Hybrid Antibacterial Nanocomposites Based on the Vermiculite/Zinc Oxide-Chlorhexidine.

The hybrid nanocomposite materials based on the vermiculite/zinc oxide-chlorhexidine were prepared in two steps. In the first step the vermiculite/zinc oxide nanocomposite was prepared by the mechanochemical method followed by a heat treatment at 650 °C for 90 min. In the second step the chlorhexidine dihydrochloride was intercalated to the vermiculite/zinc oxide nanocomposite in weight ratio 1:1, 1:2, 1:4, 2:1 and 4:1 (wt%) thereby vermiculite/zinc oxide-chlorhexidine nanocomposites were prepared. Phase analysis, crystal structure, phase transformation, chemical composition and particle size of the prepared hybrid nanocomposite materials were using X-ray diffraction methods, energy dispersive X-ray fluorescence spectroscopy, carbon phase analysis, Fourier transforms infrared spectroscopy and particle size analysis. Antibacterial activity of hybrid nanocomposite materials was investigated on Gram negative (E. coli, P. aeruginos.) and the Gram positive (S. aureus, E. faecalis) bacterial strain and against yeast Candida a. by finding the minimum inhibitory concentration. The hybrid nanocomposite materials exhibit high antibacterial activity after 30 minutes with a long-lasting effect persisting up to 5 days. Dependence of the zinc oxide and chlorhexidine concentration in vermiculite structure on the antibacterial activity was observed.

Synthesis and Antimicrobial Activity of Polyethylene/Chlorhexidine/Vermiculite Nanocomposites.

The set of polyethylene/clay nanocomposites with increasing amount of antimicrobial nanofiller (3, 6 and 10 wt%) was prepared by melt compounding procedure. The antimicrobial drug chlorhexidine diacetate was loaded into natural clay mineral vermiculite and also to its monoionic sodium form and then these organoclay nanofillers were incorporated into polymeric matrix. The structure of prepared organoclays and nanocomposites was studied by X-ray diffraction analysis and Fourier transforms infrared spectroscopy. Further thermal properties of polyethylene/clay nanocomposites were investigated by thermogravimetric analysis and the surface roughness was evaluated by atomic force microscopy. Finally, organoclays and polyethylene/clay nanocomposites were tested for antimicrobial activity against bacterial strains Staphylococcus aureus, Escherichia coli and yeast Candida albicans. Prepared samples showed a very good antimicrobial activity with long lasting effect. In the case of polyethylene/clay nanocomposites we observed some differences in antimicrobial action between two used antimicrobial nanofillers. These results suggested great potential of using the polymer/clay nanocomposites in the wide range of antimicrobial applications.

Silver/Chitosan Antimicrobial Nanocomposites Coating for Medical Devices: Comparison of Nanofiller Effect Prepared via Chemical Reduction and Biosynthesis.

Medical devices have an essential part in healthcare system in recent years, such as usage of heart valves, several types of stents and implants devices in patients. However, bacterial infection of medical devices causes critical issues for patients due to attachment of bacteria and formation of biofilm onto the medical devices. Therefore, finding an effective antibacterial coating to prevent biofilm formation and infection is our goal. In this study, we developed silver/chitosan nanocomposites for antimicrobial coating system by chemical and green methods using sodium borohydride and linden extract, respectively. Silver is known as a strong inorganic antimicrobial agent to kill bacteria by inactivating enzymes and dysfunction bacterial cell membranes. By immobilizing silver nanoparticles on chitosan biopolymer can prevent agglomeration of nanoparticles, besides it can improve the biocompatibility. We characterized properties of our silver chitosan nanocomposites samples using particle size distribution, ultraviolet-visible spectroscopy, X-ray diffraction analysis and scanning electron microscopy. Effective antimicrobial film preventing biofilm formation on medical devices was designed. Antimicrobial testing confirmed antimicrobial properties however variable for each type of nanosilver.

Comparative Study of Powder Carriers Physical and Structural Properties.

High specific surface area (SSA), porous structure, and suitable technological characteristics (flow, compressibility) predetermine powder carriers to be used in pharmaceutical technology, especially in the formulation of liquisolid systems (LSS) and solid self-emulsifying delivery systems (s-SEDDS). Besides widely used microcrystalline cellulose, other promising materials include magnesium aluminometasilicates, mesoporous silicates, and silica aerogels. Clay minerals with laminar or fibrous internal structures also provide suitable properties for liquid drug incorporation. This work aimed at a comparison of 14 carriers' main properties. Cellulose derivatives, silica, silicates, and clay minerals were evaluated for flow properties, shear cell experiments, SSA, hygroscopicity, pH, particle size, and SEM. The most promising materials were magnesium aluminometasilicates, specifically Neusilin® US2, due to its proper flow, large SSA, etc. Innovative materials such as FujiSil® or Syloid® XDP 3050 were for their properties evaluated as suitable. The obtained data can help choose a suitable carrier for formulations where the liquid phase is incorporated into the solid dosage form. All measurements were conducted by the same methodology and under the same conditions, allowing a seamless comparison of property evaluation between carriers, for which available company or scientific sources do not qualify due to different measurements, conditions, instrumentation, etc.

