Polymer Beads Research Articles

Ternary polymeric beads of chitosan-based polyaniline doped iron oxide used for removal of cadmium and lead ions from water: Kinetic, isotherm and mechanism studies

ABSTRACT In this study, the binary polymeric magnetic beads were synthesized successfully by one-pot polymerization of polyaniline (PA) doped magnetic iron oxide nanoparticles (MNPs) followed by chitosan (CTS) cross-linkage. The newly fabricated ternary magnetic beads (CTS@MPA) were applied to enhance the removal of Pb(II) and Cd(II) ions from the aqueous media. The prepared nanocomposite was characterized using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and vibrating sample magnetometry (VSM). Adsorption experiments were carried out under optimum conditions. To evaluate the experimental data, the isotherm and kinetic models were conducted. The behavior of adsorption was assessed, and the coefficient of determination values demonstrated that the adsorption process best fitted the Freundlich model due to high values of R2 (0.957 & 0.981). The maximum adsorption capacity was obtained at 150.82 mg.g−1 and 169.21 mg.g−1 for Pb(II) and Cd(II) ions, respectively. Kinetic studies showed that adsorption follows a pseudo-second-order model (R2 = 0.952 & 0.985). Weber-Morris claims that intraparticle diffusion plays a significant role in the adsorption kinetics. Finally, the thermodynamic study is demonstrated, and the adsorption is endothermic, and the mechanism follows a physisorption pattern.

Preparation and Utilization of a Highly Discriminative Absorbent Imprinted with Fetal Hemoglobin.

Development in hemoglobin-based oxygen carriers (HBOCs) that may be used as alternatives to donated blood requires an extensive supply of highly pure hemoglobin (Hb) preparations. Therefore, it is essential to fabricate inexpensive, stable and highly selective absorbents for Hb purification. Molecular imprinting is an attractive technology for preparing such materials for targeted molecular recognition and rapid separations. In this case study, we developed human fetal hemoglobin (HbF)-imprinted polymer beads through the fusion of surface imprinting and Pickering emulsion polymerization. HbF was firstly covalently coupled to silica nanoparticles through its surface-exposed amino groups. The particle-supported HbF molecules were subsequently employed as templates for the synthesis of molecularly imprinted polymers (MIPs) with high selectivity for Hb. After removing the silica support and HbF, the resulting MIPs underwent equilibrium and kinetic binding experiments with both adult Hb (HbA) and HbF. These surface-imprinted MIPs exhibited excellent selectivity for both HbA and HbF, facilitating the one-step isolation of recombinant Hb from crude biological samples. The saturation capacities of HbA and HbF were found to be 15.4 and 17.1 mg/g polymer, respectively. The present study opens new possibilities for designed resins for tailored protein purification, separation and analysis.

The Ultimate Fate of Reactive Dyes Absorbed onto Polymer Beads: Feasibility and Optimization of Sorbent Bio-Regeneration under Alternated Anaerobic–Aerobic Phases

Dyes employed in many production cycles are characterized by high toxicity and persistence in the environment, and conventional wastewater treatments often fail to reach high removal efficiencies. Consequently, there is an increasing research demand aimed at the development of more efficient and sustainable technologies. A two-step strategy consisting of dye sorption followed by sorbent bio-regeneration is proposed here, with a special focus on the regeneration step. The objective of this study was to establish the best operating conditions to achieve regeneration of dye-loaded polymers and concurrently the ultimate removal of the dyes. To this aim, the bio-regeneration of the Hytrel 8206 polymer, used as a sorbent material to remove Remazol Red dye from textile wastewater, was investigated in a two-phase partitioning bioreactor (TPPB) under alternated anaerobic–aerobic conditions. Comprehensive analysis of operational parameters, including sorbent load and initial contamination levels, was conducted to optimize bio-regeneration efficiency. Experimental data demonstrated high regeneration efficiencies (91–98%) with biodegradation efficiencies up to 89%. This study also examines the biodegradation process to investigate the fate of biodegradation intermediates; results confirmed the successful degradation of the dye without significant by-product accumulation. This research underscores the potential of TPPB-based bio-regeneration of polymeric sorbent material for sustainable wastewater treatment, offering a promising solution to the global challenge of dye pollution in water resources.

