate) (PHB) is a promising substitute to petroleum-based polymers in packaging and biomedical applications provided that its melt processability and degradability are improved. A new method to control the properties of PHB by using cheap calcium stearate (CS) as a lubricant and decomposition catalyst in melt-mixed PHB-CS compounds was first used. CS is composed of a metallic cation, which promotes PHB degradation, and a hydrophobic anion that improves the compatibility with PHB and processability. An environmentally friendly melt mixing technique was employed to obtain the PHB-CS compounds. Incorporation of 0.5 or 5 wt% CS reduced the melt viscosity and molecular weight of PHB, decreased the melting temperature with up to 5 °C, the crystallization temperature with more than 25 °C, and the degradation temperature with 15 and 40 °C, respectively. In small amounts (0.05 wt%), CS improved the processability and mechanical properties of PHB. In higher amount (0.5 wt%), CS slightly improved the Young's modulus, reduced the tensile strength and enhanced degradation. A better control of thermal and mechanical properties of PHB is, thus, possible by using different CS amount and processing conditions. These results are relevant for PHB application in the context of the global transition to biodegradable packaging.

Preliminary Study on Light-Activated Antimicrobial Agents as Photocatalytic Method for Protection of Surfaces with Increased Risk of Infections.

Preventing and controlling the spread of multidrug-resistant (MDR) bacteria implicated in healthcare-associated infections is the greatest challenge of the health systems. In recent decades, research has shown the need for passive antibacterial protection of surfaces in order to reduce the microbial load and microbial biofilm development, frequently associated with transmission of infections. The aim of the present study is to analyze the efficiency of photocatalytic antimicrobial protection methods of surfaces using the new photocatalytic paint activated by light in the visible spectrum. The new composition is characterized by a wide range of analytical methods, such as UV-VIS spectroscopy, electron microscopy (SEM), X-ray powder diffraction (PXRD) or X-ray photoelectron spectroscopy (XPS). The photocatalytic activity in the UV-A was compared with the one in the visible light spectrum using an internal method developed on the basis of DIN 52980: 2008-10 standard and ISO 10678-2010 standard. Migration of metal ions in the composition was tested based on SR EN1186-3: 2003 standard. The new photocatalytic antimicrobial method uses a type of photocatalytic paint that is active in the visible spectral range and generates reactive oxygen species with inhibitory effect against all tested microbial strains.

Influence of TEMPO oxidation on the properties of ethylene glycol methyl ether acrylate grafted cellulose sponges.

In this study, cellulose nanofibers (CNF) obtained via high-pressure microfluidization were 2,6,6-tetra-methylpiperidine-1-oxyl (TEMPO) oxidized (TOCNF) in order to facilitate the grafting of ethylene glycol methyl ether acrylate (EGA). FTIR and XPS analyses revealed a more efficient grafting of EGA oligomers on the surface of TOCNF as compared to the original CNF. As a result, a consistent covering of the TOCNF fibers with EGA oligomers, an increased hydrophobicity and a reduction in porosity were noticed for TOCNF-EGA. However, the swelling ratio of TOCNF-EGA was similar to that of original CNF grafted with EGA and higher than that of TOCNF, because the higher amount of grafted EGA onto oxidized cellulose and the looser structure reduced the contacts between the fibrils and increased the absorption of water. All these results corroborated with a good cytocompatibility and compression strength recommend TOCNF-EGA for applications in regenerative medicine.

Preparation and Characterization of Silica Nanoparticles and of Silica-Gentamicin Nanostructured Solution Obtained by Microwave-Assisted Synthesis.

In this research work, silica nanoparticles and silica-gentamicin nanostructured solution were synthesized by using the microwave-assisted synthesis, in basic medium, using two silane precursors (tetraethylorthosilicate and octyltriethoxysilane) and the antibiotic (gentamicin sulfate). The prepared materials were characterized through Fourier transform infrared (FTIR) spectroscopy, TGA analysis, transmission electron microscopy (TEM), and atomic force microscopy (AFM) to investigate the morphology and structure. Antimicrobial studies of the silica-gentamicin nanostructured solution versus silica nanoparticles were performed against Pseudomonas aeruginosa, Staphylococcus aureus, and Escherichia coli. FTIR spectra showed that the gentamicin has been loaded to the silica nanoparticles. AFM analysis showed that the morphology of the silica-gentamicin nanostructured solution has changed, and agglomerations of particles are present at the surface. Antimicrobial testing, performed using the diffusion method through spot inoculation, indicates that the silica-gentamicin nanostructured solution exhibited activity against the resistant strain. The obtained silica-gentamicin solution can be used as biochemical agent for the prevention and treatment of microorganisms which are deposited on different surfaces (e.g., glass, plastic, ceramic).

