Chitosan-based hydrogel beads with molecularly imprinted receptors on halloysite nanotubes for tetracycline separation in water and soil.

Tetracycline (TC), a commonly utilized broad-spectrum antibiotic, is frequently detected in water and soil, posing a significant risk to the natural environment and human health. In the present study, the composite hydrogel beads based on chitosan (CS) and halloysite-supported molecularly imprinted polymers, synthesized by two procedures with significantly different solvent volumes (Hal@MIPa(b)), were obtained and used to adsorb the antibiotic. The presence of Hal improved the thermal stability of the hydrogel beads. The system with a thinner polymer layer (CS_Hal@MIPb), containing polymers produced under conditions of significantly higher reagent dilution, was more resistant to higher temperatures than CS_Hal@MIPa. The adsorptive properties were compared with pure CS beads, those containing incorporated Hal, and free polymers obtained by different protocols (MIPa(b)). In the optimized pH 5.0, the maximum adsorption capacities were 175.24 and 178.05 mg g-1 for CS_Hal@MIPa and CS_Hal@MIPb, respectively. The values were slightly lower compared to the systems with free polymers, but the materials achieved equilibrium more rapidly (12 h). The adsorption process was spontaneous and exothermic. Freundlich isotherm and pseudo-second-order kinetic models most accurately described the experimental data. The hydrogel beads retained high selectivity in the presence of other antibiotics, and their high efficiency in the TC removal from real water samples was maintained. Their addition to soil enhanced adsorption capacities, surpassing that of chitosan-based beads containing free polymers. Significantly, the quantity of TC desorption diminished due to the halloysite's presence, which limited its penetration into groundwater. The primary mechanism of tetracycline adsorption on the hydrogel beads studied is pore filling, but other interactions (hydrogen bonding, π-π stacking, electrostatic attraction) are also involved.

Hybrid chitosan/molecularly imprinted polymer hydrogel beads doped with iron for selective ibuprofen adsorption.

Pharmaceutical pollutants are a group of emerging contaminants frequently found in water streams. In this study, the composite chitosan beads with incorporated molecularly imprinted polymers (monoliths or microparticles) and iron(III) hydroxide were fabricated to remove ibuprofen from aqueous solutions. The adsorptive properties were investigated in different conditions to evaluate the influence of solution pH, adsorbent dose, ibuprofen initial concentration, adsorption time, and temperature. The highest adsorption capacity (79.41 mg g-1), about twice as large as that for the chitosan beads without polymers (39.42 mg g-1), was obtained for the ones containing monoliths imprinted with ibuprofen. The theoretical maximum adsorption capacity of 103.93 mg g-1 was obtained based on the experiments in optimal pH 5. The adsorption of ibuprofen on the hybrid hydrogel beads followed the Freundlich isotherm and pseudo-second-order kinetic models. The process was found as endothermic and thermodynamically spontaneous. The adsorbent with a molecularly imprinted polymer retained its selectivity in the presence of other molecules. The imprinted cavities, chitosan functional groups, and iron hydroxide were presumably responsible for interactions with ibuprofen molecules. Additionally, the effectiveness of the adsorbent did not change significantly in real water samples and remained at a satisfactory level for up to four desorption-adsorption cycles.

Chitosan-Based Nanoparticles with Optimized Parameters for Targeted Delivery of a Specific Anticancer Drug-A Comprehensive Review.

Chitosan is a positively charged polysaccharide obtained through chitin deacetylation. It belongs to a group of biodegradable, bioavailable, and non-toxic materials of natural origin; thus, it is a promising matrix for creating delivery systems of different active agents. Recently, much attention has been paid to nanodelivery systems as carriers to enable better bioavailability, and thus higher efficiency of the loaded drug. The present review is focused on the progress in chitosan-based nanoparticles for the targeted delivery of antitumor drugs. The paper discusses literature reports from the last three years in which chitosan nanoparticles were applied as carriers for active substances used in antitumor therapy and potential new drugs with anticancer properties. Special attention was paid to the different treatments applied to increase the therapeutic effectiveness and minimize the side effects of a specific active substance.

