Search Results (97)

This study discloses the noncovalent immobilization of a bienzyme cascade composed of glucose oxidase (GOx) and horseradish peroxidase (HRP) onto magnetically responsive polyamide microparticles (PA MPs). Porous PA6, PA4, and PA12 MPs containing iron fillers were synthesized via activated anionic ring-opening polymerization in suspension, alongside neat PA6 MPs used as a reference. Four hybrid catalytic systems (GOx/HRP@PA) were prepared through sequential adsorption of HRP and GOx onto the various PA MP supports. The initial morphologies of the supports and the hybrid biocatalysts were characterized by SEM, followed by evaluation of the catalytic performance using a two-step glucose oxidation cascade process. Among all systems, the GOx/HRP@PA4-Fe complex exhibited the highest activity, being approximately 1.5 times greater than the native enzyme dyad, followed by the PA6-supported system with slightly inferior performance. All systems obeyed Michaelis–Menten kinetics, with the immobilized cascades displaying higher Kₘ and Vₘₐₓ values than the non-immobilized enzyme pair while maintaining comparable catalytic efficiencies, CE (CE = k_cat/Kₘ). Subsequently, the immobilized and native enzyme systems were employed for the polymerization of aniline. According to UV–VIS, complete monomer conversion was achieved within 24 h for selected catalysts, and FTIR analysis confirmed the formation of polyaniline in the emeraldine base form without the use of template molecules. These findings highlight the potential of Fe-containing polyamide microparticles as efficient supports for the sustainable, enzyme-mediated synthesis of intrinsically conductive aromatic polymers. Full article

Neurotransmitters such as serotonin regulate key physiological and cognitive functions, yet real-time detection remains challenging due to the limitations of conventional techniques like amperometry and microdialysis. Fluorescent molecularly imprinted polymer nanoparticles (fMIP-NPs) offer a promising alternative and are typically synthesized via solid-phase synthesis, in which template molecules are covalently immobilized on a solid support to enable site-specific imprinting. However, strong template–template interactions during this process can compromise selectivity. To overcome this, we incorporated a poly(methacrolein-co-methacrylamide)-based template anchoring strategy to minimize undesired template interactions and enhance imprinting efficiency. We optimized the synthesis of poly(methacrolein-co-methacrylamide) under three different conditions by varying the monomer compositions and reaction parameters. The poly(methacrolein-co-methacrylamide) synthesized under Condition 3 (5:1 methacrolein-to-methacrylamide molar ratio, 1:150 initiator-to-total monomer ratio, and 4.59 M total monomer concentration) yielded the most selective fMIP-NPs, whose fluorescence intensity increased with an increase in serotonin concentration, rising by up to 37% upon serotonin binding. This improvement is attributed to higher aldehyde functionality in the poly(methacrolein-co-methacrylamide) which enhances template immobilization and generates a rigid imprinted cavity to interact with serotonin. These findings suggest that the developed fMIP-NPs hold significant potential as imaging probes for neurotransmitter detection, contributing to advanced studies in neural network analysis. Full article

Methicillin-resistant Staphylococcus epidermidis (MRSE) contamination is commonly found on human skin and medical devices. Herein, we present a sensor utilizing molecularly imprinted polymer nanobodies (nanoMIP) for recognition and electrochemical impedance spectroscopy (EIS) to detect S. epidermidis. Sensor manufacturing involves synthesizing nanoMIP via solid-phase synthesis using whole bacteria as templates. Screen-printed gold electrode (AuSPE)-modified 16-mercaptohexadecanoic acid (MHDA) served to immobilize the nanoMIPs on the sensor surface through an amide bond, with the remaining functional groups blocked by ethanolamine (ETA). Scanning electron microscope (SEM) analysis of the modified AuSPE surface reveals immobilized spherical nanoMIP particles of 114–120 nm diameter, while atomic force microscope (AFM) analysis showed increased roughness and height compared to bare AuSPE. The sensor is selective for S. epidermidis, with a remarkable detection limit of 1 CFU/mL. This research demonstrates that the developed nanoMIP-based sensor effectively detects S. epidermidis. Further research will focus on developing protocols to integrate the nanoMIP-based EIS sensor into medical and industrial applications, ultimately contributing to improved safety for both humans and animals in the future. Full article

