Burn wounds present significant clinical challenges due to high infection risk, delayed healing, and extensive tissue damage. The development of biomimetic skin substitutes capable of simultaneously supporting tissue regeneration and preventing infection remains a critical need in burn wound management. In this study, a novel ceragenin (CSA-44)-loaded tri-layered skin substitute was developed to mimic the epidermis, dermis, and hypodermis and address both wound healing and infection prevention simultaneously. The substitute comprised a poly(ε-caprolactone) (PCL) film as the upper layer, polyvinyl alcohol (PVA)/sodium alginate (SA)-PCL nanofibers as the middle layer, and a CSA-44-loaded PVA/Gelatin (Gel) hydrogel as the bottom layer. The tri-layered scaffold exhibited a hierarchical porous architecture, high swelling capacity (557.75% ± 52.87%), controlled degradation behavior, and a water vapor transmission rate of 2514.92 ± 63.41 g/m2/day, indicating suitability for maintaining a moist wound environment. Drug release studies demonstrated controlled CSA-44 delivery, with 92.26% ± 6.90% cumulative release after 180 min. The scaffold exhibited strong antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and methicillin-resistant S. aureus (MRSA), with complete inhibition observed within minutes. Cytocompatibility studies using human keratinocyte (HaCaT) cells demonstrated that the ceragenin-loaded scaffold maintained acceptable cell viability within the tested concentration range. In addition, co-culture experiments with HaCaT and human umbilical vein endothelial (HUVEC) cells revealed enhanced endothelial tube formation, suggesting a favorable microenvironment for angiogenic signaling. The results suggested that the ceragenin-loaded tri-layered skin substitute holds promise as a multifunctional biomaterial for burn wound management by combining antimicrobial efficacy and tissue regeneration capability.
Phthalates (PAEs) are a group of chemicals widely used as plasticizers in various industrial and consumer products. Due to their extensive use and potentially harmful effects on human health, particularly as endocrine-disrupting compounds, the rapid and efficient detection of PAEs is crucial. Recent developments in sensor technology have significantly enhanced the monitoring of environmental and food contaminants. This study aimed to develop a surface plasmon resonance (SPR) sensor utilizing diethyl phthalate-imprinted nanoparticles (DEP-MINPs) for the sensitive and selective detection of DEP. DEP-MINPs were synthesized via microemulsion polymerization and immobilized onto a bare gold SPR chip as a recognition layer. The DEP-MINPs were characterized using FTIR, TEM, and zeta potential analyses. The kinetic performance was investigated within a concentration range of 1.0–135.0 μM, observing a strong linear correlation between DEP concentration and SPR sensor response. The calculated limit of detection was 0.30 μM. The Langmuir model best described the interaction, suggesting monolayer adsorption on a homogeneous surface. Selectivity studies using structurally similar compounds, including dimethyl phthalate, styrene, and vanillic acid, revealed that the sensor was 2.64, 5.00, and 4.83 times more selective for DEP, confirming the success of the molecular imprinting process. The developed SPR sensor was successfully used for DEP analysis in bottled water and sanitary pad samples. The DEP-MINPs SPR sensor demonstrated excellent reproducibility and stability over multiple measurements and days, supporting its potential for practical applications in environmental monitoring.
Magnetic materials have become essential for detecting and quantifying various analytes. Advances in technology and molecular recognition have further enhanced the capabilities of these materials, making them crucial components in developing efficient and versatile analytical systems across diverse fields, such as pharmaceuticals, biomedicine, and environmental analysis. One of the most promising innovations in this area is magnetic molecularly imprinted polymers. These materials combine molecular selectivity with the magnetic responsiveness of traditional magnetic materials. This hybrid technology improves analyte recognition and isolation, leading to increased extraction efficiency, speed, and reproducibility. Magnetic molecularly imprinted polymer-based materials allow for easier manipulation and separation of the polymer matrix using an external magnetic field, further enhancing their performance. They are particularly beneficial in applications that require rapid and reliable analyte extraction, facilitating faster on-site analysis and high-throughput screening. This review provides a comprehensive exploration of the principles, design strategies, and applications of magnetic molecularly imprinted polymers, focusing on their use in pharmaceuticals and biomedicine. These innovative materials also play an important role in enhancing the sensitivity and selectivity of sensor systems used in precise analyte detection. Magnetic molecularly imprinted polymers improve analyte extraction efficiency and enable rapid, real-time detection in various analytical applications. It also addresses current challenges and potential future directions for this technology.