Hybrid Nanofillers Creating the Stable PVDF Nanocomposite Films and Their Effect on the Friction and Mechanical Properties.

The solvent casting method was used for five types of polyvinylidene difluoride (PVDF) nanocomposite film preparation. The effect of nanofillers in PVDF nanocomposite films on the structural, phase, and friction and mechanical properties was examined and compared with that of the natural PVDF film. The surface topography of PVDF nanocomposite films was investigated using a scanning electron microscope (SEM) and correlative imaging (CPEM, combinate AFM and SEM). A selection of 2D CPEM images was used for a detailed study of the spherulitic morphologies (grains size around 6-10 µm) and surface roughness (value of 50-68 nm). The chemical interactions were evaluated by Fourier transform infrared spectroscopy (FTIR). Dominant polar γ-phase in the original PVDF, PVDF_ZnO and PVDF_ZnO/V, the most stable non-polar α-phase in the PVDF_V_CH nanocomposite film and mixture of γ and α phases in the PVDF_V and PVDF_ZnO/V_CH nanocomposite films were confirmed. Moderately hydrophilic PVDF nanocomposite films with water contact angle values (WCA) in the range of 58°-69° showed surface stability with respect to the Zeta potential values. The effect of positive or negative Zeta-potential values of nanofillers (ζn) on the resulting negative Zeta-potential values (ζ) of PVDF nanocomposite films was demonstrated. Interaction of PVDF chains with hydroxy groups of vermiculite and amino and imino groups of CH caused transformation of γ-phase to α. The friction properties were evaluated based on the wear testing and mechanical properties were evaluated from the tensile tests based on Young's modulus (E) and tensile strength (Rm) values. Used nanofillers caused decreasing of friction and mechanical properties of PVDF nanocomposite material films.

Alkali-Treated Alumina and Zirconia Powders Decorated with Hydroxyapatite for Prospective Biomedical Applications.

The alumina and zirconia surfaces were pretreated with chemical etching using alkaline mixtures of ammonia, hydrogen peroxide and sodium hydroxide, and followed with application of the powder layer of Ca-deficient hydroxyapatite (CDH). The influence of etching bath conditions time and concentration on surface development, chemical composition and morphology of medicinal ceramic powders were studied. The following analyses were performed: morphology (scanning electron microscopy), phase composition (X-ray diffraction analysis), changes in binding interactions and chemical composition (FT-Infrared and Energy dispersive spectroscopies). Both types of etchants did not expose the original phase composition changes or newly created phases for both types of ceramics. Subsequent decoration of the surface with hydroxyapatite revealed differences in the morphological appearance of the layer on both ceramic surfaces. The treated zirconia surface accepted CDH as a flowing layer on the surface, while the alumina was decorated with individual CDH aggregates. The goal of this study was to focus further on the ceramic fillers for polymer-ceramic composites used as a biomaterial in dental prosthetics.

Phase Transformation after Heat Treatment of Cr-Ni Stainless Steel Powder for 3D Printing.

Today, Ni-Cr steel is used for advanced applications in the high-temperature and electrical industries, medical equipment, food industry, agriculture and is applied in food and beverage packaging and kitchenware, automotive or mesh. A study of input steel powder from various stages of the recycling process intended for 3D printing was conducted. In addition to the precise evaluation of the morphology, particle size and composition of the powders used for laser 3D printing, special testing and evaluation of the heat-treated powders were carried out. Heat treatment up to 950 °C in an air atmosphere revealed the properties of powders that can appear during laser sintering. The powders in the oxidizing atmosphere change the phase composition and the original FeNiCr stainless steel changes to a two-phase system of Fe3Ni and Cr2O3, as evaluated by X-ray diffraction analysis. Observation of the morphology showed the separation of the oxidic phase in the sense of a brittle shell. The inner part of the powder particle is a porous compact core. The particle size is generally reduced due to the peeling of the oxide shell. This effect can be critical to 3D printing processing, causing defects on the printed parts, as well as reducing the usability of the precursor powder and can also change the properties of the printed part.

Polyamide 12 Materials Study of Morpho-Structural Changes during Laser Sintering of 3D Printing.