Recent Reports on Polysaccharide-Based Materials for Drug Delivery.

Polysaccharides constitute one of the most important families of biopolymers. Natural polysaccharide-based drug delivery systems are of constant interest to the scientific community due to their unique properties: biocompatibility, non-toxicity, biodegradability, and high availability. These promising biomaterials protect sensitive active agents and provide their controlled release in targeted sites. The application of natural polysaccharides as drug delivery systems is also intensively developed by Polish scientists. The present review focuses on case studies from the last few years authored or co-authored by research centers in Poland. A particular emphasis was placed on the diversity of the formulations in terms of the active substance carried, the drug delivery route, the composition of the material, and its preparation method.

Medicinal Herbs in the Relief of Neurological, Cardiovascular, and Respiratory Symptoms after COVID-19 Infection A Literature Review.

COVID-19 infection causes complications, even in people who have had a mild course of the disease. The most dangerous seem to be neurological ailments: anxiety, depression, mixed anxiety-depressive (MAD) syndromes, and irreversible dementia. These conditions can negatively affect the respiratory system, circulatory system, and heart functioning. We believe that phytotherapy can be helpful in all of these conditions. Clinical trials confirm this possibility. The work presents plant materials (Valeriana officinalis, Melissa officinalis, Passiflora incarnata, Piper methysticum, Humulus lupulus, Ballota nigra, Hypericum perforatum, Rhodiola rosea, Lavandula officinalis, Paullinia cupana, Ginkgo biloba, Murraya koenigii, Crataegus monogyna and oxyacantha, Hedera helix, Polygala senega, Pelargonium sidoides, Lichen islandicus, Plantago lanceolata) and their dominant compounds (valeranon, valtrate, apigenin, citronellal, isovitexin, isoorientin, methysticin, humulone, farnesene, acteoside, hypericin, hyperforin, biapigenin, rosavidin, salidroside, linalool acetate, linalool, caffeine, ginkgolide, bilobalide, mihanimbine, epicatechin, hederacoside C,α-hederine, presegenin, umckalin, 6,7,8-trixydroxybenzopyranone disulfate, fumaroprotocetric acid, protolichesteric acid, aucubin, acteoside) responsible for their activity. It also shows the possibility of reducing post-COVID-19 neurological, respiratory, and cardiovascular complications, which can affect the functioning of the nervous system.

EGDMA- and TRIM-Based Microparticles Imprinted with 5-Fluorouracil for Prolonged Drug Delivery.

Imprinted materials possess designed cavities capable of forming selective interactions with molecules used in the imprinting process. In this work, we report the synthesis of 5-fluorouracil (5-FU)-imprinted microparticles and their application in prolonged drug delivery. The materials were synthesized using either ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TRIM) cross-linkers. For both types of polymers, methacrylic acid was used as a functional monomer, whereas 2-hydroxyethyl methacrylate was applied to increase the final materials' hydrophilicity. Adsorption isotherms and adsorption kinetics were investigated to characterize the interactions that occur between the materials and 5-FU. The microparticles synthesized using the TRIM cross-linker showed higher adsorption properties towards 5-FU than those with EGDMA. The release kinetics was highly dependent upon the cross-linker and pH of the release medium. The highest cumulative release was obtained for TRIM-based microparticles at pH 7.4. The IC50 values proved that 5-FU-loaded TRIM-based microparticles possess cytotoxic activity against HeLa cell lines similar to pure 5-FU, whereas their toxicity towards normal HDF cell lines was ca. three times lower than for 5-FU.

The Electrospray (ESI) and Flowing Atmosphere-Pressure Afterglow (FAPA) Mass Spectrometry Studies of Nitrophenols (Plant Growth Stimulants) Removed Using Strong Base-Functionalized Materials.