This study reports the fabrication and characterization of polycaprolactone/pullulan nanofiber mats incorporating black seed oil (PCL/PUL-BSO) for potential biomedical applications. The PCL/PUL-BSO nanofiber mats with varying PCL/PUL ratios (1:1, 1:2, and 1:3) were produced by electrospinning, and their morphology, physicochemical properties, swelling, degradation, thermal stability, and drug release behavior were systematically investigated. Increasing PUL content enhanced hydrophilicity, swelling ratio, and degradation rate, primarily due to increased water uptake and reduced intermolecular interactions within the polymer matrix. BSO incorporation significantly affected the properties of the mats. Drug release studies revealed distinct release profiles depending on PCL/PUL ratios: 1:1 mats favored sustained, low-dose release (53.9 f 3.3% over 44 days), 1:2 mats exhibited a balanced profile with a moderate initial burst (23.9 f 2.8 % in 6 h) and prolonged delivery (63.4 f 5.0% over 44 days), and 1:3 mats supported rapid and high-extent release (87.2 f 2.1% over 44 days). The PCL/PUL-BSO (1:2) nanofiber mat with fiber diameters of 409 f 53 nm exhibited balanced swelling and degradation properties, making the mat suitable for medium-term biomedical applications. DSC and TGA analyses confirmed the compatibility of BSO with the polymer matrix and thermal stability under sterilization conditions. Consequently, BSO incorporation ensured well-balanced hydrophilicity, porosity, permeability, and mechanical strength, leading to a nanofiber mat with outstanding properties and excellent promise for biomedical use.
The intrinsically slow and insufficiently tunable degradation kinetics of poly(lactic-co-glycolic acid) (PLGA) limit its versatility in medium-term biomedical delivery systems. Herein, we reported a one-step electrospinning strategy to establish a PLGA/pullulan (PUL) nanofibrous platform with regulated degradation behavior and sustained release capability, using black seed oil (BSO) as a model hydrophobic bioactive compound. The PLGA/PUL-BSO nanofibers exhibited uniform bead-free morphology. The specific surface area increased from 23.27 m2/g for PLGA/PUL nanofibers to 36.82 m2/g for PLGA/PUL-BSO nanofibers. Total porosity of the PLGA/PUL nanofibers decreased from 32% to 21% after BSO incorporation. The PLGA/PUL-BSO nanofibers degraded via bulk-erosion. An initial lag phase was observed during the first 8 days, followed by a rapid mass-loss phase between days 8 and 12. Subsequently, the mass loss gradually reached 77.1 ± 1.85% after 30 days. BSO release exhibited a two-stage release profile. The cumulative release reached 60.1 ± 3.9% within the first 6 h, consistent with a diffusion-controlled mechanism described by the Korsmeyer-Peppas model. Thereafter, during the sustained release phase, the cumulative release reached 76.3 ± 5.8% after 30 days and followed zero-order kinetics. Swelling equilibrium (%) of the PLGA/PUL-BSO nanofibers was significantly higher than that of PLGA/PUL nanofibers, demonstrating that BSO incorporation influenced the nanoscale organization of PLGA and PUL. Consequently, PUL addition effectively regulated the degradation properties of PLGA and modulated therapeutic release, demonstrating that the developed PLGA/PUL-BSO nanofibers constituted a robust nanofibrous materials platform with biomedical potential.
