Innovative microwave in situ approach for crystallizing TiO2 nanoparticles with enhanced activity in photocatalytic and photovoltaic applications.

This investigation introduces an innovative approach to microwave-assisted crystallization of titania nanoparticles, leveraging an in situ process to expedite anatase crystallization during microwave treatment. Notably, this technique enables the attainment of crystalline material at temperatures below 100 °C. The physicochemical properties, including crystallinity, morphology, and textural properties, of the synthesized TiO2 nanomaterials show a clear dependence on the microwave crystallization temperature. The presented microwave crystallization methodology is environmentally sustainable, owing to heightened energy efficiency and remarkably brief processing durations. The synthesized TiO2 nanoparticles exhibit significant effectiveness in removing formic acid, confirming their practical utility. The highest efficiency of formic acid photodegradation was demonstrated by the T_200 material, reaching almost 100% efficiency after 30 min of irradiation. Furthermore, these materials find impactful application in dye-sensitized solar cells, illustrating a secondary avenue for the utilization of the synthesized nanomaterials. Photovoltaic characterization of assembled DSSC devices reveals that the T_100 material, synthesized at a higher temperature, exhibits the highest photoconversion efficiency attributed to its outstanding photocurrent density. This study underscores the critical importance of environmental sustainability in the realm of materials science, highlighting that through judicious management of the synthesis method, it becomes feasible to advance towards the creation of multifunctional materials.

Development of a novel LED-IoT photoreactor for enhanced removal of carbamazepine waste driven by solar energy.

This study introduces an innovative LED-IoT photoreactor, representing a significant advancement in response to the demand for sustainable water purification. The integration of LED-IoT installations addresses the challenge of intermittent sunlight availability, employing LEDs with a spectrum mimicking natural sunlight. Passive Infra-Red (PIR) sensors and Internet of things (IoT) technology ensure consistent radiation intensity, with the LED deactivating in ample sunlight and activating in its absence. Utilizing a visible light-absorbing photocatalyst developed through sol-gel synthesis and mild-temperature calcination, this research demonstrates a remarkable carbamazepine removal efficiency exceeding 95% under LED-IoT system illumination, compared to less than 90% efficiency with sunlight alone, within a 6-h exposure period. Moreover, the designed photocatalytic system achieves over 60% mineralization of carbamazepine after 12 h. Notably, the photocatalyst demonstrated excellent stability with no performance loss during five further cycles. Furthermore, integration with renewable energy sources facilitated continuous operation beyond daylight hours, enhancing the system's applicability in real-world water treatment scenarios. A notable application of the LED-IoT system at an operating sewage treatment plant showed nearly 80% efficiency in carbamazepine removal from sewage in the secondary settling tank after 6 h of irradiation, coupled with nearly 40% mineralization efficiency. Additionally, physicochemical analyses such as XPS and STA-FTIR confirm that the carbamazepine photooxidation process does not affect the surface of the photocatalyst, showing no adsorption for degradation products.

Quantification of 2,4-dichlorophenoxyacetic acid in environmental samples using imprinted polyethyleneimine with enhanced selectivity as a selective adsorbent in ambient plasma mass spectrometry.

Detection and quantification of various organic chemicals in the environment is critical to track their fate and control their levels. 2,4-Dichlorophenoxyacetic acid (2,4-D) is a widely applied phenoxy herbicide with potential toxicity to fish and other aquatic organisms. In this study, we address the need for improved detection of 2,4-D by introducing a novel analytical method for its quantification. This method relies on the selective extraction of 2,4-D using MIPs and their subsequent direct analysis using ambient plasma mass spectrometry. During the synthesis, MIPs with various degrees of glycidol (GLY) functionalization were obtained. Experimental data showed that MIPs with no GLY functionalization displayed the highest adsorption capacity. Conversely, MIPs with 30% GLY functionalization exhibited the greatest selectivity for 2,4-D, rendering them valuable for extraction of 2,4-D even in the presence of other contaminants. Finally, the obtained MIPs were applied for quantification of 2,4-D in various water samples through direct analysis using a specially designed ambient plasma mass spectrometry setup. This approach improved the detection limits by 200-fold compared to pure solution analysis. The quantification of 2,4-D in river water samples yielded highly satisfactory recoveries, demonstrating the effective utility of the proposed analytical setup for real-life water sample analysis.

