Microneedles Based on a Biodegradable Polymer-Hyaluronic Acid.

Transdermal transport can be challenging due to the difficulty in diffusing active substances through the outermost layer of the epidermis, as the primary function of the skin is to protect against the entry of exogenous compounds into the body. In addition, penetration of the epidermis for substances hydrophilic in nature and particles larger than 500 Da is highly limited due to the physiological properties and non-polar nature of its outermost layer, namely the stratum corneum. A solution to this problem can be the use of microneedles, which "bypass" the problematic epidermal layer by dispensing the active substance directly into the deeper layers of the skin. Microneedles can be obtained with various materials and come in different types. Of special interest are carriers based on biodegradable and biocompatible polymers, such as polysaccharides. Therefore, this paper reviews the latest literature on methods to obtain hyaluronic acid-based microneedles. It focuses on the current advancements in this field and consequently provides an opportunity to guide future research in this area.

Metal and Metal Oxides Nanoparticles as Nanofillers for Biodegradable Polymers.

Polymeric materials, despite their many undeniable advantages, nowadays are a major environmental challenge. Thus, in recent years biodegradable polymer matrices have been widely used in various sectors, including the medicinal, chemical, and packaging industry. Their widespread use is due to the properties of biodegradable polymer matrices, among which are their adjustable physicochemical and mechanical properties, as well as lower environmental impact. The properties of biodegradable polymers can be modified with various types of nanofillers, among which clays, organic and inorganic nanoparticles, and carbon nanostructures are most commonly used. The performance of the final product depends on the size and uniformity of the used nanofillers, as well as on their distribution and dispersion in the polymer matrix. This literature review aims to highlight new research results on advances and improvements in the synthesis, physicochemical properties and applications of biodegradable polymer matrices modified with metal nanoparticles and metal oxides.

SBA-15- and SBA-16-Functionalized Silicas as New Carriers of Niacinamide.

Amorphous silica as a food additive (E 551) is used in food materials (e.g., sweeteners, dairy products) for its anti-caking properties. The physicochemical properties of SiO2 also make it suitable to serve as a carrier of active substances in functional foods, dietary supplements, and drugs. Deficiency of niacinamide (vitamin B3, niacin) leads to several pathologies in the nervous system and causes one of the nutritional diseases called pellagra. The present study focuses on the use of hybrid ordered mesoporous silicas (SBA-15/SBA-16) functionalized with amino groups introduced through grafting or co-condensation with (N-vinylbenzyl)aminoethylaminopropyltrimethoxysilane (Z-6032) as novel carriers of niacinamide. They combine the characteristics of a relatively stable and chemically inert amorphous silica matrix with well-defined structural/textural parameters and organic functional groups that give specific chemical properties. The highest degree of carrier loading with niacinamide (16 wt.%) was recorded for the unmodified SBA-15. On the other hand, the highest degree of niacinamide release characterizes the functionalized SBA-15 sample (60% after 24 h), indicating that the presence of amino groups affects the release profile of niacinamide from the structure of the mesoporous silica.

Synthesis and Characterization of Hierarchical Zeolites Modified with Polysaccharides and Its Potential Role as a Platform for Drug Delivery.

Hierarchical zeolites are aluminosilicates with a crystal structure, which next to the micropores possess secondary porosity in the range of mesopores and/or small macropores. Due to their ordered structure and additional secondary porosity, they have aroused great interest among scientists in recent years. Therefore, the present work concerns the synthesis and characterization of hierarchical zeolites with secondary mesoporosity, based on commercial zeolites such as MFI (ZSM-5), BEA (ß) and FAU (Y), and modified with polysaccharides such as inulin, hyaluronic acid, and heparin. All materials were characterized by various analytical techniques and applied as a platform for delivery of selected drug molecules. On the basis of X-ray diffraction (presence of reflections in the 2θ angle range of 1.5-2.5°) and low-temperature nitrogen sorption isotherms (mixture of isotherms of I and IV type) additional secondary porosity was found in the mesopore range. Additional tests were also conducted to determine the possibility of loading selected molecules with biological activity into the aforementioned materials and then releasing them in the therapeutic process. Molecules with different therapeutic options were selected for testing, namely ibuprofen, curcumin, and ferulic acid with anti-inflammatory, potentially anticancer, antioxidant, and skin discoloration activities, respectively. Preliminary studies have confirmed the possibility of using hierarchical zeolites as potential carriers for bioactive molecules, as the loading percentage of active substances ranged from 39-79% and cumulative release for ibuprofen reached almost 100% after 8 h of testing.

KIT-5 Structural and Textural Changes in Response to Different Methods of Functionalization with Sulfonic Groups.