Recent advancements in sensor technology have enabled the detection of antibiotics in food, ensuring human safety. In this study, we developed a surface plasmon resonance (SPR) sensor based on molecularly imprinted nanoparticles (MINps) for the real-time, sensitive, and in-situ detection of tetracycline (Tc). Firstly, Tc-imprinted nanoparticles (Tc-MINps) were synthesized using microemulsion polymerization. Then, the Tc-MINps were coated onto a bare gold SPR chip to develop the Tc-MINps SPR sensor. The sensor's performance was evaluated by detecting Tc in aqueous solutions. The results demonstrated a highly selective binding of Tc to the nanocavities on the surface of the Tc-MINps SPR sensor. The relationship between Tc molecules and the SPR sensor was analyzed at 0.5-20 mg/L Tc concentrations (pH 5.0). The Langmuir isotherm model was identified as the most appropriate binding model, indicating monolayer adsorption. The selectivity of the Tc-MINps SPR sensor was investigated using oxytetracycline, ciprofloxacin, and amoxicillin due to their structural similarity. The selectivity coefficients were determined as 5.54 for oxytetracycline, 23.66 for ciprofloxacin, and 28.39 for amoxicillin. Additionally, the limit of detection (LOD) for the Tc-MINps SPR sensor for Tc analysis in milk was found to be 0.45 mg/L, while the LOD for the HPLC method was 0.55 mg/L. The developed SPR sensor is suitable for Tc detection in milk due to its advantages, such as real-time monitoring, low cost, high selectivity, and reusability.
Molecularly imprinted polymer (MIP) nanoparticles offer a promising controlled drug delivery platform. In this study, amoxicillin (AMOX)-imprinted polymer nanoparticles (similar to 60 nm) were synthesized via emulsion polymerization and incorporated into polyvinyl alcohol (PVA)/sodium alginate (SA) [PVS] electrospun nanofibers to develop a novel wound dressing. The nanoparticle-embedded PVS nanofibers (PVS-AMOX-MIP) demonstrated a sustained cumulative drug release of 43.6% over 2 days, governed by non-Fickian transport per the Korsmeyer-Peppas kinetic model. The nanofibers exhibited favorable physical properties, including a high specific surface area (39.66 m(2)/g), optimal porosity (78.8%), and a water vapor transmission rate (1053.4 +/- 5.9 g/m(2)/day), ideal for wound healing. Antibacterial activity studies showed significant inhibition against Staphylococcus aureus and Escherichia coli, while biocompatibility assays confirmed the mat's noncytotoxic nature and ability to promote cell proliferation. Furthermore, angiogenesis studies revealed enhanced vascularization, which is critical for tissue regeneration. The developed strategy offers a unique approach for advanced wound care and controlled drug delivery applications by combining MIP nanoparticles' molecular recognition capability with the structural advantages of electrospun nanofibers.
In this study, poly(2-hydroxyethyl methacrylate-N-methacryloyl-(L)-histidine methyl ester-Cu2+) [PHMCu2+] nanoparticles were synthesized by emulsion polymerization and used as carriers for L-asparaginase (L-ASNase) immobilization. The nanoparticles were characterized using SEM-EDX, TEM, FTIR, Zeta potential analyses. The binding affinity of L-ASNase on metal-chelated polymeric nanoparticles was investigated via surface plasmon resonance (SPR) analysis. The immobilized enzyme (PHM-Cu2+-L-ASNase) achieved an immobilization yield of 86.4 %, activity yield of 73.6 %, and immobilization efficiency of 85.1 %. The optimum pH shifted from 8.5 (free) to 7.0 (immobilized), and the optimum temperature from 45 °C to 50 °C. The PHM-Cu2+-L-ASNase presented enhanced resistance to proteolysis. Kinetic studies revealed that Km and Vmax values decreased after immobilization, indicating increased substrate affinity. Immobilization also resulted in a slightly lower turnover number (kcat) compared to the free enzyme. The PHM-Cu2+-L-ASNase preserved 60 % activity after ten reuse cycles and maintained higher activity in the presence of various metal ions and organic solvents. Thermal, storage, and in vitro artificial human serum stability studies revealed that the PHM-Cu2+-L-ASNase exhibited slower inactivation and extended half-life compared to the free L-ASNase. SPR analysis demonstrated high binding affinity (KD = 0.016 IU/mL), fitting the Langmuir model. Consequently, the PHMCu2+ nanoparticles were effective carriers for L-ASNase enzyme, enhancing its catalytic activity, stability, and reusability for pharmaceutical and industrial use.