Effects of Spherical and Rod-like Gold Nanoparticles on the Reactivity of Human Peripheral Blood Leukocytes.

Gold nanoparticles (GNPs) are widely used in the technological and biomedical industries, which is a major driver of research on these nanoparticles. The main goal of this study was to determine the influence of GNPs (at 20, 100, and 200 µg/mL concentrations) on the reactivity of human peripheral blood leukocytes. Flow cytometry was used to evaluate the respiratory burst activity and pyroptosis in monocytes and granulocytes following incubation with GNPs for 30 and 60 min. Furthermore, the concentration of interleukin-1ß (IL-1ß) in human blood samples was assessed using enzyme-linked immunosorbent assay (ELISA) after their incubation with GNPs for 24 h. Under the conditions tested in the study, the GNPs did not significantly affect the production of reactive oxygen species in the granulocytes and monocytes that were not stimulated using phorbol 12-myristate 13-acetate (PMA) in comparison to the samples exposed to PMA (p < 0.05). Compared to the control sample, the greatest significant increase in the mean fluorescence intensity of the granulocytes occurred in the samples incubated with CGNPs = 100 and 200 µg/mL for tinc = 30 and 60 min (p < 0.05). From our results, we conclude that the physicochemical properties of the nanoparticles, chemical composition, and the type of nanoparticles used in the unit, along with the unit and incubation time, influence the induced toxicity.

The Influence of TiO2-Lignin Hybrid Fillers in Low-Density Polyethylene Composites on Photocatalytic Performance and UV-Barrier Properties.

The main objective of this study was to discover new packaging materials that could integrate one of the most expected properties, such as UV protection, with a self-cleaning ability defined as photocatalytic performance. Accordingly, new hybrid additives were used to transform LDPE films into materials with complex performance properties. In this study, titanium dioxide-lignin (TL) hybrid systems with a weight ratio of inorganic to organic precursors of 5-1, 1-1, and 1-5 were prepared using a mechanical method. The obtained materials and pristine components were characterized using measurement techniques and research methods, such as Fourier-transform infrared spectroscopy (FTIR), thermal stability analysis (TGA/DTG), measurement of the electrokinetic potential as a function of pH, scanning electron microscopy (SEM), and particle size distribution measurement. It was found that hydrogen bonds were formed between the organic and inorganic components, based on which the obtained systems were classified as class I hybrid materials. In the next step, inorganic-organic hybrid systems and pristine components were used as fillers for a low-density polyethylene (LDPE) composite, 5 and 10% by weight, in order to determine their impact on parameters such as tensile elongation at break. Polymer composites containing titanium dioxide in their matrix were then subjected to a test of photocatalytic properties, based on which it was found that all materials with TiO2 in their structure exhibit photocatalytic properties, whereby the best results were obtained for samples containing the TiO2-lignin hybrid system (1-1). The mechanical tests showed that the thin sheet films had a strong anisotropy due to chill-roll extrusion, ranging from 1.98 to 3.32. UV-Vis spectroscopy revealed four times higher light absorption for composites in which lignin was present than for pure LDPE, in the 250-450 nm range. On the other hand, the temperature at 5% and 30% weight loss revealed by TGA testing increased the highest performance for LDPE/TiO2 materials (by 20.4 °C and 8.7 °C, respectively).

Unraveling the impact of microwave-assisted techniques in the fabrication of yttrium-doped TiO2 photocatalyst.

In this study, we investigate the role of microwave technology in the fabrication of yttrium-doped TiO2 through a comparative analysis of hydrothermal techniques. Microwave-assisted hydrothermal synthesis offers advantages, but a comprehensive comparison between microwave-assisted and conventional methods is lacking. Therefore, in our investigation, we systematically evaluate and compare the morphological, structural, and optical properties of yttrium-doped TiO2 samples synthesized using both techniques. The X-ray diffraction (XRD) patterns confirm the anatase tetragonal structure of the synthesized TiO2-Y systems, while the larger ion radius of yttrium (Y3+) compared to titanium (Ti4+) presents challenges for yttrium to incorporate into the TiO2 lattice. The X-ray Photoelectron Spectroscopy (XPS) revealed a significant difference in the atomic content of yttrium between the TiO2-Y systems synthesized using microwave-assisted and conventional methods. This finding suggests that the rapid microwave method is more effective in successfully doping TiO2 with rare earth metals such as yttrium. The photo-oxidation of carbamazepine (CBZ) using TiO2-Y systems demonstrated high efficiency under UV-LED light. Microwave-synthesized TiO2-Y demonstrates improved photo-oxidation efficiency of CBZ, attributed to enhanced absorption, charge transfer, surface area, and crystallite size. Overall, the microwave-synthesized TiO2-Y systems showed promising performance for the photo-oxidation of CBZ, with improved efficiency compared to conventional synthesis methods.