The functional silica-based materials functionalized with a strong nitrogen base TBD (SiO2-TBD) deposited via a linker or with a basic poly(amidoamine) dendrimer containing multiple terminal amine groups -NH2 (SiO2-EDA) and functional polymers containing a strong phosphazene base (Polymer-Phosphazene) or another basic poly(amidoamine) dendrimer (PMVEAMA-PAMAM) were tested as sorbents dedicated to a mixture of nitrophenols (p-nitrophenol and 2-methoxy-5-nitrophenol), which are analogs of nitrophenols used in plant growth biostimulants. The adsorptive potential of the studied materials reached 0.102, 0.089, 0.140, and 0.074 g of the nitrophenols g-1, for SiO2-TBD, SiO2-EDA, polymer-phosphazene, and PMVEAMA-PAMAM, respectively. The sorptive efficiency of the analytes, i.e., their adsorption on the functional materials, the desorption from the obtained [(sorbent)H+ - nitrophenolates-] complexes, and interactions with the used soil, were monitored using mass spectrometry (MS) technique with electrospray (ESI) and flowing atmosphere-pressure afterglow (FAPA) ionizations, for the analysis of the aqueous solutions and the solids, respectively. The results showed that the adsorption/desorption progress is determined by the structures of the terminal basic domains anchored to the materials, which are connected with the strength of the proton exchange between the sorbents and nitrophenols. Moreover, the conducted comprehensive MS analyses, performed for both solid and aqueous samples, gave a broad insight into the interactions of the biostimulants and the presented functional materials.

ESR Method in Monitoring of Nanoparticle Endocytosis in Cancer Cells.

Magnetic nanoparticles are extensively studied for their use in diagnostics and medical therapy. The behavior of nanoparticles after adding them to cell culture is an essential factor (i.e., whether they attach to a cell membrane or penetrate the membrane and enter into the cell). The present studies aimed to demonstrate the application of electron spin resonance (ESR) as a suitable technique for monitoring of nanoparticles entering into cells during the endocytosis process. The model nanoparticles were composed of magnetite iron (II, III) oxide core functionalized with organic unit containing nitroxide radical 4-hydroxy-TEMPO (TEMPOL). The research studies included breast cancer cells, as well as model yeast and human microvascular endothelial cells. The results confirmed that the ESR method is suitable for studying the endocytosis process of nanoparticles in the selected cells. It also allows for direct monitoring of radical cellular processes.

ESR as a monitoring method of the interactions between TEMPO-functionalized magnetic nanoparticles and yeast cells.

Potential application of magnetic nanoparticles as drug carriers in medical treatment requires prior determination of their effects on cells. In this work different spin labels and magnetic nanoparticles functionalized with spin labels as well as their interaction with yeast cells were investigated using electron spin resonance (ESR) method. ESR was demonstrated to be a suitable method for monitoring of magnetic core and attached spin labels. Particular emphasis was placed on characterization of endocytosis and redox processes running inside the cell, resulting in recombination of spin labels. Such data could only be obtained at reduced temperature of ESR measurements.

The influence of cross-linking agent onto adsorption properties, release behavior and cytotoxicity of doxorubicin-imprinted microparticles.

Molecularly imprinted polymers (MIPs) are synthetic polymers that possess cavities selective towards their molecular templates and have found many applications in separation science, drug delivery, and catalysis. Here, we report the synthesis of doxorubicin-imprinted microparticles cross-linked with two different compounds (ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate) and examination of their physicochemical properties. During the synthesis methacrylic acid was used as functional monomer and 2-hydroxyethyl methacrylate was added into polymerization mixture to increase hydrophilicity of the obtained materials and therefore improve interactions with aqueous release medium. The influence of initial concentration and contact time onto doxorubicin adsorption by obtained MIPs microparticles have been investigated. The microparticles obtained using ethylene glycol dimethacrylate as a cross-linker showed 3 times higher adsorption properties towards doxorubicin, than the ones obtained using trimethylolpropane trimethacrylate cross-linker. The release kinetics of doxorubicin from drug-loaded MIPs microparticles has been proven to be dependent upon cross-linker used and pH of the release medium. For drug-loaded MIPs microparticles obtained using both cross-linkers the IC50 values measured for cancer cell were comparable to the ones measured for pure doxorubicin, whereas the cytotoxicity towards normal HDF cell lines was lower.

