Remediation of microplastics using bionanomaterials: A review.

Pollution by microplastics (MPs) formed by the physicochemical breakdown of plastics are a worldwide issue with long-lasting and hazardous natural effects. The natural expulsion of MPs takes several years and can be dangerous. Several effective technological innovations have been developed over the years to remediate harmful MPs. Among them, a blend of nanotechnological techniques using bionanomaterials has been investigated to a large extent. The objective of this review is to compile the MPs found in the environment and bionanomaterial-based approaches for their removal. This information is important for researchers who are exploring the adverse consequences of MPs and their remediation and developing advanced eco-friendly strategies to control and eradicate MPs in the future. The control and eradication of MPs depend on all of us; hence, the proper awareness of MPs pollution must be provided to every individual, as all of us are a part of the environment.

Surface functionalized magnetic nanoparticles shift cell behavior with on/off magnetic fields.

Magnetic nanoparticles (MNPs) are used as contrast agents and targeted drug delivery systems (TDDS) due to their favorable size, surface charge, and magnetic properties. Unfortunately, the toxicity associated with MNPs limits their biological applications. Surface functionalization of MNPs with selective polymers alters the surface chemistry to impart better biocompatibility. We report the preparation of surface functionalized MNPs using iron oxide NPs (MNPs), poly (lactic-co-glycolic acid) (PLGA), and sodium alginate via co-precipitation, emulsification, and electro-spraying, respectively. The NPs are in the nanosize range and negatively charged. Morphological and structural analyses affirm the surface functionalized nanostructure of the NPs. The surface functionalized MNPs are biocompatible, and demonstrate enhanced intracellular delivery under an applied magnetic field (H), which evinces the targeting ability of MNPs. After NP treatment, the physico-mechanical properties of fibroblasts are decided by the selective MNP uptake under "on" or "off" magnetic field conditions. We envision potential use of biocompatible surface functionalized MNP for intracellular-, targeted-DDS, imaging, and for investigating cellular mechanics.

Red Fluorescent Copper Nanoclusters for Fluorescence, Smartphone, and Electrochemical Sensor Arrays to Detect the Monkeypox A29 Protein.

An Orthopox zoonotic viral infection called monkeypox (MPXV) is the leading infectious disease globally. MPXV can easily spread from human to human through direct and indirect sexual contact; therefore, accurate and early detection of MPXV is crucial for reducing mortality. Fluorescence-based materials have received significant attention in recent years for biomedical applications. In this study, we synthesized red-fluorescent copper nanoclusters (CuNCs) with a size of less than 10 nm, which was confirmed by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (Bio-AFM) analysis. The synthesized CuNCs had a high fluorescence nature and were utilized for the detection of the MPXV (A29P) by an antigen-antibody conjugation using fluorescence, smartphone colorimetric, and electrochemical sensing techniques. The antigen (A29P) and antibody (Ab A29) interaction mechanisms were studied by X-ray photoelectron spectroscopic (XPS) analysis. Furthermore, fluorescence and electrochemical sensing were performed in PBS with detection limits of 0.096 and 0.114 nM, respectively. For real-world applications, the prepared immunosensor array can detect A29P in spiked serum samples, and point-of-care (POC) analysis, a smartphone-integrated sensor array, was used to measure the RGB color changes. The results showed that synthesized CuNCs are potential materials for detecting A29P via fluorescence and smartphone colorimetric and electrochemical sensing techniques.

Surface-constructing of visible-light Bi2WO6/CeO2 nanophotocatalyst grafted PVDF membrane for degradation of tetracycline and humic acid.