This review explores the application of nanomaterial-based sensing systems for precisely detecting neuropharmaceutical compounds and neurotransmitters, delving into the connections between nanotechnology and neuropharmacology. Nanotechnology appears as a promising solution for many significant challenges posed by the complexities of the brain’s biochemical nature. Using nanoscale materials, scientists have created novel sensors with high selectivity, sensitivity, and adaptability. Developing neuropharmaceutical compounds and monitoring their side effects on our neurological system raised the need for these nanomaterial-based sensors. In this review, we demonstrate the effectiveness of these technologies in real-time neuroactive compound detection and monitoring by illuminating the underlying principles through an examination of significant studies and recent developments. This review also highlights collaborative efforts at the intersection of nanotechnology and neuropharmacology and their direct and indirect effects on the understanding and controlling several neurological disorders. This review covers both sensors under research and those already applied in vivo or clinical monitoring of drug side effects.
In this study, a composite poly(2-hydroxyethyl methacrylate)/graphene oxide (PHEMA-GO) cryogel column was developed for removal of methylene blue (MB) from aqueous solution. The PHEMA-GO composite cryogel column was synthesized by adding GO into cryogelation mixture and comprehensive characterization studies were conducted via Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), mercury porosimetry, and swelling study. The total porosity was determined as 66.72%. The pore size was in the range of 4.31-220.6 mu m. The MB adsorption capacity of PHEMA-GO cryogel column was investigated considering different parameters, including GO amount, pH, contact time, ionic strength, temperature, and initial MB concentration. The maximum MB amount adsorbed amount onto the PHEMA-GO composite cryogel column was determined as 253 mg/g at 298 K (pH:5.3). The adsorption data were obeyed to Langmuir isotherm model and pseudo-second-order kinetic model. The adsorbed amount of MB was not affected from ionic strength, which is important for the dye removal from the textile wastewater. The composite cryogel column was reused 10 times without a decrease in the MB adsorption capacity. The application potential of the PHEMA-GO composite cryogel column was demonstrated using a real textile wastewater sample.
The removal of persistent dyes from aqueous environments is a critical concern due to their ecological toxicity and resistance to degradation. In this study, poly(ethylene glycol dimethacrylate-N-methacryloyl-amido-L-tryptophan methyl ester) [PEDMT] microbeads were synthesized via suspension polymerization and utilized as efficient adsorbents for the removal of Congo Red (CR), a emodel anionic azo dye. The microbeads exhibited a high specific surface area of 1103 m(2)/g and a porous morphology favorable for adsorption. Batch adsorption experiments were conducted to investigate the effects of pH, contact time, adsorbent dosage, dye concentration, and temperature on adsorption performance. Batch adsorption studies showed a maximum adsorption capacity of 86.32 +/- 3.63 mg/g at 277 K, 75.69 +/- 2.51 mg/g at 298 K, and 73.64 +/- 4.34 mg/g at 308 K at pH 6.0. Kinetic data fitted best to the pseudo-second-order model, with an activation energy of 25.24 kJ/mol. Equilibrium data were well described by both Langmuir and Freundlich isotherm models, suggesting a mixed adsorption mechanism. Thermodynamic parameters confirmed that the adsorption process was spontaneous (Delta G degrees = -7.15 to -7.76 kJ/mol) and exothermic (Delta H degrees = -1.78 kJ/mol). Consequently, the PEDMT microbeads has an application potential as reusable adsorbents for the treatment of azo dye-contaminated waters.