In this study, we present the design of a molecularly imprinted polymer (MIP) for the detection of the antibiotic sparfloxacin (SPFK), combined with a high-precision quartz crystal microbalance (QCM) sensor. Green-synthesized ZIF-67@PDA-MIP was directly immobilized on the gold electrode surface of the QCM. This configuration takes advantage of the selective recognition capabilities of the MIP and the high-sensitivity response characteristics of the QCM sensor. It overcomes the limitations of traditional SPFK detection methods, offering both accurate detection and rapid responses for practical applications. The MIP-QCM sensor demonstrated enhanced sensitivity and affinity, achieving a detection limit as low as 10.3 ng/mL. Additionally, the selectivity of the sensor for SPFK was superior to that of other non-template molecules. It effectively detected SPFK residues in milk with acceptable accuracy, as indicated by recoveries ranging from 96.16% to 104.64% and a relative standard deviation (RSD) of less than 4.64%. These results suggest that the proposed MIP-QCM sensor provides an accurate, sensitive, rapid, and cost-effective method for detecting SPFK residues in animal products, and this advancement is expected to promote the widespread adoption of high-precision sensors in food safety testing. Full article

Polymers with micro- and mesoporous structure are promising as materials for gas storage and separation, encapsulating agents for controlled drug release, carriers for catalysts and sensors, precursors of nanostructured carbon materials, carriers for biomolecular immobilization and cellular scaffolds, as materials with a low dielectric constant, filtering/separating membranes, proton exchange membranes, templates for replicating structures, and as electrode materials for energy storage. Sol–gel technologies, track etching, and template synthesis are used for their production, including in micelles of surfactants and microemulsions and sublimation drying. The listed methods make it possible to obtain pores with variable shapes and sizes of 5–50 nm and achieve a narrow pore size distribution. However, all these methods are technologically multi-stage and require the use of consumables. This paper presents a review of the use of macromolecular architecture in the synthesis of micro- and mesoporous polymers with extremely high surface area and hierarchical porous polymers. The synthesis of porous polymer frameworks with individual functional capabilities, the required chemical structure, and pore surface sizes is based on the unique possibilities of developing the architecture of the polymer matrix. Full article

The cell immobilization technique, which restricts living cells to a certain space, has received widespread attention as an emerging biotechnology. In this study, a yeast (Saccharomyces cerevisiae)-loaded highly open-cell emulsion-templated polyethylene glycol (PEG-polyHIPE) was synthesized to be a reusable enzymatic catalyst. An emulsion was prepared with polyethylene glycol diacrylate (PEGDA) aqueous solution, cyclohexane, and polyethylene-polypropylene glycol (F127) as the continuous phase, dispersed phase, and surfactant, respectively. Then PEG-polyHIPE was obtained by polymerization of the PEGDA in emulsion. The highly porous materials obtained by the emulsion-templating method are suitable for use as carrier materials for yeast immobilization, due to their favorable structural designability. During the activation process, the yeast S. cerevisiae can readily gain access to the interior of the material via the interconnected pores and immobilize itself inside the voids. The yeast-loaded polyHIPE was then used to ferment glucose for ethanol production. The yeast immobilized inside the polyHIPE has high fermentation efficiency, good recoverability, and storage stability. After seven cycles, the yeast maintained 70% initial fermentation efficiency. The S. cerevisiae kept more than 90% of the initial cellular activity after one week of storage both in the dry state and in yeast extract peptone dextrose medium (YPD) at 4 °C. This study strongly demonstrates the feasibility of using high-throughput porous materials as cell immobilization carriers to efficiently osmotically immobilize cells in polyHIPEs for high-performance fermentation. Full article