In this project, KIT-5 materials were effectively functionalized with sulfonic groups introduced by grafting or the co-condensation method and tested as heterogeneous solid acid catalyst. A co-condensation procedure leading to the stable, -SO3H functionalized KIT-5 materials was successfully established. Moreover, the influence of both synthesis methods on the structural and textural parameters, as well as surface chemistry, morphology, and catalytic activity of -SO3H/KIT-5 materials was thoroughly investigated. The syntheses with 3-mepkaptopropyltrimethoxysilane (MPTMS) acting as a modifying agent resulted in samples in which functional groups were introduced into the structure and/or onto the mesoporous silica surface. The oxidation stage of -SH to -SO3H groups was carried out under mild conditions, using a "green" oxidant (H2O2). The application of different functionalization techniques and the introduction of different amounts of modifying agent allowed for an evaluation of the influence of these parameters on the ordering of the mesoporous structure of KIT-5 materials. The applied methods of assessment of the physicochemical parameters (XRD, low-temperature N2 sorption, TEM) showed that, especially when the co-condensation method was applied, as the number of functional groups increased, the ordering of structure characteristic of KIT-5 decreased. On the other hand, the samples modified by grafting had a stable structure, regardless of the amount of introduced MPTMS. Test reactions carried out on the basis of Friedel-Crafts alkylation process showed that the synthesized materials can be considered promising acid catalysts in heterogeneous catalysis reactions.

Possibilities of Using Medicinal Plant Extracts and Salt-Containing Raw Materials from the Aral Region for Cosmetic Purposes.

The aim of this work was to study the possibility of using medicinal plants in combination with salt-containing raw materials from the Aral Sea region for cosmetic purposes. The chemical and mineralogical compositions of salts occurring in this region were studied for pharmacological and cosmetic purposes. The salt-containing raw materials were studied by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The microflora of saline-containing raw materials and flora of the Zhaksy-Klych lake were studied. Fifty-six plant species were identified, of which 25% belong to the Asteraceae family, 32% were Poaceae, 22% were Amaranthaceae, and 21% were Tamaricaceae. Using the solid-phase microextraction (SPME) method and comprehensive two-dimensional gas chromatography−mass spectrometry, the composition of volatile compounds in such plant species as Artemisia alba L., Achilleamillifolium L., Eleagus commutate Bernh. Ex Rydb., Psoraleadrupacea Bunge, Artemisia cipa O. Vegd., Thymus vulgaris L., Morus alba L., Salvia pratensis L., Glycyrhizaglabra L., Tanacetum vulgare L., Polygonumaviculare L., Alhagipseudoalhagi Gagnebin and Peganumharmala L., chosen on the basis of their herbal components for future cosmetic products, was determined. In total, 187 different volatile compounds were found in the endemic plant species Glycyrrhizaglabra L., of which the following were dominant: 1,7-octadiene-3-, 2,6-dimethyl- with a peak area of 4.71%; caryophyllenes; bicyclo[7.2.0]4,11,11-trimethyl-8-methylene-, [1R-(1R*,4E,9S*)]­3.70%; bicyclo[2.2.1] heptane-2-1,7,7-trimethyl-,(1S)­3.46%; cyclohexanone, 5-methyl-2-(1-methylethyledene)-; 2-isopropyledene-5­2.97%; menthol; cyclohexanol, 5-methyl-2-(1-methylethyl)-; p-menthane-3-ol; menthol alcohol; and 2-isopropyl-5­2.08%. The remaining compounds were detected in amounts of less than 2.0%. Tests of seven cosmetic compositions developed on the basis of plant extracts and salt-containing raw materials revealed that three samples had a moisturizing effect. Launching the production of cosmetic products in the Aral region will not only reduce social tensions but also significantly improve the environmental situation in the region.

Surface Studies on Glass Powders Used in Commercial Glass-Ionomer Dental Cements.

The surface properties of three commercial ionomer glass powders, i.e., Fuji IX, Kavitan Plus and Chemadent G-J-W were studied. Samples were analyzed by X-ray fluorescence spectroscopy (XRF), and the density was determined by gas pycnometry. Morphology was studied using scanning electron microscopy (SEM) and laser diffraction (LD) technique, whereas low-temperature nitrogen sorption measurements determined textural parameters like specific surface area and pore volume. Thermal transformations in the materials studied were evaluated by thermogravimetric analysis (TGA), which was carried out in an inert atmosphere between 30 °C and 900 °C. XRF showed that Fuji IX and Kavitan Plus powders were strontium-based, whereas Chemadent G-J-W powder was calcium-based. Powders all had a wide range of particle sizes under SEM and LD measurements. Specific surface areas and pore volumes were in the range 1.42-2.73 m2/g and 0.0029 to 0.0083 cm3/g, respectively, whereas densities were in the range 2.6428-2.8362 g/cm3. Thermogravimetric analysis showed that the glass powders lost mass in a series of steps, with Fuji IX powder showing the highest number, some of which are attributed to the dehydration and decomposition of the polyacrylic acid present in this powder. Mass losses were more straightforward for the other two glasses. All three powders showed distinct losses at around 780 °C and 835 °C, suggesting that similar dehydration steps occur in all these glasses. Other steps, which differed between glass powders, are attributed to variations in states of water-binding on their surfaces.