Polymeric Antibiotic Beads for Canine Osteomyelitis: Advancing Localized Antibiotic Treatment with Enhanced Efficacy and Minimized Side Effects

Antibiotic beads represent a compelling treatment method for the treatment and prevention of canine osteomyelitis, as they provide localized antibiotic concentrations at the infection site with minimal systemic toxicity. The therapeutic efficacy of these beads has been demonstrated, highlighting their potential as a valuable local antibiotic therapy. In particular, the introduction of vancomycin - polymethylmethacrylate (PMMA) beads is highlighted as a promising new form of local antibiotic therapy. This article focuses on the use of antibiotic-impregnated beads to treat localized bacterial infections in the bones and joints of canines. Typically composed of poly(lactic-co-glycolic acid) (PLGA) or polymethylmethacrylate (PMMA), these beads contain antibiotics such as vancomycin, placed directly into the affected area, providing a high antibiotic concentration at the site of infection. These beads were developed for a slow antibiotic release over time; they ensure a constant protective effect against a broad spectrum of bacteria, demonstrating high efficacy and biocompatibility with the animal's body. This localized antibiotic treatment option offers several advantages over systemic antibiotics, such as reduced side effects and improved efficacy. It could be a promising option for the treatment of bone and joint infections in canines.

Impact of Surface Modification on the Oxidation of Linear Aliphatic Alcohols by Vanadium Complexes Supported on Merrifield Resin with Mixed Functionality Ligands

AbstractTwo oxidovanadium(IV) complexes [VO(xbp‐sc)] (1) and [VO(xbp‐tc)] (2) were prepared using hydrazine‐ether mixed functionality ligands Hxbp‐sc (I) and Hxbp‐tc (II), respectively. Complexes 1 and 2 were carefully grafted separately into imidazole‐modified chloromethylated polystyrene (Ps−Im) and unmodified chloromethylated polystyrene (PS−Cl) beads. Successfully anchored vanadium complexes Ps−Im‐[VO(xbp‐sc)] (3), Ps−Im‐[VO(xbp‐tc)] (4), Ps‐[VO(xbp‐sc)] (5), and Ps‐[VO(xbp‐tc)] (6) were tested for their catalytic potential towards the oxidation of aliphatic alcohols in the presence of hydrogen peroxide. Polymer‐grafted catalysts display excellent substrate conversion compared to most recent reports and good recyclability up to three cycles without losing much reactivity. High TOF values in the range of 183–591 h−1 are observed for the supported catalysts 3–6. The highest substrate conversion is observed for ethanol (63–97 %) under the optimized reaction conditions. Mainly, better substrate conversion is obtained with imidazole‐modified polymer beads grafted catalysts 3 and 4 than those grafted on unmodified polymer beads (5 and 6). Moreover, catalysts with the semicarbazide group in their ligand framework (3 and 5) show better reactivity towards alcohol with fewer carbon atoms. On the contrary, alcohols with longer carbon chains oxidize more easily in the presence of the catalyst with thiosemicarbazide frameworks (4 and 6).

Machine learning‐based time series analysis of polylactic acid bead foam extrusion

AbstractUnderstanding the behavior of polymer melts during extrusion is essential for optimizing processes and developing new materials. However, analyzing the continuous data generated by an extruder poses significant challenges. This paper investigates the utility of machine learning in predicting melt pressure at the die plate in polylactic acid (PLA) bead foam extrusion, a critical parameter in the extrusion process. Utilizing a random forest (RF) model, we examine how various processing parameters influence melt pressure. By segmenting the data into time‐delayed intervals, we achieve accurate predictions. We present forecasts of melt pressure at the die for intervals of 5 s, 1 min, and 5 min, demonstrating particularly strong performance for the 5‐min forecast with a Mean Absolute Error (MAE) of 1.88 and the coefficient of determination ( score) of 0.90. By exploring time series data, our study demonstrates the effectiveness of the RF model and provides a foundation for more advanced and precise control strategies in polymer bead extrusion processes.

