An electrochemical immunosensor based on MXene-GQD/AuNPs for the detection of trace amounts of CA-125 as specific tracer of ovarian cancer.

An electrochemical immunoassay system was developed to detect CA-125 using a glassy carbon electrode (GCE) modified with MXene, graphene quantum dots (GQDs), and gold nanoparticles (AuNPs). The combined MXene-GQD/AuNPs modification displayed advantageous electrochemical properties due to the synergistic effects of MXene, GQDs, and AuNPs. The MXene-GQD composite in the modified layer provided strong mechanical properties and a large specific surface area. Furthermore, the presence of AuNPs significantly improved conductivity and facilitated the binding of anti-CA-125 on the modified GCE, thereby enhancing sensitivity. Various analytical techniques such as FE-SEM and EDS were utilized to investigate the structural and morphological characteristics as well as the elemental composition. The performance of the developed immunosensor was assessed using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), square wave voltammetry (SWV), and differential pulse voltammetry (DPV). Under optimized conditions in a working potential range of -0.2 to 0.6 V (vs. Ag/AgCl), the sensitivity, linear range (LR), limit of detection (LOD), and correlation coefficient (R2) were determined to be 315.250 µA pU.mL-1/cm2, 0.1 to 1 nU/mL, 0.075 nU/mL, and 0.9855, respectively. The detection of CA-125 in real samples was investigated using the developed immunoassay platform, demonstrating satisfactory results including excellent selectivity and reproducibility.

Fabrication of MXene/chitosan/polyurea nanocomposite decorated on a graphenized substrate for electro-enhanced solid-phase microextraction of diclofenac followed by its determination using differential pulse voltammetry.

A novel solid-phase microextraction fiber based on MXene-chitosan-polyurea (MXene/CS/EPPU) nanocomposite decorated on a graphenized pencil lead fiber (MXene/CS/EPPU/GPLF) was prepared and utilized for electro-enhanced solid-phase microextraction (EE-SPME) of diclofenac (DCF) in biological samples. After extraction and desorption of DCF, it was determined by differential pulse voltammetry (DPV). For this purpose, the working electrode was prepared by deposition of the mentioned MXene/CS/EPPU nanocomposite onto the graphenized pencil lead. The synthesized SPME fiber was characterized using scanning electron microscopy and X-ray diffraction techniques. The effect of various parameters influencing the extraction and the desorption process were investigated, including applied voltage in the extraction and desorption steps, extraction and desorption times, and pH. The developed method exhibited a rather wide linearity in the range 2-1200 ng mL-1 (R2 = 0.985) for the determination of DCF in plasma samples. The limit of detection and the limit of quantification for plasma samples were estimated to be 0.58 and 1.9 ng mL-1 based on the 3Sb/m and 10Sb/m definitions, respectively. The method's accuracy and applicability have been evaluated by the analysis of plasma samples, leading to the relative recoveries in the range 87.0% and 98.0% with the relative standard deviations lower than 3.1%.

Copper (II) complexes with N, S donor pyrazole-based ligands as anticancer agents.

A group of bidentate nitrogen and sulfur donor pyrazole derivative ligands abbreviated as Na[RNCS(Pz)], Na[RNCS(PzMe2)], Na[RNCS(PzMe3)], Na[RNCS(PzPhMe)], Na[RNCS(PzPh2)], where (R = Et, Ph), and their Cu (II) complexes were synthesized and characterized by spectroscopic and physicochemical methods. The crystal structure of [Cu(PhNCSPzMe3)2] was determined by X-ray crystallography analysis and the results described a distorted square planar coordination geometry for this complex. Also, the cyclic voltammetry investigations indicated that the synthesized copper complex is an electrochemically active species. Moreover, the cytotoxic activity of all of the twenty synthesized compounds was evaluated using MTT assay against the MCF-7 (human breast carcinoma) cell lines, in vitro. Cu (II) complexes indicate significant cytotoxicity against the MCF-7 cell lines as compared with the free ligands. The docking studies showed that the copper complexes have better interactions with EGFR and CDK2 proteins, compared to the free ligands, and most of the studied compounds have a higher value of binding energy relative to the studied controls. The results of QSAR analysis suggest that dipole moment is in direct correlation with the obtained IC50 values, and it strongly impact the anticancer effects generated by the compounds. Our findings suggest that the developed copper complexes can be good candidates for further evaluations as chemotherapeutic agents in the treatment of cancer.

Simultaneous removal of cationic and anionic dyes from simulated industrial effluents using a nature-inspired adsorbent.

Alginate-grafted polyaniline (Alg-g-PANI) microparticles were synthesized through the grafting of aniline onto functionalized Alg followed by double crosslinking by glutaraldehyde and calcium chloride. The performance of the developed microparticles as adsorbent in simultaneous removal of malachite green (MG) and congo red (CR) dyes were examined by the batch method. Experimental parameters, including adsorbent amount, pH, initial dyes concentrations, and contact time were optimized. Langmuir and Freundlich adsorption models were employed to explore the equilibrium isotherm. As the Langmuir model results, the maximum adsorption capacities (Qm) of microparticles for the MG and CR dyes were obtained as 578.3 and 409.6 mgg-1, respectively. Adsorption kinetics for both dyes were well-fitted with the pseudo-second-order model that confirm the rate-limiting step might be the chemical adsorption. The adsorbent was regenerated via desorption process and was reusable five times without a substantial decrease in its adsorption efficacy in first three cycles. Adsorbent-dyes interactions were computationally evaluated using Gromacs package, and it was found that both MG and CR are able to interact strongly with the adsorbent. In accordance with experimental results, simulation data revealed that MG can be removed more efficiently than those of the CR. As the experimental results, we could conclude that the synthesized Alg-g-PANI microparticles can be used as a nature-inspired adsorbent for simultaneous removals of CR and MG dyes.