The synthesis of Bi2WO6 and CeO2 photocatalytic nanomaterials exhibit a great ability to photodegrade the antibiotics and shown excellent oxidation of various organic pollutants. Heterostructure 1:1 & 2:1 Bi2WO6/CeO2 nanocomposite was successfully synthesized via the facile sono-dispersion method and exquisite photocatalytic activity. The 0.5 wt% of nanocomposites were well-grafted on PVDF membrane surface via an in-situ polymerization method using polyacrylic acid. The fourier transform infrared (FTIR) spectra demonstrated that the network formation in PVDF induced by the -COOH functional group in acrylic acid. The grafted membrane morphology and strong binding ability over the membranes were validated by scanning electron microscope with energy dispersion (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), respectively. The permeate flux of 49.2 L.m-2 h-1 and 41.65 L.m-2 h were observed for tetracycline and the humic acid solution respectively for 1 wt% of PVP and 0.5 wt% of photocatalytic nanomaterials in PVDF membrane. The tetracycline and humic acid photodegradation rate of 82% and 78% and total resistance of 1.43 × 1010 m-1 and 1.64 × 1010 m-1, 83.5% and 77% flux recovery ratio were observed with N5 membrane. The 2:1 Bi2WO6/CeO2 nanocomposite grafted membrane showed a high permeate flux and better photodegradation ability of organic pollutants in the wastewater.

Copper-glucosamine microcubes: synthesis, characterization, and C-reactive protein detection.

Cubelike microstructures of glucosamine-functionalized copper (GlcN-CuMC's) have been fabricated by the integration of injection pump and ultrasonochemistry. Although bulk microstructures and the nanostructure of metallic copper exhibit distinct applications, the amino sugar surface-functionalized copper is almost biocompatible and exhibits advanced features such as more crystallinity, high thermal stability, and electrochemical feasibility toward biomolecule (C-reactive protein, CRP) detection. An electrochemical test of this GlcN-CuMC's was demonstrated by immobilization on a conventional gold-PCB (Au-PCB) electrode. The combination of a biointerface membrane, from glucosamine functionalization, and electroactive sites of metallic copper provides a very efficient electrochemical response against various concentration of CRP. A perfect scaling of steady-state currents with r(2) values of 0.9862 (I(pa)) and 0.9972 (I(pc)) indicate the promise of this kind of biofunctionalized microstructure electrode for many surface and interface applications.

PEGylated polyethyleneimine grafted silica nanoparticles: enhanced cellular uptake and efficient siRNA delivery.

The present paper reports the utilization of hybrid nanocomposite particles consisting of PEI25k-PEG5k copolymer grafted silica nanoparticles (SiO(2)NPs) for enhanced cellular uptake and siRNA delivery. High-resolution transmission electron microscopy and dynamic light scattering measurements ensured the average particle size of the final hybrid component as 45 nm (core SiO(2), 28-30 nm and shell PEI25k-PEG5k, 12-15 nm). Surface morphology from atomic force microscopy analysis showed the significant relationship between the particle size and shape. (29)Si and (13)C cross-polarization-magic angle spinning solid state nuclear magnetic resonance (NMR), (1)H-NMR, and Fourier transform infrared spectroscopy were used to obtain the relevant structural information (such as Q3, silanol; Q4, siloxane functional groups of SiO(2)NPs; resonance shifts and bending vibrations of PEI25k, -CH(2)-CH(2)-NH-; and PEG5k, -CH(2)-CH(2)-O-) from copolymer nanoparticle. Stable complexation of siRNA and nanocomposite particle (wt.%:wt.%) was achieved from 1:5 to 1:15 ratio. Nanocomposite particle (N/P) ratio and siRNA concentration determine the stability and knockdown efficiency of the PEI25k-PEG5k-graft-SiO(2)NPs-siRNA complexes. It was shown that highly positively charged (zeta potential, +66 mV) PEI25k-PEG5k-graft-SiO(2)NPs result in strong affinity with negatively charged siRNA. Confocal microscopy showed intensified cellular uptake of siRNA into cytoplasm of A549 cancer cell utilized for in vitro study. In conclusion, the coherence, graft density of copolymer-SiO(2)NPs, and siRNA concentration were found to strongly influence the stability, and hence determine the knockdown efficiency, of PEI25k-PEG5k-graft-SiO(2)NPs-siRNA complexes.

Structural and biological evaluation of a multifunctional SWCNT-AgNPs-DNA/PVA bio-nanofilm.