Highly Efficient and Robust Platinum Nanocluster Catalyst Mediated by Polyamine Amidine‐Decorated Mesoporous Polymer Beads

AbstractPlatinum nanoclusters (PtNCs) are promising in catalysis due to their large specific surface area and unique physicochemical properties. Here, ultrasmall and uniform PtNCs are facilely synthesized with the mediation of amidine‐functionalized polyamines patched on mesoporous poly(divinylbenzene‐4‐vinylbenzyl chloride) beads. When each ligand patch has 14 amidines, ultrafine PtNCs (with the size as low as 1.1±0.1 nm) are formed as a result of several factors: deprotonated amidines (carbenes) strongly passivate on Pt atoms, amidines act as co‐stabilizers along with weak polyamine ligands, and PtNCs are confined to discrete ligand patches. When one ligand patch contains 9.3 amidines, the resulting PtNCs (1.7±0.3 nm) reach the highest turnover frequency of 536 h−1 for the catalytic reduction of 4‐nitrophenol in a batch reaction. This catalyst remains rather stable in a continuous flow test as a 4‐nitrophenol conversion of over 95 % is still achieved after running consecutively for 10 h.

4-Vinylpyridine copolymers for improved LC–MS tryptophan and kynurenine determination in human serum

Tryptophan (an essential amino acid) and its clinically important metabolite—kynurenine contribute to several fundamental biological processes and methods that allow their determination in biological samples are in demand. The novelty of the work was a demonstration of the utility of two polymers: 4-vinylpyridine crosslinked with trimethylolpropane trimethacrylate (poly(4VP-co-TRIM)) or 1,4-dimethacryloyloxybenzene (poly(4VP-co-14DMB))—in terms of human serum clean-up for simultaneous LC–MS determination of tryptophan and kynurenine. The goal was to achieve a reduction of the matrix effect, which is responsible for signal suppression, with minimal capture of analytes. The adsorption properties of the polymeric beads were studied by evaluating the adsorption kinetics and isotherms in model matrices. Therefore, the adsorption capacities of both molecules were not efficient, the tested 4-vinylpyridine-based copolymers have shown great promise (especially poly(4VP-co-TRIM)) as sorbents for serum clean-up. In the model human serum matrix, poly(4VP-co-TRIM) provided good recoveries of tryptophan and kynurenine (76% and 87%, respectively) and allowed for the reduction of the matrix effect. Performances of both copolymers were compared to those of commercially available sorbents (octadecylsilane, activated charcoal, and primary secondary amine).

Trace Thiol Moieties in the Ligand Layer Induce Superior Catalytic Gold Nanoclusters.

We here show that the typical poison of thiols, if below a certain level, promotes rather than suppresses the catalytic activity of gold nanoclusters (AuNCs). A few thiol groups functionalized hyperbranched polyethylenimine (PEI, Mn = 2000 Da) patched on a mesoporous polymeric bead aid the direct synthesis of AuNCs. The nucleation efficiency of AuNC is 93-fold favored at a level of 2 thiols per PEI (0.04 equiv of the amino units) than that by neat PEI, and AuNCs (1.3 nm) are obtained up to a gold load of 6.3% on the support. Unexpectedly, the catalytic activity of AuNCs is favored by the thiol up to 2 thiols per PEI, as evaluated from the surface-normalized rate constant of the model reaction of 4-nitrophenol-reduction. The catalytic promotion by thiols probably stems from optimized electron density on AuNC. If the residual NH groups of PEI were further fully treated with glycidyltrimethylammonium chloride, the catalytic activity is again enhanced, where the accelerated mass transfer is responsible for the promotion. Overall, the catalytic activity reaches an unprecedented value (metal-normalized rate constant kc = 29.4 L mmol-1 s-1 and turnover frequency = 1623 h-1, as evaluated with the model reaction of 4-nitrophenol reduction) ever reported for supported AuNCs. Our results suggest that orthogonal ligand optimization is an effective manner of triggering the release of the catalytic potential of AuNCs, among which thiol is unique.