Recent Developments in the Detection of Organic Contaminants Using Molecularly Imprinted Polymers Combined with Various Analytical Techniques.

Molecularly imprinted polymers (MIPs) encompass a diverse array of polymeric matrices that exhibit the unique capacity to selectively identify a designated template molecule through specific chemical moieties. Thanks to their pivotal attributes, including exceptional selectivity, extended shelf stability, and other distinct characteristics, this class of compounds has garnered interest in the development of highly responsive sensor systems. As a result, the incorporation of MIPs in crafting distinctive sensors and analytical procedures tailored for specific analytes across various domains has increasingly become a common practice within contemporary analytical chemistry. Furthermore, the range of polymers amenable to MIP formulation significantly influences the potential utilization of both conventional and innovative analytical methodologies. This versatility expands the array of possibilities in which MIP-based sensing can be employed in recognition systems. The following review summarizes the notable progress achieved within the preceding seven-year period in employing MIP-based sensing techniques for analyte determination.

Unveiling the Latest Developments in Molecularly Imprinted Photocatalysts: A State-of-the-Art Review.

Responding to the growing concerns about environmental pollutants, scientists are increasingly turning to innovative solutions rooted in the field of environmental science. One such promising avenue combines the robustness of traditional photocatalysis with the precision of molecular imprinting, leading to the proposition of molecularly imprinted photocatalysts (MIPCs). These MIPCs hold the potential to specifically target and eliminate environmental pollutants, marking them as a promising tool in modern environmental remediation. As researchers delve deeper into this field, the design and optimization of MIPCs have become hotbeds for scientific inquiry. This comprehensive overview delves into the multifaceted approaches to MIPC design, elucidating on aspects like the selection of appropriate photocatalytic bases, the pivotal role of templates, the choice of monomeric building blocks, and the integration of effective cross-linking agents. However, as with all burgeoning technologies, the development of MIPCs is not without its challenges. These potential impediments to the successful innovation and implementation of MIPCs are also explored.

Explosives removal and quantification using porous adsorbents based on poly(2-oxazoline)s with various degree of functionalization.

Polymeric porous adsorbents are reported for removal of explosives, namely picric acid, 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN) and their subsequent quantification using direct analysis with ambient plasma mass spectrometry. The adsorbents are obtained by functionalization of short-chain poly(2-oxazoline)s with methyl ester side chains using 4-(aminomethyl)pyridine with a degree of functionalization equal to 0, 5, 10, and 20%. The subsequent step consist of cross-linking using a high internal phase emulsion procedure by further side-chain amidation with diethylenetriamine as crosslinker. Picric acid, RDX, and PETN were chosen as the model compounds as they belong to three different groups of explosives, in particular nitroaromatics, nitroamines, and nitrate esters, respectively. The adsorption isotherms, kinetics, as well as the influence of pH and temperature on the adsorption process was investigated. The porous adsorbents showed the highest maximum adsorption capacity towards picric acid, reaching 334 mg g-1, while PETN (80 mg g-1) and RDX (17.4 mg g-1) were less efficiently adsorbed. Subsequent quantification of the adsorbed explosives is performed by a specially designed ambient mass spectrometry setup equipped with a thermal heater. The obtained limits of detection were found to be 20-times improved compared to direct analysis of analyte solutions. The effectiveness of the proposed analytical setup is confirmed by successful quantification of the explosives in river water samples. The research clearly shows that functional porous adsorbents coupled directly with ambient mass spectrometry can be used for rapid quantification of explosives, which can be, e.g., used for tracking illegal manufacturing sites of these compounds.

Editorial: Advance in Molecularly Imprinted Polymers.

Molecularly imprinted polymers (MIPs), due to their unique recognition properties, have found various applications, mainly in extraction and separation techniques; however, their implementation in other research areas, such as sensor construction and drug delivery, has also been substantial [...].

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.

Rapid quantification of 2,4-dichlorophenol in river water samples using molecularly imprinted polymers coupled to ambient plasma mass spectrometry.