Ceragenins are synthetic molecules that mimic antimicrobial peptides (AMPs) in the human immune system. They feature a bile acid-based structure with appended positively charged groups that disrupt bacterial cell membranes, leading to microbial cell death or inactivation. In this study, ceragenin CSA-44 was incorporated into a polyvinyl alcohol (PVA)/gelatin (G)/sodium alginate (SA)-based hydrogel (PGA-CSA). The hydrogel was cross-linked with glutaraldehyde (GA) for 20 min using a 0.125% GA (v/v) solution. The optimized volume ratios of the polymer solutions in the hydrogel were determined to be 2:1:3 (PVA:SA:G). PGA-CSA and PGA hydrogels were characterized using scanning electron microscopy (SEM), mercury porosimetry, and Fourier transform infrared spectroscopy (FTIR). The maximum swelling ratio of PGA-CSA was 780.48% +/- 14.80%, and the WVTR value was 905.4 +/- 35.4 g/m2/d. Drug release studies showed a cumulative CSA-44 release of 29.07% over 7 days. The antibacterial activity of the hydrogel was tested against Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 19151, Staphylococcus aureus ATCC 29213, and MRSA. The tested bacteria were inhibited within 2, 2.5, 3, and 3.5 h, respectively. The developed PGA-CSA hydrogel demonstrated outstanding potential and unique characteristics as an antibacterial dressing for burn wounds.
Pesticides are hazardous compounds widely used to prevent pests in agriculture. Detecting pesticides with high selectivity and sensitivity is crucial in food safety and environmental protection. Molecularly imprinted polymers (MIPs) are innovative materials for enriching target analytes from complex matrices. The conventional procedure for preparing MIPs results in a massive solid and liquid waste generation contradicting the green chemistry concepts. To ensure environmental protection, food quality, and safety, trace-level detection of pesticide residues with MIPs is always demanded using a more economical, reliable, and greener approach. In this chapter, green MIPs strategies for pesticide recognition are comprehensively overviewed. The most common pesticides that green MIPs have prepared and the analytical methods used for their analysis are introduced. Green approaches are discussed regarding various template strategies, solvents, polymerization techniques, and magnetic MIPs.
Bu çalışmada yenilebilir bir mantar türü olan Craterellus cornucopioides biyokütlesinin sulu çözeltilerden Kongo kırmızısının biyosorpsiyonunda biyosorbent olarak kullanımı araştırılmıştır. Biyosorbentin karakterizasyonu gerçekleştirildikten sonra biyosorpsiyon koşulları optimize edilmiştir. Elde edilen verilere göre 0,01 g biyosorbent miktarı kullanılarak pH: 6,0’da 25 ⁰C ortam sıcaklığında 2 saatlik biyosorpsiyonun ardından biyosorpsiyon kapasitesi (qe) 150 mg/L başlangıç Kongo kırmızısı derişimi için 46,22±2,14 mg/g olarak bulunmuştur. Biyosorpsiyonun doğasının aydınlatılabilmesi için biyosorpsiyon izotermleri, biyosorpsiyon kinetiği ve termodinamiği araştırılmıştır. Elde edilen deneysel sonuçların kullanılmasıyla hesaplanan fizikokimyasal parametrelere göre, biyosorpsiyon prosesinin Freundlich izoterm modeline ve yalancı-ikinci derece kinetik modele uygun olduğu görülmüştür. Proses ekzotermik karakterde ve kendiliğinden oluşmaktadır. Son olarak biyosorpsiyon-desorpsiyon çalışmaları gerçekleştirilmiş ve kullanılan biyosorbentin etkin bir şekilde tekrar kullanılabileceği gösterilmiştir. Hazırlanan biyosorbentin sulu çözeltilerden boyar madde gideriminde ucuz, verimli ve etkin bir biyosorbent olacağı düşünülmektedir.