Architecting Polymeric Beads with Covalent Organic Framework Nanostrands for Fast and Selective Extraction of Neodymium

Architecting Polymeric Beads with Covalent Organic Framework Nanostrands for Fast and Selective Extraction of Neodymium

Multimodal interactions in Stomoxys navigation reveal synergy between olfaction and vision

Stomoxys flies exhibit an attraction toward objects that offer no rewards, such as traps and targets devoid of blood or nectar incentives. This behavior provides an opportunity to develop effective tools for vector control and monitoring. However, for these systems to be sustainable and eco-friendly, the visual cues used must be specific to target vector(s). In this study, we modified the existing blue Vavoua trap, which was originally designed to attract biting flies, to create a deceptive host attraction system specifically biased toward attracting Stomoxys. Our research revealed that Stomoxys flies are attracted to various colors, with red proving to be the most attractive and selective color for Stomoxys compared to the other colors tested. Interestingly, our investigation of the cattle–Stomoxys interaction demonstrated that Stomoxys flies do not prefer a specific livestock fur color phenotype, despite variation in the spectrum. To create a realistic sensory impression of the trap in the Stomoxys nervous system, we incorporated olfactory cues from livestock host odors that significantly increased trap catches. The optimized novel polymer bead dispenser is capable of effectively releasing the attractive odor carvone + p-cresol, with strong plume strands and longevity. Overall, red trap baited with polymer bead dispenser is environmentally preferred.

Diglycolamic Acid-Functionalized MWCNT-Augmented Polymeric Beads for Efficient Separation of Trivalent Lanthanides and Actinides

Diglycolamic Acid-Functionalized MWCNT-Augmented Polymeric Beads for Efficient Separation of Trivalent Lanthanides and Actinides

Engineering Porosity-Tuned Chitosan Beads: Balancing Porosity, Kinetics, and Mechanical Integrity.

Chitosan, a cationic natural polysaccharide derived from the deacetylation of chitin, is known for its solubility in diluted acidic solutions, biodegradability, biocompatibility, and nontoxicity. This study introduces three innovative methods for preparing various types of porous chitosan beads: solvent extraction, surfactant extraction, and substance decomposition. These methods involve the integration and subsequent extraction or decomposition of materials during the synthesis process, eliminating the need for additional steps. We used state-of-the-art characterization techniques to analyze and evaluate the chemical and physical properties of the beads, such as Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and three-dimensional (3D) computed tomography (CT) scanning. The 3D CT scans visualized and measured the porosity of different bead types, ranging from 68.4% to 39.3%. This study also evaluated the mechanical properties of the particle beads under compressive forces in both wet and dry conditions, highlighting the influence of porosity on their mechanical integrity and compression pressure behavior. The adsorptive properties of these chitosan beads were studied using methylene blue as a model pollutant, emphasizing the importance of balancing porous structure, surface area, kinetics, and structural integrity. This study paves the way for the development of environmentally sustainable polymeric beads, highlighting the crucial need to balance porosity, surface area, and structural integrity to optimize their effectiveness in real-world applications.

Purely Optical, Reversible, Read‐Write‐Erase Cycling Using Photoswitchable Beads in Micropatterned Arrays

AbstractUsing surface‐templated electrophoretic deposition, arrays of polymer beads (photonic units) incorporating photo‐switchable DAE molecules are created, which can be reversibly and individually switched between high and low emission states by direct photo‐excitation, without any energy or electron transfer processes within the molecular system. The micropatterned array of these photonic units is spectroscopically characterized in detail and optimized with respect to both signal contrast and cross‐talk. The optimum optical parameters including laser intensity, wavelength and duration of irradiation are elucidated and ideal conditions for creating reversible on/off cycles in a micropatterned array are determined. 500 such cycles are demonstrated with no obvious on/off contrast attenuation. The ability to process binary information is demonstrated by selectively writing information to the given photonic unit, reading the resultant emissive signal pattern and finally erasing the information again, which in turn demonstrates the possibility of continuous recording. This basic study paves the way for building complex circuits using spatially well‐arranged photonic units.