The polyamide (PA)-12 material used for additive manufacturing was studied in aspects of morphology and their structural properties for basic stages received during 3D laser printing. Samples were real, big-scale production powders. The structure of polymer was evaluated from the crystallinity point of view using XRD, FTIR, and DSC methods and from the surface properties using specific surface evaluation and porosity. Scanning electron microscopy was used to observe morphology of the surface and evaluate the particle size and shape via image analysis. Results were confronted with laser diffraction particles size measurement along with an evaluation of the specific surface area. Fresh PA12 powder was found as inhomogeneous in particle size of material with defective particles, relatively high specific surface, high lamellar crystallite size, and low crystallinity. The scrap PA12 crystallinity was about 2% higher than values for fresh PA12 powder. Particles had a very low, below 1 m2/g, specific surface area; particles sintered as twin particles and often in polyhedral shapes.

Development of Novel Thin Polycaprolactone (PCL)/Clay Nanocomposite Films with Antimicrobial Activity Promoted by the Study of Mechanical, Thermal, and Surface Properties.

Infection with pathogenic microorganisms is of great concern in many areas, especially in healthcare, but also in food packaging and storage, or in water purification systems. Antimicrobial polymer nanocomposites have gained great popularity in these areas. Therefore, this study focused on new approaches to develop thin antimicrobial films based on biodegradable polycaprolactone (PCL) with clay mineral natural vermiculite as a carrier for antimicrobial compounds, where the active organic antimicrobial component is antifungal ciclopirox olamine (CPX). For possible synergistic effects, a sample in combination with the inorganic antimicrobial active ingredient zinc oxide was also prepared. The structures of all the prepared samples were studied by X-ray diffraction, FTIR analysis and, predominantly, by SEM. The very different structure properties of the prepared nanofillers had a fundamental influence on the final structural arrangement of thin PCL nanocomposite films as well as on their mechanical, thermal, and surface properties. As sample PCL/ZnOVER_CPX possessed the best results for antimicrobial activity against examined microbial strains, the synergic effect of CPX and ZnO combination on antimicrobial activity was proved, but on the other hand, its mechanical resistance was the lowest.

Tribo-Mechanical Properties of the Antimicrobial Low-Density Polyethylene (LDPE) Nanocomposite with Hybrid ZnO-Vermiculite-Chlorhexidine Nanofillers.

Materials made from low-density polyethylene (LDPE) in the form of packages or catheters are currently commonly applied medical devices. Antimicrobial LDPE nanocomposite materials with two types of nanofillers, zinc oxide/vermiculite (ZnO/V) and zinc oxide/vermiculite_chlorhexidine (ZnO/V_CH), were prepared by a melt-compounded procedure to enrich their controllable antimicrobial, microstructural, topographical and tribo-mechanical properties. X-ray diffraction (XRD) analysis and Fourier transform infrared spectroscopy (FTIR) revealed that the ZnO/V and ZnO/V_CH nanofillers and LDPE interacted well with each other. The influence of the nanofiller concentrations on the LDPE nanocomposite surface changes was studied through scanning electron microscopy (SEM), and the surface topology and roughness were studied using atomic force microscopy (AFM). The effect of the ZnO/V nanofiller on the increase in indentation hardness (HIT) was evaluated by AFM measurements and the Vickers microhardness (HV), which showed that as the concentration of the ZnO/V nanofiller increased, these values decreased. The ZnO/V and ZnO/V_CH nanofillers, regardless of the concentration in the LDPE matrix, slightly increased the average values of the friction coefficient (COF). The abrasion depths of the wear indicated that the LDPE_ZnO/V nanocomposite plates exhibited better wear resistance than LDPE_ZnO/V_CH. Higher HV and HIT microhardness values were measured for both nanofillers than the natural LDPE nanocomposite plate. Very positive antimicrobial activity against S. aureus and P. aeruginosa after 72 h was found for both nanofiller types.

Effects of Ultrasound on Zinc Oxide/Vermiculite/Chlorhexidine Nanocomposite Preparation and Their Antibacterial Activity.