Modeling the Properties of Curcumin Derivatives in Relation to the Architecture of the Siloxane Host Matrices.

Research in the field of natural dyes has constantly focused on methods of conditioning curcumin and diversifying their fields of use. In this study, hybrid materials were obtained from modified silica structures, as host matrices, in which curcumin dyes were embedded. The influence of the silica network structure on the optical properties and the antimicrobial activity of the hybrid materials was monitored. By modifying the ratio between phenyltriethoxysilane:diphenyldimethoxysilane (PTES:DPDMES), it was possible to evaluate the influence the organosilane network modifiers had on the morphostructural characteristics of nanocomposites. The nanosols were obtained by the sol-gel method, in acid catalysis. The nanocomposites obtained were deposited as films on a glass support and showed a transmittance value (T measured at 550 nm) of around 90% and reflectance of about 11%, comparable to the properties of the uncovered support. For the coatings deposited on PET (polyethylene terephthalate) films, these properties remained at average values of T550 = 85% and R550 = 11% without significantly modifying the optical properties of the support. The sequestration of the dye in silica networks reduced the antimicrobial activity of the nanocomposites obtained, by comparison to native dyes. Tests performed on Candida albicans fungi showed good results for the two curcumin derivatives embedded in silica networks (11-18 mm) by using the spot inoculation method; in comparison, the alcoholic dye solution has a spot diameter of 20-23 mm. In addition, hybrids with the CA derivative were the most effective (halo diameter of 17-18 mm) in inhibiting the growth of Gram-positive bacteria, compared to the curcumin derivative in alcoholic solution (halo diameter of 21 mm). The results of the study showed that the presence of 20-40% by weight DPDMES in the composition of nanosols is the optimal range for obtaining hybrid films that host curcumin derivatives, with potential uses in the field of optical films or bioactive coatings.

Bio-Based Polyamide 1010 with a Halogen-Free Flame Retardant Based on Melamine-Gallic Acid Complex.

This work aims at developing polyamide 1010 (PA1010) composites with improved fire behavior using a halogen-free flame-retardant system based on melamine (Me) and gallic acid (GA) complexes (MA). The MA complexes were formed by hydrogen bonding, starting from 1:2, 1:1, 2:1 Me:GA molar ratios. PA1010 composites were obtained by melt mixing, followed by compression molding. MA provided a plasticizing effect on the PA1010 matrix by decreasing the glass transition temperature. The influence of MA on PA1010 chain packaging was highlighted in the X-ray diffraction patterns, mainly in the amorphous phase, but affected also the α and γ planes. This was reflected in the dynamic mechanical properties by the reduction of the storage modulus. H-bonds occurrence in MA complexes, improved the efficiency in the gaseous form during fire exposure, facilitating the gas formation and finally reflected in thermal stability, thermo-oxidative stability, LOI results, and vertical burning behavior results. PA1010 containing a higher amount of GA in the complex (MA12) displayed a limiting oxygen index (LOI) value of 33.6%, much higher when compared to neat PA1010 (25.8%). Vertical burning tests showed that all the composites can achieve the V-0 rating in contrast with neat PA1010 that has V-2 classification.

Morpho-Structural, Thermal and Mechanical Properties of PLA/PHB/Cellulose Biodegradable Nanocomposites Obtained by Compression Molding, Extrusion, and 3D Printing.

Biodegradable blends and nanocomposites were produced from polylactic acid (PLA), poly(3-hydroxybutyrate) (PHB) and cellulose nanocrystals (NC) by a single step reactive blending process using dicumyl peroxide (DCP) as a cross-linking agent. With the aim of gaining more insight into the impact of processing methods upon the morphological, thermal and mechanical properties of these nanocomposites, three different processing techniques were employed: compression molding, extrusion, and 3D printing. The addition of DCP improved interfacial adhesion and the dispersion of NC in nanocomposites as observed by scanning electron microscopy and atomic force microscopy. The carbonyl index calculated from Fourier transform infrared spectroscopy showed increased crystallinity after DCP addition in PLA/PHB and PLA/PHB/NC, also confirmed by differential scanning calorimetry analyses. NC and DCP showed nucleating activity and favored the crystallization of PLA, increasing its crystallinity from 16% in PLA/PHB to 38% in DCP crosslinked blend and to 43% in crosslinked PLA/PHB/NC nanocomposite. The addition of DCP also influenced the melting-recrystallization processes due to the generation of lower molecular weight products with increased mobility. The thermo-mechanical characterization of uncross-linked and cross-linked PLA/PHB blends and nanocomposites showed the influence of the processing technique. Higher storage modulus values were obtained for filaments obtained by extrusion and 3D printed meshes compared to compression molded films. Similarly, the thermogravimetric analysis showed an increase of the onset degradation temperature, even with more than 10 °C for PLA/PHB blends and nanocomposites after extrusion and 3D-printing, compared with compression molding. This study shows that PLA/PHB products with enhanced interfacial adhesion, improved thermal stability, and mechanical properties can be obtained by the right choice of the processing method and conditions using NC and DCP for balancing the properties.