A bio-nanofilm consisting of a tetrad nanomaterial (nanotubes, nanoparticles, DNA, polymer) was fabricated utilizing in situ reduction and noncovalent interactions and it displayed effective antibacterial activity and biocompatibility. This bio-nanofilm was composed of homogenous silver nanoparticles (AgNPs) coated on single-walled carbon nanotubes (SWCNTs), which were later hybridized with DNA and stabilized in poly(vinyl alcohol) (PVA) in the presence of a surfactant with the aid of ultrasonication. Electron microscopy and bio-AFM (atomic force microscopy) images were used to assess the morphology of the nanocomposite (NC) structure. Functionalization and fabrication were examined using FT-Raman spectroscopy by analyzing the functional changes in the bio-nanofilm before and after fabrication. UV-visible spectroscopy and X-ray powder diffraction (XRD) confirmed that AgNPs were present in the final NC on the basis of its surface plasmon resonance (370 nm) and crystal planes. Thermal gravimetric analysis was used to measure the percentage weight loss of SWCNT (17.5%) and final SWCNT-AgNPs-DNA/PVA (47.7%). The antimicrobial efficiency of the bio-nanofilm was evaluated against major pathogenic organisms. Bactericidal ratios, zone of inhibition, and minimum inhibitory concentration were examined against gram positive and gram negative bacteria. A preliminary cytotoxicity analysis was conducted using A549 lung cancer cells and IMR-90 fibroblast cells. Confocal laser microscopy, bio-AFM, and field emission scanning electron microscopy (FE-SEM) images demonstrated that the NCs were successfully taken up by the cells. These combined results indicate that this bio-nanofilm was biocompatible and displayed antimicrobial activity. Thus, this novel bio-nanofilm holds great promise for use as a multifunctional tool in burn therapy, tissue engineering, and other biomedical applications.

Electrochemical detection of hydrocortisone using green-synthesized cobalt oxide nanoparticles with nafion-modified glassy carbon electrode.

Developing highly sensitive and selective sensors is important for the detection of steroid hormones. Electrochemical sensors are of great interest in this regard. Also utilization of bio-derived substances as an electrode material is environment friendly. In this study, we used green-synthesized cobalt oxide nanoparticles (CoO NPs) along with nafion (Naf) on a glassy carbon electrode to detect hydrocortisone (HC) by voltammetry. Electron microscopy, X-ray diffraction, Raman spectroscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy were used to characterize the CoO NPs prepared using Nigella sativa seeds extract. Cyclic voltammetry and differential pulse voltammetry was utilized for the detection of HC. Only one reduction peak at -0.5 V was observed in the presence of HC in 0.1 M sodium hydroxide, indicating an irreversible electrode process. The Naf-CoO NPs enhanced the active surface area of the glassy carbon electrode (GCE) that resulted in a good response for detecting HC with two linear ranges: 0.001-1 µM and 1-9 µM. In comparison to other published electrochemical sensors, the current sensor displayed a low limit of detection of 0.49 nM, as well as remarkable stability and reproducibility. The sensor exhibited credibility for the sensing of HC in pharmaceutical injections and blood serum samples with recovery percentages ranging from 97.7% to 102.5%. The electrochemical sensor has proved to be valuable for HC detection.

Non-noble metal (Ni, Cu)-carbon composite derived from porous organic polymers for high-performance seawater electrolysis.

The hydrothermal preparation of o-dianisidine and triazine interlinked porous organic polymer and its successive derivatisation via metal infusion (Ni, Cu) under hydrothermal and calcination conditions (700 °C) to yield pristine (ANIPOP-700) and Ni/Cu decorated porous carbon are described here (Ni-ANIPOP-700 and Cu-ANIPOP-700). To confirm their chemical and morphological properties, the as-prepared materials were methodically analyzed using solid state 13C and 15N NMR, X-ray diffraction, Raman spectroscopy, field emission scanning and high resolution transmission electron microscopic techniques, and x-ray photoelectron spectroscopy. Furthermore, the electrocatalytic activities of these electrocatalysts were thoroughly investigated under standard oxygen evolution (OER) and hydrogen evolution reaction (HER) conditions. The results show that all of the materials demonstrated significant activity in water splitting as well as displayed excellent stability (22 h) in both acidic (HER) and basic conditions (OER). Among the electrocatalysts reported in this study, Ni-ANIPOP-700 exhibited a lower overpotential η10 of 300 mV in basic medium (OER) and 150 mV in acidic medium (HER), as well as a lower Tafel slope of 69 mV/dec (OER) and 181 mV/dec (HER), indicating 30% lower energy requirement for overall water splitting. Gas chromatography was used to examine the electrolyzed products.