This study aimed to prepare a polyvinyl alcohol/sodium alginate (PVSA) nanofibrous mat as an amoxicillin (AMOX) delivery system. AMOX was loaded to the PVSA nanofibers during electrospinning, and the AMOX-loaded PVSA (PVSA/AMOX) nanofibrous mat was cross-linked by glutaraldehyde (GA). The PVSA/AMOX nanofibrous mat was characterized by Fourier Transform infrared spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller, and mercury porosimetry analyses. The thickness, air permeability, and water vapor transmission rate of the PVSA/AMOX nanofibrous mat were 0.43 ± 0.08 mm, 17.2 ± 4.91 L/m2/s, and 1485 ± 13.6 g/m2/d, respectively, which were suitable for wound dressing applications. The tensile strength was 6.73 ± 0.48 MPa and elongation at a maximum load was 81.9 ± 17.0
In this study, a cryogel/nanofiber hybrid material was developed using a new lotus-leaf-inspired strategy. The lotus effect was generated via beaded poly( ε -caprolactone) (PCL) nanofibers produced from the 9 wt% PCL solution with low viscosity and high surface tension via electrospinning. A poly(hydroxyethyl methacrylate) (PHEMA) cryogel layer was constructed through polymerization onto the beaded PCL nanofibrous mat. The thickness of the PHEMA cryogel/beaded PCL nanofiber hybrid material was 3.19 ± 0.07 mm. Morphological characterization studies of the hybrid material were conducted by scanning electron microscopy (SEM). The mean diameter of the beaded PCL nanofibers was 97.22 ± 21.18 nm. The lotus effect created by the beaded PCL nanofibers was investigated by water contact angle (WCA) measurements. The WCA of beadless and beaded PCL nanofibers was 93.42° ± 1.4° and 117.97° ± 5.04°, respectively. The PHEMA cryogel layer was chemically characterized via Fourier transform infrared spectroscopy (FTIR) analysis and the specific groups belonging to 2-hydroxyethyl methacrylate (HEMA) was observed. The porosity of the PHEMA cryogel layer was determined via mercury porosimetry. The total porosity of the PHEMA cryogel was 64.42%, and the pore sizes were in the range of 5–200 µm. Swelling kinetics of the PHEMA cryogel/beaded PCL nanofiber hybrid material were also investigated and compared to those of PHEMA cryogel and beaded PCL nanofibers. The maximum swelling ratio of the hybrid material was 509.69% and reached after 180 min. The developed PHEMA cryogel/beaded PCL nanofiber hybrid material met the criteria required for layered structures and biomedical applications whereby its eligible stability, morphology, porosity, and swelling capacity. Consequently, the lotus-leaf-inspired strategy was successful in constructing the cryogel/nanofiber hybrid materials.
An analytical approach has been developed for the sensitive determination of Phenobarbital, which is used as an antiepileptic drug molecule. The analysis of this active molecule, which has a very limited study even for its direct determination in the literature review, is mostly done with highly complex device systems such as LC-MS. In analysis with conventional HPLC systems, the limit of detection cannot be in most cases lower than 1 µg mL-1 With this study, a separation and preconcentration method based on solid phase extraction (SPE) was developed for trace phenobarbital molecules, so that even very low concentrations could be monitored. In the proposed method, the target molecules were enriched with column type SPE method, and then their analysis were carried out by with the HPLC-DAD system. As an SPE sorbent, a polymeric material, poly(ethylene glycol dimethacrylate-N-methacryloyl-L-tryptophan methyl ester) [poly(EGDMA-MATrp)], was used in extraction experiments. Experimental variables such as pH of medium, type and amount of desorption solvent, electrolyte effect have been studied and optimized step by step. The linear working range under the optimized conditions were determined in the range of 10.00-400.00 ng mL-1 with the limit of detection as 3.57 ng mL-1. Quantitative results were obtained in recovery experiments with the help of model solutions including phenobarbital molecule
In this study, Lactarius deliciosus biomass was used as a biosorbent for the biosorption of three tetracycline antibiotics, chlortetracycline (CTC), doxycycline (DC), and tetracycline (TC), from aqueous solution. The biomass was characterized by Fourier Transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The effect of biosorbent amount (0.01-0.1g), pH (3.0-8.0), initial antibiotic concentration (30-300 mg/L for CTC and DC, and 5-50 mg/L for TC), contact time (2-120 min), and temperature (7 degrees C, 16 degrees C, 25 degrees C) were investigated. The maximum biosorption amount of CTC, DC, and TC was 216.4 +/- 4.2 mg/g (pH 4.0), 121.2 +/- 6.2 mg/g (pH 3.0), and 23.2 +/- 2.1 mg/g (pH 7.0) at 25 degrees C, respectively. The biosorption amount of tetracyclines decreased with increasing temperature demonstrating that the biosorption processes were exothermic. The biosorptions of tetracyclines were favorable with negative Delta G degrees values for all temperatures. CTC and DC biosorption processes were well fitted to the pseudo-second-order kinetic and Freundlich isotherm models. TC biosorption data obeyed the pseudo-first-order kinetic model. Tap and drinking water samples spiked with tetracyclines were used as real samples for biosorption. The results showed that L. deliciosus biomass could be effectively used as a biosorbent for tetracycline antibiotics with high adsorption capacities.