Palladium (Pd) catalysts play a crucial role in facilitating Suzuki cross-coupling reactions for the synthesis of valuable organic compounds. However, conventional heterogeneous Pd catalysts often encounter challenges such as leaching and deactivation during reactions, leading to reduced catalytic efficiency. In this study, we employed an innovative intercalation templating strategy to prepare two-dimensional carbon nanosheets with high nitrogen doping derived from petroleum asphalt, which were utilized as a versatile support for immobilizing Pd nanoparticles (Pd/N-CNS) in efficient Suzuki cross-coupling reactions. The results indicate that the anchoring effect of high-pyridinic N species on the two-dimensional carbon nanosheets enhances interactions between Pd and the support, effectively improving both the dispersibility and stability of the Pd nanoparticles. Notably, the Pd/N-CNS catalyst achieved an overall turnover frequency (TOF) of 2390 h⁻¹ for the Suzuki cross-coupling reaction under mild conditions, representing approximately a nine-fold increase in activity compared to commercial Pd/C catalysts. Furthermore, this catalyst maintained an overall TOF of 2294 h⁻¹ even after five reaction cycles, demonstrating excellent stability. Theoretical calculations corroborate these observed enhancements in catalytic performance by attributing them to improved electron transfer from Pd to the support facilitated by abundant pyridinic N species. This work provides valuable insights into feasible strategies for developing efficient catalysts aimed at sustainable production of biaromatic compounds. Full article

Hand disorders can reduce wrist range of motion (ROM). The SARS-CoV-2 pandemic highlighted challenges in routine follow-up exams, making telemedicine a viable solution. This study evaluates the feasibility and accuracy of patient self-measured wrist ROM using a self-designed goniometer template. The template was designed to measure flexion/extension and radial/ulnar abduction movements. A cohort of 50 adults (25 males/25 females) participated in this prospective study. The exclusion criteria included wrist immobilization and ages outside of 18–65 years. Participants self-assessed their wrist ROM with the goniometer template. Measurements were independently performed by a student and a specialist using standard goniometry, as well as a resident using the self-designed goniometer. The results were blinded for unbiased analysis. Mean differences in ROM varied across movement directions, with minimal differences for ulnar abduction and more substantial deviations for radial abduction, extension and flexion. The patient–specialist comparison showed deviations below 5 degrees for flexion and ulnar abduction in 50% of cases. Telemedicine, expanded by the COVID-19 pandemic, offers significant potential for hand rehabilitation. Current methods of ROM assessment lack cost-effectiveness and simplicity. Our method, demonstrating comparable accuracy for most movements, provides a cost-effective, reliable alternative for remote ROM assessment, enhancing telemedicine practices in hand rehabilitation. Full article

The thermal stability of DNA immobilized on a solid surface is one of the factors that affects the efficiency of solid-phase amplification (SP-PCR). Although variable temperature amplification ensures high specificity of the reaction by precisely controlling temperature changes, excessively high temperatures during denaturation can negatively affect DNA stability. Formamide (FA) enables DNA denaturation at lower temperatures, showing potential for SP-PCR. Research on FA’s impacts on DNA microarrays is still limited, necessitating further optimization in exploring the characteristics of FA in SP-PCR according to particular application needs. We immobilized DNA on a chip using a crosslinker and generated DNA microarrays through bridge amplification based on FA denaturation on our automated reaction device. We optimized the denaturation and hybridization parameters of FA, achieving a maximum cluster density of 2.83 × 10⁴ colonies/mm². Compared to high-temperature denaturation, FA denaturation required a lower template concentration and milder reaction conditions and produced higher cluster density, demonstrating that FA effectively improves hybridization rates on surfaces. Regarding the immobilized DNA stability, the FA group exhibited a 45% loss of DNA, resulting in a 15% higher DNA retention rate compared to the high-temperature group, indicating that FA can better maintain DNA stability. Our study suggests that using FA improves the immobilized DNA stability and amplification efficiency in SP-PCR. Full article