Solvent Vapor Annealing and Plasma Treatment Stabilize Silver Nanowire Layers

AbstractSilver nanowires (AgNW) find use in transparent conductive electrodes with applications in solar cells, touch screens, and wearables. Unprotected AgNW are prone to atmospheric corrosion and lose conductivity over time. Known passivation techniques either require submersion of pre‐deposited AgNW in liquid compounds or the modification of AgNW inks prior to deposition, which alters viscosity and complicates deposition. Here, new possibilities for stabilization of pre‐deposited AgNW networks without need for submersion are explored. It is demonstrated that AgNW networks can be stabilized either by argon or hydrogen plasma treatment or by solvent vapor annealing with ethanol, methanol, or ethyl acetate. These treatments yielded stable electrical resistance over at least nine weeks, whereas untreated or thermally annealed AgNW layers quickly lost conductivity. The potential of solvent vapor annealing is further explored by demonstrating a new processing technique for stable polymer matrix composites containing AgNW. Co‐deposited layers of AgNW with polystyrene microbeads are annealed in ethyl acetate vapor to stabilize the AgNW while at the same time merging polymer beads into a closed film around the AgNW. The resulting composites maintained stable resistance and transmittance for at least seven weeks.

Competition between bead boundary fusion and crystallization kinetics in material extrusion-based additive manufacturing

Assembling polymer beads into well-defined 3D geometries through a layer by layer deposition process, such as material extrusion additive manufacturing, remains challenging due to the complex interplay between the several kinetics involved (flow, inter-beads diffusion/fusion, cooling, solidification, etc). Here, we explore the influence of physical parameters like bead cross section geometry, partial bead fusion (also called bead coalescence or bead welding) and crystallization kinetics on the 3D printing of isotactic polypropylene as a model semi-crystalline polymer. New methods for the characterization of printed stacks cross sections, interlayer cohesion and viscoelastic coalescence are introduced. Our results demonstrate how printing conditions, through input parameters like layer height and nozzle temperature, can greatly affect interlayer cohesion in relation to polymer interdiffusion at the interface. We show that the relevant timescale for fusion is mainly driven by the polymer’s rheology, and that fusion is many-fold faster under Hertzian compression, i.e. due to the effect of contact pressure. Quantitative description of the influence of the extrusion nozzle and build platform temperatures on the crystallization time of printed beads highlights how the processability window is defined by the competition between fusion and crystallization. Our approach therefore provides a framework for the optimization of process parameters based on the physical processes involved during the production run of semi-crystalline polymers.

Time-of-flight resolved stimulated Raman scattering microscopy using counter-propagating ultraslow Bessel light bullets generation

We present a novel time-of-flight resolved Bessel light bullet-enabled stimulated Raman scattering (B2-SRS) microscopy for deeper tissue 3D chemical imaging with high resolution without a need for mechanical z-scanning. To accomplish the tasks, we conceive a unique method to enable optical sectioning by generating the counter-propagating pump and Stokes Bessel light bullets in the sample, in which the group velocities of the Bessel light bullets are made ultraslow (e.g., vg ≈ 0.1c) and tunable by introducing programmable angular dispersions with a spatial light modulator. We theoretically analyze the working principle of the collinear multicolor Bessel light bullet generations and velocity controls with the relative time-of-flight resolved detection for SRS 3D deep tissue imaging. We have also built the B2-SRS imaging system and present the first demonstration of B2-SRS microscopy with Bessel light bullets for 3D chemical imaging in a variety of samples (e.g., polymer bead phantoms, biological samples such as spring onion tissue and porcine brain) with high resolution. The B2-SRS technique provides a > 2-fold improvement in imaging depth in porcine brain tissue compared to conventional SRS microscopy. The method of optical sectioning in tissue using counter-propagating ultraslow Bessel light bullets developed in B2-SRS is generic and easy to perform and can be readily extended to other nonlinear optical imaging modalities to advance 3D microscopic imaging in biological and biomedical systems and beyond.