Rapid quantification of environmental pollutants is important for water quality control and environmental monitoring. In this work, we report the development of molecularly imprinted polymers (MIPs) obtained from poly(methyl vinyl ether-alt-maleic acid) polymer. The synthesized materials were used for selective preconcentration of 2,4-dichlorophenol, a priority pollutant which creates a threat to public health. The structure of poly(methyl vinyl ether-alt-maleic acid) was functionalized with 4-aminomethylpyridine (4-AMP) to incorporate pyridine groups presumably responsible for increased affinity towards 2,4-dichlorophenol. The synthesis was performed with different degree (10%, 20% and 30%) of 4-AMP functionalization to investigate the influence of pyridine group content on the final MIPs properties. The molecular imprinting process was conducted by amidation of polymers' anhydride groups with diethylenetriamine. Moreover, the experimental data indicated that maximum adsorption capacity was observed for the highest 4-AMP functionalization degree. Similarly, MIPs with the highest 4-AMP content proved to possess the highest selectivity towards the analyte. Finally, the functionalized MIPs were used to quantify 2,4-dichlorophenol by their direct introduction into a specially designed ambient mass spectrometry setup. The detection limits were improved significantly over the ones measured for pure analyte solution. The proposed analytical technique was used to quantify 2,4-dichlorophenol in river water and wastewater samples. Good recovery results were obtained, which proves that the method can be used for analysis of complex real-life samples.

Poly(2-oxazoline)s as Stimuli-Responsive Materials for Biomedical Applications: Recent Developments of Polish Scientists.

Poly(2-oxazoline)s are the synthetic polymers that are the products of the cationic ring-opening polymerization (CROP) of 2-oxazoline monomers. Due to their beneficial properties, from which biocompatibility, stealth behavior, high functionalization possibilities, low dispersity, stability, nonionic character, and solubility in water and organic solvents should be noted, they have found many applications and gained enormous interest from scientists. Additionally, with high versatility attainable through copolymerization or through post-polymerization modifications, this class of polymeric systems has been widely used as a polymeric platform for novel biomedical applications. The chemistry of polymers significant expanded into biomedical applications, in which polymeric networks can be successfully used in pharmaceutical development for tissue engineering, gene therapies, and also drug delivery systems. On the other hand, there is also a need to create 'smart' polymer biomaterials, responsive to the specified factor, that will be sensitive to various environmental stimuli. The commonly used stimuli-responsive biomedical materials are based mostly on temperature-, light-, magnetic-, electric-, and pH-responsive systems. Thus, creating selective and responsive materials that allow personalized treatment is in the interest of the scientific world. This review article focuses on recent discoveries by Polish scientists working in the field of stimuli-responsive poly(2-oxazoline)s, and their work is compared and contrasted with results reported by other world-renowned specialists.

Mucus-penetrating nanoparticles based on chitosan grafted with various non-ionic polymers: Synthesis, structural characterisation and diffusion studies.

Transmucosal administration offers numerous advantages for drug delivery as it usually helps to avoid first pass metabolism, provides rapid onset of action, and is a non-invasive route. Mucosal surfaces are covered by a viscoelastic mucus gel layer which acts as a protective barrier preventing the entrance of harmful substances into the human tissues. This function of mucus also inhibits the diffusion of drugs and nano-formulations and can result in a significant reduction of their efficacy. The design of mucus-penetrating nanoparticles can overcome the barrier function of mucus which may lead to better therapeutic outcomes. In this study, chitosan was chemically modified by grafting short chains of poly(ethylene glycol), poly(2-hydroxyethyl acrylate), poly(2-ethyl-2-oxazoline), or poly(N-vinyl pyrrolidone) and the resulting chitosan derivatives were used to prepare nanoparticles using an ionic gelation method with sodium tripolyphosphate. These nanoparticles were characterised using dynamic light scattering, transmission electron microscopy, small-angle neutron scattering and nanoparticle tracking analysis. Small-angle neutron scattering data revealed the presence of a large amount of water inside these nanoparticles and lack of a heterogeneous internal structure. The nanogel model with low crosslinking density is suggested as the most feasible model to describe the structure of these nanoparticles. The studies of the behaviour of these nanoparticles in bovine submaxillary mucin solutions and their penetration into sheep nasal mucosa indicated greater diffusivity of modified chitosan nanoparticles compared to unmodified chitosan nanoparticles with the best results achieved for the chitosan grafted with poly(N-vinyl pyrrolidone).