In this study, we explored the surface modification of a glassy carbon electrode through the electrografting of 4-Aminophenyl phosphate, which features heteroatoms and ionic properties. The electrochemical grafting process involves reducing in situ-generated diazonium derivatives. The primary objective of this research was to immobilize organic layers and assess their electrochemical and surface properties. Subsequently, the generated surface serves as a template for the electrochemical growth of Pd and Co nanoparticles on functionalized electrodes. The electrocatalytic performances of these hybrid electrodes in driving the hydrogen evolution reaction were investigated. The obtained results indicate an enhancement in the electrocatalytic activity of the modified electrodes, where lower overpotential and higher stability were observed when the catalyst was electrodeposited onto the attached ionic layer. These findings highlight the synergistic effect between the attached phenyl phosphate moieties and electrocatalysts. Full article

In recent decades, there has been increased attention to the role of layer-by-layer assembled bio-polymer 3D structures (capsules, beads, and microgels) for biomedical applications. Such free-standing multilayer structures are formed via hard templating onto sacrificial cores such as vaterite CaCO₃ crystals. Immobilization of these structures onto solid surfaces (e.g., implants and catheters) opens the way for the formulation of advanced bio-coating with a patterned surface. However, the immobilization step is challenging. Multiple approaches based mainly on covalent binding have been developed to localize these multilayer 3D structures at the surface. This work reports a novel strategy to formulate multilayer surface-supported microgels (ss-MG) directly on the surface via hard templating onto ss-CaCO₃ pre-grown onto the surface via the direct mixing of Na₂CO₃ and CaCl₂ precursor solutions. ss-MGs were fabricated using biopolymers: polylysine (PLL) as polycation and three polyanions—hyaluronic acid (HA), heparin sulfate (HS), and alginate (ALG). ss-MG biodegradation was examined by employing the enzyme trypsin. Our studies indicate that the adhesion of the ss-MG to the surface and its formation yield directly correlate with the mobility of biopolymers in the ss-MG, which decreases in the sequence of ALG > HA > HS-based ss-MGs. The adhesion of HS-based ss-MGs is only possible via heating during their formation. Dextran-loading increases ss-MG formation yield while reducing ss-MG shrinking. ss-MGs with higher polymer mobility possess slower biodegradation rates, which is likely due to diffusion limitations for the enzyme in more compact annealed ss-MGs. These findings provide valuable insights into the mechanisms underlying the formation and biodegradation of surface-supported biopolymer structures. Full article

As heterogeneous catalysis is a practical method for activating Oxone, the immobilization of transition metals (e.g., Co, Fe) on carbonaceous supports is a promising platform. Thus, this study attempts to develop a carbon-supported metallic catalyst by growing Co/Fe on carbon foam (CF) via adopting melamine foam as a readily available template which could be transferred to nitrogen-doped CF with marcoporous structures. Specifically, a unique adornment of Co/Fe species on this CF is facilely fabricated through a complexation of Co/Fe with a plant extract, tannic acid, on melamine foam, followed by carbonization to produce nano-needle-like Co/Fe on N-doped CF, forming a magnetic CF (MCF). This resultant MCF exhibits a much higher surface area of 54.6 m²/g than CF (9.5 m²/g), and possesses a much larger specific capacitance of 9.7 F/g, than that of CF as 4.0 F/g. These superior features of MCF enable it to accelerate Oxone activation in order to degrade an emerging contaminant, bis(4-hydroxyphenyl)methanone (BHPM). Furthermore, MCF + Oxone exhibits a lower activation energy as 18.6 kJ/mol for BHPM elimination and retains its effectiveness in eliminating BHPM over multiple rounds. More importantly, the CF is also prepared and directly compared with the MCF to study the composition-structure-property relationship to provide valuable insights for further understanding of catalytic behaviors, surficial characteristics, and application of such a functional carbon material. Full article