Development of a novel sensory material for rapid detection of mercury ions in various water sources: Solution and solid-state analysis

A xanthene propane nitrile-based sensor material was successfully prepared, and an attempt towards the preparation of polymer bead form was made for the sensitive or selective detection of mercury ions (Hg2+) in water. The sensor material in solution as well as in polymeric form showed amazing selectivity over other added metal ions with a naked eye color change, UV visible spectral and fluorescence spectral change, and a rapid and excellent color change from colorless to purple. The 1H NMR study exposed the probable binding site of the probe with the added mercury ion. In this study, the imine nitrogen and the C = O interact with the mercury ion, resulting in the ring opening of lactam with a vivid color change. The EDTA test was done to verify the reversible behavior of the probe and confirmed its reversibility by UV–visible and fluorescence spectral studies. The polymer bead made using this probe can be used as a tool for monitoring mercury ions in real time in different sources of water samples. The sensor molecule itself senses the mercury ion in its solid state by simple grinding and changes its color from pale yellow to deep purple. The sensor color change response is very rapid towards mercury detection, which is confirmed by the prepared test strip.

Porous Semiconducting Polymer Nanoparticles as Intracellular Biophotonic Mediators to Modulate the Reactive Oxygen Species Balance.

The integration of nanotechnology with photoredox medicine has led to the emergence of biocompatible semiconducting polymer nanoparticles (SPNs) for the optical modulation of intracellular reactive oxygen species (ROS). However, the need for efficient photoactive materials capable of finely controlling the intracellular redox status with high spatial resolution at a nontoxic light density is still largely unmet. Herein, highly photoelectrochemically efficient photoactive polymer beads are developed. The photoactive material/electrolyte interfacial area is maximized by designing porous semiconducting polymer nanoparticles (PSPNs). PSPNs are synthesized by selective hydrolysis of the polyester segments of nanoparticles made of poly(3-hexylthiophene)-graft-poly(lactic acid) (P3HT-g-PLA). The photocurrent of PSPNs is 4.5-fold higher than that of nonporous P3HT-g-PLA-SPNs, and PSPNs efficiently reduce oxygen in an aqueous environment. PSPNs are internalized within endothelial cells and optically trigger ROS generation with a >1.3-fold concentration increase with regard to nonporous P3HT-SPNs, at a light density as low as a few milliwatts per square centimeter, fully compatible with in vivo, chronic applications.

Cold-chain free nucleic acid preservation using porous super-absorbent polymer (PSAP) beads to facilitate wastewater surveillance

The instability of viral targets including SARS-CoV-2 in sewage is an important challenge in wastewater monitoring projects. The unrecognized interruptions in the ‘cold-chain’ transport from the sample collection to RNA quantification in the laboratory may undermine the accurate quantification of the virus. In this study, bovine serum albumin (BSA)-modified porous superabsorbent polymer (PSAP) beads were applied to absorb raw sewage samples as a simple method for viral RNA preservation. The preservation efficiency for SARS-CoV-2 and pepper mild mottle virus (PMMoV) RNA were examined during storage for 14 days at 4 °C or room temperature against the control (no beads applied). While a non-significant difference was observed at 4 °C (∼80 % retention for both control and PSAP-treated sewage), the reduction of SARS-CoV-2 RNA concentrations was significantly lower in sewage retrieved from PSAP beads (25–40 % reduction) compared to control (>60 % reduction) at room temperature. On the other hand, the recovery of PMMoV, known for its high persistence in raw sewage, from PSAP beads or controls were consistently above 85 %, regardless of the storage temperature. Our results demonstrate the applicability of PSAP beads to wastewater-based epidemiology (WBE) projects for preservation of SARS-CoV-2 RNA in sewage, especially in remote settings with no refrigeration capabilities.