Microbial infection and biofilm formation are both problems associated with medical implants and devices. In recent years, hybrid organic-inorganic nanocomposites based on clay minerals have attracted significant attention due to their application potential in the field of antimicrobial materials. Organic drug/metal oxide hybrids exhibit improved antimicrobial activity, and intercalating the above materials into the interlayer of clay endows a long-term and controlled-release behavior. Since antimicrobial activity is strongly related to the structure of the material, ultrasonic treatment appears to be a suitable method for the synthesis of these materials as it can well control particle size distribution and morphology. This study aims to prepare novel, structurally stable, and highly antimicrobial nanocomposites based on zinc oxide/vermiculite/chlorhexidine. The influence of ultrasonic treatment at different time intervals and under different intercalation conditions (ultrasonic action in a breaker or in a Roset's vessel) on the structure, morphology, and particle size of prepared hybrid nanocomposite materials was evaluated by the following methods: scanning electron microscopy, X-ray diffraction, energy dispersive X-ray fluorescence spectroscopy, carbon phase analysis, Fourier transforms infrared spectroscopy, specific surface area measurement, particle size analysis, and Zeta potential analysis. Particle size analyses confirmed that the ultrasonic method contributes to the reduction of particle size, and to their homogenization/arrangement. Further, X-ray diffraction analysis confirmed that ultrasound intercalation in a beaker helps to more efficiently intercalate chlorhexidine dihydrochloride (CH) into the vermiculite interlayer space, while a Roset's vessel contributed to the attachment of the CH molecules to the vermiculite surface. The antibacterial activity of hybrid nanocomposite materials was investigated on Gram negative (Escherichia coli, Pseudomonas aeruginosa) and Gram positive (Staphylococcus aureus, Enterococcus faecalis) bacterial strains by finding the minimum inhibitory concentration. All hybrid nanocomposite materials prepared by ultrasound methods showed high antimicrobial activity after 30 min, with a long-lasting effect and without being affected by the concentration of the antibacterial components zinc oxide (ZnO) and CH. The benefits of the samples prepared by ultrasonic methods are the rapid onset of an antimicrobial effect and its long-term duration.

Carmellose Mucoadhesive Oral Films Containing Vermiculite/Chlorhexidine Nanocomposites as Innovative Biomaterials for Treatment of Oral Infections.

Infectious stomatitis represents the most common oral cavity ailments. Current therapy is insufficiently effective because of the short residence time of topical liquid or semisolid medical formulations. An innovative application form based on bioadhesive polymers featuring prolonged residence time on the oral mucosa may be a solution to this challenge. This formulation consists of a mucoadhesive oral film with incorporated nanocomposite biomaterial that is able to release the drug directly at the target area. This study describes the unique approach of preparing mucoadhesive oral films from carmellose with incorporating a nanotechnologically modified clay mineral intercalated with chlorhexidine. The multivariate data analysis was employed to evaluate the influence of the formulation and process variables on the properties of the medical preparation. This evaluation was complemented by testing the antimicrobial and antimycotic activity of prepared films with the aim of finding the most suitable composition for clinical application. Generally, the best results were obtained with sample containing 20 mg of chlorhexidine diacetate carried by vermiculite, with carmellose in the form of nonwoven textile in its structure. In addition to its promising physicomechanical, chemical, and mucoadhesive properties, the formulation inhibited the growth of Staphylococcus and Candida; the effect was prolonged for tens of hours.

Antibacterial efficiency of vermiculite/chlorhexidine nanocomposites and results of the in vivo test of harmlessness of vermiculite.

Clay minerals have been proposed as very useful materials for modulating drug delivery. These are the commonly used materials in pharmaceutical production both as inorganic carriers or active agents. We focused on the development of suitable long-acting material for local treatment of oral infection where clay minerals act as inorganic drug carriers. Organovermiculites with antibacterial activity were prepared by ion exchange reactions using different concentrations of chlorhexidine diacetate. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal analysis (TGA). The antibacterial activity was evaluated by finding the minimum inhibitory concentration (MIC). All studied organoclays possessed good antibacterial activity after 24h exposure against Escherichia coli, Enterococcus faecalis and particularly against Staphylococcus aureus. Pseudomonas aeruginosa however proved very resistant as only the sample with the highest concentration of CA that successfully inhibited bacterial growth. Furthermore, clay mineral vermiculite was subjected to in vivo toxicological analysis and its influence on gastrointestinal tract during its oral application was investigated. Tissue samples from buccal mucosa, tongue, esophagus, stomach, terminal duodenum, small intestine, caecum, distal colon and liver were subjected to histological examination, both macroscopically and microscopically. Neither systemic nor local reactions were observed. Therefore the toxicity of vermiculite to a mammal model organism can be excluded.

Preparation of novel organovermiculites with antibacterial activity using chlorhexidine diacetate.

The novel antibacterial organovermiculites with different mass ratios of chlorhexidine diacetate (CA) were successfully prepared by ion exchange reactions. The resultant organovermiculites were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal properties of prepared organovermiculites were investigated by simultaneous thermogravimetry (TG) and differential thermal analysis (DTA). The antibacterial activity of prepared organovermiculites against Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa was evaluated by finding minimum inhibitory concentration (MIC). Antibacterial studies showed that the organovermiculites strongly inhibited the growth of variety of microorganisms.