Ordered mesoporous carbon CMK-3 sieves with a hexagonal structure and uniform pore size have recently emerged as promising materials for applications as adsorbents and electrodes. In this study, using sucrose as the sustainable carbon source and SBA-15 as a template, CMK-3 sieves are synthesized to form bioelectrocatalytic immobilization matrices for enzymatic biofuel cell (EFC) electrodes. Their electrochemical performance, capacitive features, and the stability of enzyme immobilization are analyzed and compared to commercially available multi-walled carbon nanotubes (MWCNT) using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The anodic reaction in the presence of glucose oxidase (GOx) and ferrocene methanol (FcMeOH) on the sustainably sourced CMK-3-based electrodes produces bioelectrocatalytic current responses at 0.5 V vs. saturated calomel electrode (SCE) that are twice as high as on the MWCNT-based electrodes under saturated glucose conditions. For the cathodic reaction, the MWCNT-based cathode performs marginally better than the CMK-3-based electrodes in the presence of bilirubin oxidase (BOD) and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS²⁻). The CMK-3-based EFCs assembled from the GOx anode and BOD cathode results in a power output of 93 μW cm⁻². In contrast, the output power of MWCNT-based EFCs is approximately 53 μW cm⁻². The efficiency of CMK-3 as a support material for biofuel cell applications is effectively demonstrated. Full article

Using density functional theory (DFT) B3PW91/TZVP, M06/TZVP, and OPBE/TZVP chemistry models and the Gaussian09 program, a quantum-chemical calculation of geometric and thermodynamic parameters of Ni(II), Cu(II), and Zn(II) macrotetracyclic chelates, with (NNNN)-coordination of ligand donor centers arising during template synthesis between the indicated ions of 3d elements, thiocarbohydrazide H₂N–HN–C(=S)–NH–NH₂ and diacetyl Me–C(=O)–C(=O)–Me, in gelatin-immobilized matrix implants was performed. The key bond lengths and bond angles in these coordination compounds are provided, and it is noted that in all these complexes the MN₄ chelate sites, the grouping of N₄ atoms bonded to the M atom, and the five-membered and six-membered metal chelate rings are practically coplanar. NBO analysis of these compounds was carried out, on the basis of which it was shown that all these complexes, in full accordance with theoretical expectations, are low-spin complexes. The standard thermodynamic characteristics of the template reactions for the formation of the above complexes are also presented. Good agreement between the data obtained using the above DFT levels is noted. Full article

Charantin is a mixture of β-sitosterol and stigmastadienol glucosides, which effectively lowers high blood glucose. Novel molecularly imprinted polymers coated magnetic nanoparticles (Fe₃O₄@MIPs) and filter paper (paper@MIPs) were synthesized by sol-gel polymerization to selectively extract charantin. β-sitosterol glucoside was selected as a template for imprinting a specific recognition owing to its larger molecular surface area than that of 5,25-stigmastadienol glucoside. Factorial designs were used to examine the effects of the types of porogenic solvents and cross-linkers on the extraction efficiency and imprinting factor before investigating other factors (for example, amounts of template and coated MIPs, and types of substrates for MIP immobilization). Compared to traditional liquid–liquid extraction, the optimal Fe₃O₄@MIP-based dispersive micro-solid phase extraction and paper@MIP extraction provided excellent extraction efficiency (87.5 ± 2.1% and 85.0 ± 2.9%, respectively) and selectivity. Charantin was well separated, and a new unidentified sterol glucoside was observed using the developed high-performance liquid chromatography with diode-array detection (Rs ≥ 2.0, n > 16,400). The developed methods were successfully utilized to extract and quantify charantin from M. charantia fruit powder and herbal products. Moreover, these methods are rapid (<10 min), inexpensive, simple, reproducible, and environmentally friendly. Full article