Method development for determination of trace amounts of palladium in environmental water samples by ICP-MS/MS after pre-concentration on thiol-functionalized MCM-41 materials.

The anthropogenic cycle of Pd in the environment, its fate and impact is still unknown due to limitations of measurement techniques. For separation and pre-concentration of Pd(II) ions, mesoporous silica materials MCM-41 were synthesized and functionalized with different amounts of 3-mercaptopropyltrimethoxysilane (MPTMS) by co-condensation and grafting methods. The structural and textural properties of materials were characterized using XRD, TEM, SEM and BET techniques. The results proved that functionalization with thiol groups did not significantly affect structural and textural parameters of synthesized sorbents. The Pd(II) ions were quantitatively retained on sorbents functionalized by grafting in acidic solutions (pH 2), efficiently eluted with 0.1 mol L-1 thiourea solution in 1 mol L-1 HCl and determined by electrothermal atomic absorption spectrometry (ETAAS). The limit of detection (LOD) of the developed SPE ETAAS method was 0.06 ng mL-1, and the pre-concentration factor was 30. For analysis of Pd in environmental water samples inductively coupled plasma mass spectrometry (ICP-MS) in MS/MS mode was used. Spectral interferences on 105Pd caused by the presence of Sr in water samples were eliminated using helium (5 mL min-1) or ammonia (7 mL min-1) gas in collision/reaction cell. The developed SPE ICP-MS method is characterized by good selectivity in the presence of interfering elements and chloride ions and detection limit of 0.0002 ng mL-1. Its accuracy was confirmed by analysis of spiked water samples. The application of ICP-MS together with efficient separation/pre-concentration of analyte on thiol-functionalized MCM-41 sorbents allows to determine Pd in environmental water samples at pg mL-1 level.

Toward Exploiting the Behavior of Niobium-Containing Mesoporous Silicates vs. Polyoxometalates in Catalysis.

Classification of polyoxometalates (POMs) is based on their chemical composition, basically represented by two general formulae: a) [MmOy]p- b) [XxMmOy]q-, where M is the main transition metal, O is the oxygen atom and X can be a non-metal atom such as Si. Additionally, in the most cases, the structure of the polyoxometalates is derived from a combination of octahedral units MO6 with a central metal atom M and the oxygen atoms placed at their corners. In such octahedra, oxygen atoms allow the condensation between two octahedral units, while one oxygen atom (or max. two atoms) makes double bond with the central metal atom and is not shared with other metal atoms within the complex (terminal oxygens). On the other hand, niobium-containing mesoporous silicates contain mainly MO4 tetrahedra and reveal superior activity in heterogeneous catalysis. Thus, the proper coordination of niobium is crucial for the catalytic activity and will be deeply discussed. The similarity in the catalytic behavior of niobium-polyoxometalates and heterogeneous niobium single-site catalysts in selective oxidations will be demonstrated.

Effect of Solvent Variations in the Alcothermal Synthesis of Template-Free Mesoporous Titania for Dye-Sensitized Solar Cells Applications.

A series of 14 mesoporous titania materials has been synthesized using the simple alcothermal template-free method and various alcohols, such as methanol, propanols and butanols, as solvents. All materials were characterized by both wide and small angle XRD, which exhibited the anatase phase with short-range ordered mesoporous structure that is still forming during post synthetic temperature treatment in most of the investigated materials. Nitrogen adsorption-desorption isotherms confirmed the mesoporous structure with surface area ranging from 241 to 383 m2g- 1 and pore volumes from 0.162 to 0.473 m3g-1, UV-Vis diffuse reflectance showed the redshift of the absorption edge and the bandgap decrease after post synthetic calcination of the materials presented. The TEM, FT-IR, DTA and TG measurements have been made to well characterize the materials synthesized. The mesoporous samples obtained were applied as anode materials for dye-sensitized solar cells and showed good activity in photon-to-current conversion process with efficiency values ranging from 0.54% to 4.6% and fill factors in the 52% to 67% range. The photovoltaic performances were not as high as those obtained for the materials synthesized by us earlier employing ethanol as a solvent. The differences in the electron lifetime, calculated from electrochemical impedance spectroscopy results and varying between 4.3 to 17.5 ms, were found as a main factor determining the efficiency of the investigated photovoltaic cells.