Cobalt-modified 2D porous organic polymer for highly efficient electrocatalytic removal of toxic urea and nitrophenol.

The urea oxidation reaction (UOR) and nitrophenol reduction are safe and key limiting reactions for sustainable energy conversion and storage. Urea and nitrophenol are abundant in industrial and agricultural wastes, human wastewater, and in the environment. Catalytic oxidative and reductive removal is the most effective process to remove urea and 4-nitrophenol from the environment, necessary to protect human health. 2D carbon-supported, cobalt nanoparticle-based materials are emerging catalysts for nitrophenol reduction and as an anode material for the UOR. In this work, cobalt modified on a porous organic polymer (CoPOP) was synthesized and carbonized at 400 and 600 °C. The formation of CoPOP was confirmed by FT-IR spectroscopy, the 2D graphitic layer and amorphous carbon with cobalt metal by TEM, SEM, and PXRD, and the elemental composition by TEM mapping, EDX, and XPS. The catalytic activity for the 4-nitrophenol reduction was studied and the related electrocatalytic UOR was scientifically evaluated. The catalytic activity toward the reduction of 4-NP to 4-AP was tested with the addition of NaBH4; CoPOP-3 exhibited enhanced activity at a rate of 0.069 min-1. Furthermore, LSV investigated the catalytic activity of materials toward UOR, producing hydrogen gas, the products of which were analyzed via gas chromatography. Among the electrocatalysts studied, CoPOP-2 exhibited a lower onset potential, and the Tafel slope was 1.34 V and 80 mV dec-1. This study demonstrates that cobalt metal-doped porous organic polymers can be used as efficient catalysts to remove urea and nitrophenol from wastewater.

Ultrasonochemically conjugated metalloid/triblock copolymer nanocomposite and subsequent thin solid laminate growth for surface and interface studies.

Polymer and metalloid nanoparticles can be conjugated in a symphonized manner using ultrasonochemical force to obtain hybrid nanocomposites. The process is demonstrated using polymer poly(ethylene glycol) (PEG), metalloid SiO(2)@Ag, and triblock copolymer ABA. The acoustic microstreaming and cavitation force from the ultrasonics are crucial parameters that determine the harmonized PEG stabilization and ABA blending of the metalloid nanocomposites that are obtained. Surface plasmon resonance in the resulting hybrid systems are examined by UV-vis absorbance spectroscopy. The resulting PEG-stabilized SiO(2)-Ag conjugated with a triblock copolymer poly(p-dioxanone-co-caprolactone)-block-poly(ethylene oxide)-block-poly(p-dioxanone-co-caprolactone) (PPDO-co-PCL-b-PEG-b-PPDO-co-PCL/ABA) (PEG-SiO(2)@Ag/ABA) shows a red shift of 20 nm (410 nm) from its initial resonance at 390 nm (PEG-SiO(2)@Ag). Nanocomposite particles were then spin-coated on a glass substrate to obtain the growth of thin solid laminates (thickness 27 microm). Structural functionality was studied by FT-IR, (1)H NMR, and FT-Raman spectroscopy. Morphological properties were ensured from FE-SEM, HRTEM, AFM, and FIB-SEM. Identity and crystallinity of the prepared nanocomposite were confirmed by XRD analysis. A very low weight percentile loss of the fabricated nanocomposites ensures its high thermal stability. Fabricated nanocomposite laminate might have a role in coating, reinforcement, and resistance and as substrate additives for a variety of surface and interface studies. Further, the ultrasonochemical approach utilized here could also be a smart system to fabricate other heteronanostructures in a single platform.

DNA chip replication for a personalized DNA chip.

We report the replication technology of DNA chip using by sequence specific localization of nucleic acids via hybridization and electric transfer of the nucleic acids onto a new substrate without losing their array information. The denatured DNA fragments are first spotted and UV-cross-linked on a nylon membrane. The membrane is then immersed and hybridized in a DNA mixture solution that contains all complementary sequences of the nucleic acids to be hybridized with the DNA fragments on the membrane. The hybridized DNA fragments are transferred to another membrane at the denatured condition. After separating two membranes, the transferred membrane contains a complementary array of DNA fragments. This method can be used for the replication of the same copy of DNA chip repeatedly and moreover could be applied for a personalized DNA chip fabrication, where specific information of each spot of DNA chip is originated from the genetic information of a personal sample.