Alginate/PAMAM dendrimer - Halloysite beads for removal of cationic and anionic dyes.

The alginate beads have been widely used for dye removal. However, most of the systems described in literature refer to one type of dyes and the adsorbents of cationic ones are dominant. In this study, the composite alginate beads were prepared and characterized. The system was obtained by encapsulation of polyamidoamine - functionalized halloysite nanotubes in alginate (Alg/Hal_PAMAM beads). The adsorptive properties of the beads towards model dyes - cationic methyl green (MG) and anionic sunset yellow FCF (SY) - were investigated with reference to pH, adsorbent dose, time, dye concentration and temperature. The adsorption capacities were improved compared to pure alginate beads. The kinetic data were best correlated to the pseudo-second-order model. The intraparticle diffusion model showed two (MG) or one (SY) adsorptive steps of mass transport. The Freundlich isotherm model was suitable for describing the adsorption process thus the composite beads were characterized by heterogeneous sites. The thermodynamic parameters indicated the spontaneous and endothermic nature of the adsorption process. It was also found that the process was favorable. Additionally, the beads could be reused with satisfactory removal efficiency in several cycles. Therefore, Alg/Hal_PAMAM beads could be considered as promising material for simultaneous removal of cationic and anionic dyes.

Halloysite nanotubes as carriers of vancomycin in alginate-based wound dressing.

The influence of an inorganic support - halloysite nanotubes - on the release rate and biological activity of the antibiotic encapsulated in alginate-based dressings was studied. The halloysite samples were loaded with approx. 10 wt.% of the antibiotic and then encapsulated in Alginate and Gelatin/Alginate gels. The material functionalized with aliphatic amine significantly extended the release of vancomycin from alginate-based gels as compared to that achieved when silica was used. After 24 h, the released amounts of the antibiotic immobilized at silica reached 70%, while for the drug immobilized at halloysite the released amount of vancomycin reached 44% for Alginate discs. The addition of gelatin resulted in even more prolonged sustained release of the drug. The antibiotic was released from the system with a double barrier with Higuchi kinetic model and Fickian diffusion mechanism. Only the immobilized drug encapsulated in Alginate gel demonstrated very good antimicrobial activity against various bacteria. The inhibition zones were greater than those of the standard discs for the staphylococci and enterococci bacteria tested. The addition of gelatin adversely affected the biological activity of the system. The inhibition zones were smaller than those of the reference samples. A reduction in the drug dose by half had no significant effect on changing the release rate and microbiological activity. The in vivo toxicity studies of the material with immobilized drug were carried out with Acutodesmus acuminatus and Daphnia magna. The material studied had no effect on the living organisms used in the bioassays. The proposed system with a double barrier demonstrated high storage stability.

Will the use of double barrier result in sustained release of vancomycin? Optimization of parameters for preparation of a new antibacterial alginate-based modern dressing.

The aim of this research was to prepare and characterize an alginate-based wound dressing containing vancomycin immobilized at the silica surface. The silica samples functionalized with amine, diol and carboxylic acid groups were loaded with 7.8, 5.7 and 7.1wt.% of the antibiotic respectively. The immobilized drug was encapsulated in alginate or gelatin/alginate gels and the average concentration of vancomycin was about 10mg per g of the dried gel. The effect of functional organic groups at the silica surface on the release rate of the drug was investigated. Only the drug immobilized at Si-amine in alginate matrix was found to demonstrate slower release from the proposed wound dressing. The in vitro release profiles for other silica carriers did not show significant differences in relation to the free loaded drug. The presence of gelatin had a favourable impact on the slowing down of the drug release from the dressing with a double barrier. All the gels studied with vancomycin immobilized at the silica surface demonstrated antimicrobial activity against various bacteria. A reduction of the drug dose to a half had no effect on changing microbiological activity of gels.

