Pharmaceutical grade bentonite, containing a high amount of montmorillonite, enriched with zinc (Zn) or copper (Cu) (ZnBent and CuBent, respectively) was used as the main component for the creation of formulations for cutaneous use and tested for their antimicrobial capacity. Bentonite (Bent) with added phenoxyethanol (PH) as a preservative and unmodified bentonite were used as control groups. The mineralogical composition, structural state, and physical or chemical properties, before and after the modification of the samples, were characterized utilizing X-ray Diffraction Analysis (XRD), Fourier-Transform Infrared Spectroscopy (FTIR) and X-ray Fluorescence (XRF) techniques, and Scanning Electron Microscope-Energy Dispersive Spectroscopy (SEM, SEM-EDS) analyses. In addition, the profile of zinc and copper concentration from two types of surfaces ZnBent and CuBent, and into Phosphate-Buffered Saline (PBS) are discussed. Finally, the formulations in the form of basic pastes were challenged against bacteria, molds, and yeasts, and their performance was evaluated based on the European Pharmacopeia criteria. The Cu-modified bentonite performed excellently against bacteria and yeasts, while the Zn-modified bentonite only showed great results against yeasts. Therefore, Cu-modified bentonite formulations could offer antimicrobial protection without the use of preservatives.

The main objective of this work was to synthesize composites of polyurethane (PU) with organoclays (OC) exhibiting antimicrobial properties. Layered silicate (saponite) was modified with octadecyltrimethylammonium cations (ODTMA) and functionalized with phloxine B (PhB) and used as a filler in the composites. A unique property of composite materials is the increased concentration of modifier particles on the surface of the composite membranes. Materials of different compositions were tested and investigated using physico-chemical methods, such as infrared spectroscopy, X-ray diffraction, contact angle measurements, absorption, and fluorescence spectroscopy in the visible region. The composition of an optimal material was as follows: n_ODTMA/m_Sap = 0.8 mmol g⁻¹ and n_PhB/m_Sap = 0.1 mmol g⁻¹. Only about 1.5% of present PhB was released in a cultivation medium for bacteria within 24 h, which proved good stability of the composite. Anti-biofilm properties of the composite membranes were proven in experiments with resistant Staphylococcus aureus. The composites without PhB reduced the biofilm growth 100-fold compared to the control sample (non-modified PU). The composite containing PhB in combination with the photodynamic inactivation (PDI) reduced cell growth by about 10,000-fold, thus proving the significant photosensitizing effect of the membranes. Cell damage was confirmed by scanning electron microscopy. A new method of the synthesis of composite materials presented in this work opens up new possibilities for targeted modification of polymers by focusing on their surfaces. Such composite materials retain the properties of the unmodified polymer inside the matrix and only the surface of the material is changed. Although these unique materials presented in this work are based on PU, the method of surface modification can also be applied to other polymers. Such modified polymers could be useful for various applications in which special surface properties are required, for example, for materials used in medical practice.

Six pharmaceutical pastes were prepared using chemically modified kaolin and talc powders. Tests were conducted to determine their structural and chemical characteristics as well as their antimicrobial protection, thus rendering them suitable for cosmetic and pharmaceutical uses. Kaolin and talc were treated chemically via the cation exchange method to load the clay particles with copper and zinc ions, two cations well known for their antimicrobial properties. Mineralogical analyses were conducted by using X-ray diffraction (XRD) before and after the modification, confirming the mineralogical purity of the samples. Scanning electron microscopy was also used in conjunction with energy dispersed spectroscopy (SEM-EDS) to obtain chemical mapping images, revealing the dispersion of the added metals upon the clay minerals surfaces. Moreover, chemical analysis has been performed (XRF) to validate the enrichment of the clays with each metal utilizing the cation exchange capacity. All modified samples showed the expected elevated concentration in copper or zinc in comparison to their unmodified versions. From the X-ray photoelectron spectroscopy (XPS), the chemical state of the samples’ surfaces was investigated, revealing the presence of salt compounds and indicating the oxidation state of adsorbed metals. Finally, the resistance of pastes in microbial growth when challenged with bacteria, molds, and yeasts was assessed. The evaluation is based on the European Pharmacopeia (EP) criteria.

Polymer/layered silicate composites have gained huge attention in terms of research and industrial applications. Traditional nanocomposites contain particles regularly dispersed in a polymer matrix. In this work, a strategy for the formation of a composite thin film on the surface of a polycaprolactone (PCL) matrix was developed. In addition to the polymer, the composite layer was composed of the particles of saponite (Sap) modified with alkylammonium cations and functionalized with methylene blue. The connection between the phases of modified Sap and polymer was achieved by fusing the chains of molten polymer into the Sap film. The thickness of the film of several μm was confirmed using electron microscopy and X-ray tomography. Surfaces of precursors and composite materials were analyzed in terms of structure, composition, and surface properties. The penetration of polymer chains into the silicate, thus joining the phases, was confirmed by chemometric analysis of spectral data and changes in some properties upon PCL melting. Ultimately, this study was devoted to the spectral properties and photoactivity of methylene blue present in the ternary composite films. The results provide directions for future research aimed at the development of composite materials with photosensitizing, photodisinfection, and antimicrobial surfaces.