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.

Molecularly Imprinted Polymers as State-of-the-Art Drug Carriers in Hydrogel Transdermal Drug Delivery Applications.

Molecularly Imprinted Polymers (MIPs) are polymeric networks capable of recognizing determined analytes. Among other methods, non-covalent imprinting has become the most popular synthesis strategy for Molecular Imprinting Technology (MIT). While MIPs are widely used in various scientific fields, one of their most challenging applications lies within pharmaceutical chemistry, namely in therapeutics or various medical therapies. Many studies focus on using hydrogel MIPs in transdermal drug delivery, as the most valuable feature of hydrogels in their application in drug delivery systems that allow controlled diffusion and amplification of the microscopic events. Hydrogels have many advantages over other imprinting materials, such as milder synthesis conditions at lower temperatures or the increase in the availability of biological templates like DNA, protein, and nucleic acid. Moreover, one of the most desirable controlled drug delivery applications is the development of stimuli-responsive hydrogels that can modulate the release in response to changes in pH, temperature, ionic strength, or others. The most important feature of these systems is that they can be designed to operate within a particular human body area due to the possibility of adapting to well-known environmental conditions. Therefore, molecularly imprinted hydrogels play an important role in the development of modern drug delivery systems.

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.

Mass Spectrometric Investigation of Organo-Functionalized Magnetic Nanoparticles Binding Properties toward Chalcones.

Chalcones are naturally occurring compounds exhibiting multiple biological functions related to their structure. The investigation of complexes formed by chalcones, namely 2',4'-dihydroxy-2-methoxychalcone (DH-2-MC) and 2',4'-dihydroxy-3-methoxychalcone (DH-3-MC), with organo-functionalized Fe3O4 magnetic nanoparticles using mass spectrometric techniques is reported. The magnetic nanoparticles were obtained by the silanization of Fe3O4 particles with 3-aminopropyltrimethosysilane, which were subsequently reacted with 3-hydroxybenzaldehyde (3-HBA) or 2-pyridinecarboxaldehyde (2-PCA), resulting in the formation of Schiff base derivatives. The formation of their complexes with chalcones was studied using electrospray (ESI) and flowing atmosphere-pressure afterglow (FAPA) mass spectrometric (MS) ionization techniques. The functional nanoparticles which were synthesized using 3-hydroxybenzaldehyde displayed higher affinity towards examined chalcones than their counterparts obtained using 2-pyridinecarboxaldehyde, which has been proved by both ESI and FAPA techniques. For the examined chalcones, two calibration curves were obtained using the ESI-MS method, which allowed for the quantitative analysis of the performed adsorption processes. The presence of Cu(II) ions in the system significantly hindered the formation of material-chalcone complexes, which was proved by the ESI and FAPA techniques. These results indicate that both mass spectrometric techniques used in our study possess a large potential for the investigation of the binding properties of various functional nanoparticles.

Reduction-Responsive Molecularly Imprinted Poly(2-isopropenyl-2-oxazoline) for Controlled Release of Anticancer Agents.

Trigger-responsive materials are capable of controlled drug release in the presence of a specific trigger. Reduction induced drug release is especially interesting as the reductive stress is higher inside cells than in the bloodstream, providing a conceptual controlled release mechanism after cellular uptake. In this work, we report the synthesis of 5-fluorouracil (5-FU) molecularly imprinted polymers (MIPs) based on poly(2-isopropenyl-2-oxazoline) (PiPOx) using 3,3'-dithiodipropionic acid (DTDPA) as a reduction-responsive functional cross-linker. The disulfide bond of DTDPA can be cleaved by the addition of tris(2-carboxyethyl)phosphine (TCEP), leading to a reduction-induced 5-FU release. Adsorption isotherms and kinetics for 5-FU indicate that the adsorption kinetics process for imprinted and non-imprinted adsorbents follows two different kinetic models, thus suggesting that different mechanisms are responsible for adsorption. The release kinetics revealed that the addition of TCEP significantly influenced the release of 5-FU from PiPOx-MIP, whereas for non-imprinted PiPOx, no statistically relevant differences were observed. This work provides a conceptual basis for reduction-induced 5-FU release from molecularly imprinted PiPOx, which in future work may be further developed into MIP nanoparticles for the controlled release of therapeutic agents.

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.