Osteogenic/angiogenic dual growth factor delivery microcapsules for regeneration of vascularized bone tissue.

Growth factors (GFs) are major biochemical cues for tissue regeneration. Herein, a novel dual GF delivery system is designed composed of poly(lactic-co-glycolic acid) (PLGA) nanoparticles (NPs) and alginate microcapsules (MCs) via an electrodropping method. While bone morphogenetic protein (BMP)-2 is encapsulated in the PLGA NPs, vascular endothelial growth factor (VEGF) is included in the alginate MCs, where BMP-2-loaded PLGA NPs are entrapped together in the fabrication process. The initial loading efficiencies of BMP-2 and VEGF are 78% ± 3.6% and 43% ± 1.7%, respectively. When our dual GF-loaded MCs are assessed for in vitro osteogenesis of umbilical cord blood-derived mesenchymal stem cells (UCB-MSCs) on 2D and 3D environment, MCs contribute to much better UCB-MSCs osteogenesis as confirmed by von Kossa staining, immunofluorescence (osteocalcin, collagen 1), calcium content measurement, and osteogenic markers expression. In addition, when dual GF-encapsulated MCs are combined with collagen and then applied to 8 mm diameter rat calvarial defect model, the positive effects on vascularized bone regeneration are much more pronounced; micro computed tomography (CT) and histology analyses exhibit 82.3% bone healing coupled with 12.6% vessel occupied area. Put together, current study indicates a synergistic effect of BMP-2/VEGF and highlights the great potential of dual GF delivery modality (PLGA NPs-in-MC) for regeneration of vascularized bone.

Graphene oxide functionalized with silver@silica-polyethylene glycol hybrid nanoparticles for direct electrochemical detection of quercetin.

A direct electrochemical detection of quercetin based on functionalized graphene oxide modified on gold-printed circuit board chip was demonstrated in this study. Functionalized graphene oxide materials are prepared by the covalent reaction of graphene oxide with silver@silica-polyethylene glycol nanoparticles (~12.35nm). Functionalized graphene oxide electrode shows a well-defined voltammetric response in phosphate buffered saline and catalyzes the oxidation of quercetin to quinone without the need of an enzyme. Significantly, the functionalized graphene oxide modified electrode exhibited a higher sensitivity than pristine gold-printed circuit board and graphene oxide electrodes, a wide concentration range of 7.5 to 1040nM and detection limit of 3.57nM. Developed biosensor platform is selective toward quercetin in the presence of an interferent molecule.

Evaluation of cytotoxicity, biophysics and biomechanics of cells treated with functionalized hybrid nanomaterials.

Hybrids consisting of carboxylated, single-walled carbon nanotube (c-SWNT)-silver nanoparticles (AgNPs)-DNA-poly vinyl alcohol (PVA) are synthesized via sequential functionalization to mimic the theragnostic (therapy and diagnosis) system. Carboxylation of SWNT has minimized the metal impurities with plenty of -COOH groups to produce hybrid (c-SWNT-AgNPs). The hybrid is further wrapped with DNA (hybrid-DNA) and encapsulated with PVA as hybrid composite (HC). Materials were tested against human alveolar epithelial cells (A549), mouse fibroblasts cells (NIH3T3) and human bone marrow stromal cells (HS-5). The composition-sensitive physico-chemical interactions, biophysics and biomechanics of materials-treated cells are evaluated. The cell viability was improved for HC, hybrid-PVA and c-SWNT when compared with SWNT and hybrid. SWNT and hybrid showed cell viability less than 60% at high dose (40 µg ml(-1)) and hybrid-PVA and HC retained 80% or more cell viability. The treatment of hybrid nanomaterials considerably changed cell morphology and intercellular interaction with respect to the composition of materials. Peculiarly, PVA-coated hybrid was found to minimize the growth of invadopodia of A549 cells, which is responsible for the proliferation of cancer cells. Surface roughness of cells increased after treatment with hybrid, where cytoplasmic regions specifically showed higher roughness. Nanoindentation results suggest that changes in biomechanics occurred owing to possible internalization of the hybrid. The changes in force spectra of treated cells indicated a possible greater interaction between the cells and hybrid with distinct stiffness and demonstrated the surface adherence and internalization of hybrid on or inside the cells.