SBA-15 Mesoporous Silica Modified with Gallic Acid and Evaluation of Its Cytotoxic Activity.

Gallic acid has been covalently conjugated to SBA-15 mesoporous silica surface through different linkers. Cytotoxic activity of the hybrid organic-inorganic systems against HeLa and KB cell lines has been analyzed. Up to 67% of HeLa or KB tumor cells growth inhibition has been achieved at low silica concentration used (10 µg mL(-1)).

Magnetic scavengers as carriers of analytes for flowing atmospheric pressure afterglow mass spectrometry (FAPA-MS).

In this paper, a procedure for the preconcentration and transport of mixtures of acids, bases, and drug components to a mass spectrometer using magnetic scavengers is presented. Flowing atmospheric pressure afterglow mass spectrometry (FAPA-MS) was used as an analytical method for identification of the compounds by thermal desorption from the scavengers. The proposed procedure is fast and cheap, and does not involve time-consuming purification steps. The developed methodology can be applied for trapping harmful substances in minute quantities, to transport them to specialized, remotely located laboratories.

Vancomycin-modified silica: Synthesis, controlled release and biological activity of the drug.

Vancomycin was immobilized on three different organically functionalized silicas. The materials obtained were used for a controlled release of the antibiotic. The influence of the type of chemical bond on the in vitro drug release was investigated. A weak ionic bonding caused burst release of the drug within one day. A covalent bonding resulted in a slowdown in the release process and uniformity of dosage release. For these two carriers, biological activity of the drug was retained because the minimal inhibitory concentration values against the strains tested were similar to that of a free form of the drug (about 2 µg/mL). A strong ionic bonding of vancomycin adversely affected both the drug release, as well as its biological activity. A strong base on the surface of the silica prevented disconnection of the antibiotic which then became ineffective.

Molecular scavengers as carriers of analytes for mass spectrometry identification.

Storage and preconcentration of various molecules by molecular scavengers for thermal desorption and identification by mass spectrometry is presented. A dielectric barrier discharge ionization source combined with a heating element for the chemical characterization of amines and organic acids, initially trapped by molecular scavengers, is described. The developed technique can be applied for preconcentration of minute amounts of molecules in liquid and gaseous phases, as well as their transportation and thorough analysis. The method, operating at ambient pressure, can also be complementary to electron impact ionization, with no need for sample derivatization.

Double barrier as an effective method for slower delivery rate of ibuprofen.

Ibuprofen (IBU) was chosen as a model drug to investigate the drug delivery rate. Mesoporous MCM-41 has been charged with ibuprofen (MCM-41_IBU). Calcium alginate was applied to encapsulate free drug and the mesoporous material. The system with double barrier demonstrated a slower release of IBU than free ibuprofen-loaded alginate beads and MCM-41_IBU. The IBU release from alginate matrix can be controlled by adjusting the free IBU/MCM-41_IBU ratio.

Synthesis of silica chemically bonded with poly(ethylene oxide) 4-arm, amine-terminated for copper cation removal.

Chemically modified silica containing a poly(ethylene oxide) 4-arm, amine-terminated unit has been obtained in the multi-step synthesis. The synthesized material was characterized by elemental, thermogravimetric analysis and infrared spectroscopy. The surface morphology was analyzed by scanning electron microscopy. The support studied was applied for selective extraction of copper(II) [Cu(II)] from water solutions. The influence of different parameters (pH, amount of the support studied, and contact time) on the copper extraction was investigated. At the optimum conditions, the copper extraction was approximately 90%, significantly greater than that of the other coexisting ions--nickel(II) [Ni(II)], cobalt(II) [Co(II)], and manganese(II) [Mn(II)]. The exception was calcium(II) [Ca(II)], which reached 30% of the extraction percentage. The solid support retained its properties after treatment with different organic and inorganic solvents. The recovery of adsorbed Cu(II) ions was approximately 97%. The sorbent studied can be applied effectively for the pre-concentration of a low level of Cu(II) in the different water samples.