Block Copolymer Elastomer with Graphite Filler: Effect of Processing Conditions and Silane Coupling Agent on the Composite Properties.

The control of morphology and interface in poly(styrene-ethylene/butylene-styrene) (SEBS) composites with graphitic fillers is extremely important for the design of piezoresistive sensors for body motion or flexible temperature sensors. The effects of a high amount of graphite (G) and silane coupling agent on the morphology and properties of SEBS composites with anisotropic mechanical properties are reported. The physical and chemical bonding of silane to both G and SEBS surface was proved by EDX and TGA results; this improved interface influenced both the thermal and mechanical properties of the composite. The vinyltriethoxysilane (VS) promoted the formation of char residue and, being tightly bound to both SEBS and G, did not show separate decomposition peak in the TGA curve of composites. The mechanical properties were measured on two perpendicular directions and were improved by both the addition of VS and the increased amount of G; however, the increase of storage modulus due to orientation (from 5 to 15 times depending on the composition and direction of the test) was more important than that provided by the increase of G concentration, which was a maximum of four times that obtained for 15 wt % graphite. A mechanism to explain the influence of G content and treatment on the variation of storage modulus and tan δ depending on the direction of the test was also proposed.

Morphological and Tribological Properties of PMMA/Halloysite Nanocomposites.

From an environmental and cost-effective perspective, a number of research challenges can be found for electronics, household, but especially in the automotive polymer parts industry. Reducing synthesis steps, parts coating and painting, or other solvent-assisted processes, have been identified as major constrains for the existing technologies. Therefore, simple polymer processing routes (mixing, extrusion, injection moulding) were used for obtaining PMMA/HNT nanocomposites. By these techniques, an automotive-grade polymethylmethacrylate (PMMA) was modified with halloysite nanotubes (HNT) and an eco-friendly additive N,N'-ethylenebis(stearamide) (EBS) to improve nanomechanical properties involved in scratch resistance, mechanical properties (balance between tensile strength and impact resistance) without diminishing other properties. The relationship between morphological/structural (XRD, TEM, FTIR) and tribological (friction) properties of PMMA nanocomposites were investigated. A synergistic effect was found between HNT and EBS in the PMMA matrix. The synergy was attained by the phase distribution resulted from the selective interaction between partners and favourable processing conditions. Modification of HNT with EBS improved the dispersion of nanoparticles in the polymer matrix by increasing their interfacial compatibility through hydrogen bonding established by amide groups with aluminol groups. The increased interfacial adhesion further improved the nanocomposite scratch resistance. The PMMA/HNT-EBS nanocomposite had a lower coefficient of friction and lower scratch penetration depth than PMMA/HNT nanocomposite.

On the photocatalytic reduction of MTT tetrazolium salt on the surface of TiO2 nanoparticles: Formazan production kinetics and mechanism.

HYPOTHESIS: The MTT [3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium-bromide] cell cytotoxicity indicator is photocatalytically reduced on the surface of TiO2 nanoparticles in phosphate-buffered-saline (PBS) environment. We hypothesize that specific phosphate adsorption may be used to modulate the efficiency of the TiO2-MTT reaction through colloidal and semiconductor-liquid interface processes. EXPERIMENTS: The TiO2-MTT reaction kinetics was studied in PBS, with respect to photocatalyst and MTT concentrations and irradiation wavelength. The effects of PBS and electron scavengers (Fe(3+) ions) on reaction efficiency and the role of colloidal surface charge in the photocatalytic process were investigated. The structural and spectroscopic characteristics of relevant TiO2-formazan systems were studied by X-ray diffraction, transmission electron microscopy and IR-spectroscopy. FINDINGS: The reaction was pseudo-first order with respect to photocatalyst and showed a negative and fractional partial order with respect to MTT. Formazan production rates were directly proportional to radiation wavelength and TiO2 concentration and inversely proportional to the MTT initial concentration. The addition of Fe(3+) ions, as well as the absence of PBS, induced strong reaction inhibition. Reaction efficiency and catalyst Zeta potential were enhanced by Na2HPO4 (PBS component) and showed a maximum around the phosphate concentration 0.005 M. Structural/spectroscopic characterization confirmed the formation of amorphous MTT-formazan on the surface of TiO2 and the TiO2-phosphate binding.