A cell-repellent sulfonated PEG comb-like polymer for highly resolved cell micropatterns.

This paper investigates the chemical modification of a cell-repellent poly(ethylene glycol) (PEG)-based polymer to enhance its hydrophilicity with sulfonate groups, and its application in the fabrication of a cell microarray. First, a polymer comprised of a methyl methacrylate (MMA) backbone with PEG side-chains (PMMA-b-PEG) was synthesized from three monomers by radical polymerization and purified. Despite the hydrophilic side-groups in the amphiphilic polymer, the backbone structure's hydrophobicity allows for local adsorption of biomolecules in incubation media with or without serum. To enhance the hydrophilicity of the polymer, we tethered sulfonate groups to the hydroxyl groups on the PEG side chains (PMMA-b-PEG-SO3). The sulfate groups' physical and mechanical movement competitively repels biomolecules approaching the PMMA-b-PEG surface. Polymers modified with sulfonate were characterized by contact angle measurement, FT-IR, NMR, AFM and GPC. PMMA-b-PEG and PMMA-b-PEG-SO3 were successfully micropatterned on polystyrene and glass surfaces, and cell attachment was performed in either serum-free or serum-containing media, resulting in highly resolved cell micropatterns.

Polystyrene microbeads modified with an elastin-like biopolymer for stimuli-responsive immunodetection.

An efficient and controlled method for immunodetection, using polystyrene (PS) microbeads conjugated with an elastin-like polypeptide (ELP), was investigated. ELP is a temperature-sensitive polymer that exhibits a hydrophilic-hydrophobic phase transition at the lower critical solution temperature. To introduce amine groups, ELP was modified with lysine for conjugation with PS microbeads functionalized with carboxylic groups. Prostate-specific antigen (PSA), a cancer marker, was detected from a biomolecular mixture using ELP-conjugated PS microbeads and ELP-conjugated antiPSA. External stimuli were used to reversibly separate the PSA-antiPSA complex. The stimuli-responsiveness of the ELP provided a designable generic biosurface for diagnostic detection.

Polymeric optical microscreen for high-resolution surface plasmon resonance microarray imaging.

In this study, we demonstrate a simple method to fabricate surface plasmon resonance (SPR) imaging microarrays using polymer micropatterns. The use of a micrometer-scale polymeric optical screen (microPOS) passivates the region deposited with polymer by completely removing SPR signals or by saturating the SPR signal far beyond the detection range of SPR imaging. Two schemes were suggested to create a surface microPOS by either micropatterning a thick insulating layer before deposition of a metal layer (complete removal of SPR) or after deposition of a metal layer (saturation of SPR signal). The two schemes were successfully applied for the imaging of biological adsorption with a high imaging resolution of approximately 100 microm/pattern and 10 microm separation. The validity of the system was verified with a biotin-streptavidin system as a model for the systematic binding of biomolecules. Further, binding of prostate-specific antigen (PSA) onto the anti-PSA SPR microarray was demonstrated as a useful method for detecting a cancer marker.

Conjugation of heparin into carboxylated pullulan derivatives as an extracellular matrix for endothelial cell culture.

A carboxylated pullulan, for use as a structural material for a number of tissue engineering applications, was synthesized and conjugated with heparin. By immobilization of heparin to pullulan, endothelial cells (ECs) attached on the heparin-conjugated pullulan were more aggregated than when attached to other pullulan derivatives. Attachments were 50, 45, 49, and 90% for a polystyrene dish, pullulan acetate, carboxylated pullulan, and heparin-conjugated pullulan, respectively. Heparin-conjugated pullulan inhibited the proliferation of smooth muscle cells (SMCs) in vitro. Heparin-conjugated pullulan material can thus be used for the proliferation of vascular ECs and to inhibit the proliferation of SMCs.