A dummy molecularly imprinted polymer-based solid-phase extraction (SPE) sorbent was used for the selective extraction of some phthalate monoesters, monoethyl phthalate (MEP), monobutyl phthalate (MnBP) and mono-(2-ethylhexyl) phthalate (MEHP) in urine prior to gas-chromatography-mass spectrometry (GC-MS) analysis. Diethyl phthalate (DEP), a phthalate ester, was successfully used as a dummy template to prepare selective sorbent for MEP, MnBP, and MEHP extraction. DEP-imprinted poly(ethylene glycol dimethacrylate N-meth-acryloyl-L-tryptophan methyl ester) (DPEMT) microbeads were synthesized by suspension polymerization and characterized by Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Brunauer Emmet Teller (BET) analysis. The critical parameters (i.e., pH, sorbent amount, ionic strength, sample volume, elution solvent) affecting the extraction performance of the DPEMT-SPE sorbent were optimized. Under optimum conditions, good linearities were obtained in the concentration range of 4 to 60 ng/mL with deter-mination coefficients (R2) of greater than 0.9959. The developed SPE method provided low limits of detection (LOD) of 0.05-1.20 ng/mL and limits of quantification (LOQ) of 0.18-4.01 ng/mL with relative standard de-viations (RSDs) of less than 8.95 % for intra-and inter-day analyses. The proposed SPE method was used to analyze phthalate monoesters in spiked urine samples, and recoveries of 97.45-109.26 % were obtained. DPEMT-SPE sorbent was reused for 15 times without any losses of performance. Consequently, a highly selective and sensitive SPE method based on a dummy molecularly imprinted polymer combined with GC-MS was suc-cessfully developed to monitor human phthalate exposure via urine samples.
A new series of thioethers containing a 1,2,4-oxadiazole ring were synthesized by the modified Riemschneider reaction. The corresponding thiocyanate derivatives of 1,2,4-oxadiazoles were obtained in good yields by the reaction of 3-aryl-5-chloromethyl-1,2,4-oxadiazole compounds with NH4SCN in triethylene glycol at 60 °C as a new method. Thioether derivatives were synthesized by reacting 5-thiocyanato-3-aryl-1,2,4-oxadiazole with various tertiary or secondary alcohols in solvent-free conditions for 10–30 min at 60 °C. The synthesized compounds were characterized by various spectroscopic methods (FTIR, 1H NMR, 13C NMR, and HRMS). All 1,2,4-oxadiazole-thioethers were tested for xanthine oxidase (XO), acetylcholinesterase (AChE), and butyrylcholinesterase (BChE) inhibition potential. The results showed that 4 h has more potential inhibition activity than positive control for XO (IC50 = 0.41 ± 0.067 µM) and AChE/BChE (IC50 = 0.95 ± 0.42 µM/1.49 ± 0.45 µM) and is considerably greater than other compounds. Moreover, our experimental study was supported by molecular docking to describe the binding mode of new structures to enzymes. The molecular docking calculations showed that molecules with high binding energy with at least one enzyme were 4b, 4d, 4g, 4h, 4i, 4j, 4k, and 4l. The physicochemical, ADMET, and drug-likeness parameters were computed using the SwissADMET online program. In silico studies of the molecules demonstrated that five molecules, 4b, 4d, 4g, 4h, and 4l, had relatively optimum drug similarity and medicinal chemistry properties. The five molecules synthesized and characterized in this study can be further investigated as drug or drug-like compound candidates.