A novel bio-inspired conductive, biocompatible, and adhesive terpolymer based on polyaniline, polydopamine, and polylactide as scaffolding biomaterial for tissue engineering application.

A novel electrically conductive nanofibrous scaffold based on polyaniline-co-(polydopamine-grafted-poly(d,l-lactide)) [PANI-co-(PDA-g-PLA)] was fabricated using electrospinning technique and its physicochemical as well as biological characteristics toward bone tissue engineering (TE) were investigated extensively. In detail, PANI-co-PDA was synthesized via a one-step chemical oxidization approach. Then, d,l-lactaide monomer was grafted onto PDA segment using a ring opening polymerization (ROP) to afford PANI-co-(PDA-g-PLA) terpolymer. The successful synthesis of PANI-co-(PDA-g-PLA) terpolymer was confirmed using FTIR spectroscopy as well as TGA analysis. Finally, a solution of the synthesized terpolymer was electrospun to fabricate a conductive nanofibrous scaffold. Some physicochemical features such as mechanical, conductivity, electroactivity, hydrophobicity, and morphology as well as biological characteristics including biocompatibility, biodegradability, as well as enhancing the cells adhesion and proliferation were investigated. According to the above-mentioned experimental results, the fabricated electrospun nanofibers can be considered as a potential scaffold for TE application, mainly due to its proper physicochemical and biological properties.

Preconcentration of mercury(II) using a magnetite@carbon/dithizone nanocomposite, and its quantification by anodic stripping voltammetry.

A new adsorbent is described that consists of a magnetite@carbon/dithizone nanocomposite. It was characterized using energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and field emission scanning electron microscopy. The magnetic sorbent is shown to be a viable material for the preconcentration of mercury(II) before its quantification by differential pulse anodic stripping voltammetry. The effects of pH value, eluent, adsorbent amount, sample volume, and adsorption/desorption time were optimized. The calibration plot extends from 0.25 to 30 ng.mL-1, and the detection limit is 27 pg.mL-1. The preconcentration factor and intra-day and inter-day relative standard deviations are 100, 3.8, and 4.5%, respectively, for six measurements at 5 ng.mL-1 concentrations of mercury(II). The method was validated by the analysis of the certified reference material NIST SRM 1566b, and successfully applied to the preconcentration and quantification of mercury(II) in industrial wastewaters and spiked water samples. Graphical abstractSchematic representation of magnetic solid-phase extraction of mercury(II) ion by dithizone-modified Fe3O4@C nanocomposite (Fe3O4@C/Dz NC) before its quantification by anodic stripping voltammetry (ASV).

Scaffolding polymeric biomaterials: Are naturally occurring biological macromolecules more appropriate for tissue engineering?

Nowadays, tissue and organ failures resulted from injury, aging accounts, diseases or other type of damages is one of the most important health problems with an increasing incidence worldwide. Current treatments have limitations including, low graft efficiency, shortage of donor organs, as well as immunological problems. In this context, tissue engineering (TE) was introduced as a novel and versatile approach for restoring tissue/organ function using living cells, scaffold and bioactive (macro-)molecules. Among these, scaffold as a three-dimensional (3D) support material, provide physical and chemical cues for seeding cells and has an essential role in cell missions. Among the wide verity of scaffolding materials, natural or synthetic biopolymers are the most commonly biomaterials mainly due to their unique physicochemical and biological features. In this context, naturally occurring biological macromolecules are particular of interest owing to their low immunogenicity, excellent biocompatibility and cytocompatibility, as well as antigenicity that qualified them as popular choices for scaffolding applications. In this review, we highlighted the potentials of natural and synthetic polymers as scaffolding materials. The properties, advantages, and disadvantages of both polymer types as well as the current status, challenges, and recent progresses regarding the application of them as scaffolding biomaterials are also discussed.

Target-triggered three-way junction in conjugation with catalytic concatemers-functionalized nanocomposites provides a highly sensitive colorimetric method for miR-21 detection.

With the great advances in DNA nanotechnology, scientists have shown interest in developing dynamic nanostructures for theranostic applications, analyte sensing and cargo delivery. Here, we present a specific enzyme-free ultrasensitive platform based on a multilayer coupled signal amplification strategy to quantify miR-21 molecule. The biosensor was integrated based on three signal amplification gadgets, namely a translator-mediated catalytic hairpin assembly (CHA), a multilayer DNA concatemer on the surface of gold decorated magnetic nanoparticle (GMNP), and a DNAzyme-mediated catalytic signal amplification. MiR-21 mediates the release of a DNA translator from an immobilized duplex to engage in a CHA reaction using three hairpins, including a GMNP-conjugated hairpin 1 (H1), biotin-labeled hairpin 2 (H2) and a GMNP-conjugated hairpin 3 (H3) to form a three-way junction (3WJ). Meanwhile, a plenty of initiator strand 0 (S0) on GMNPs - each of which has been bifunctionalized with S0/H1 or S0/H3 - drive several multilayer peroxidase-mimicking DNAzyme concatemers in the presence of two accessory oligonucleotides; strand 1 (S1) and strand 2 (S2). Since a G-rich sequence was attached at the 5'-end of S1 strand, in the presence of hemin cofactor, an active G-quadruplex DNAzyme with peroxidase activity was formed. The concatemers on the surface of GMNPs can convert a colorless substrate to a green product. The biosensor can detect as low as 1 aM of miR-21 and provide an excellent capability to discriminate single-base mismatches. The required time for the formulation of the assay reagents is about three days and the reaction time for the detection of miR-21 takes place in less than four hours.

PEGylated graphene oxide/Fe3O4 nanocomposite: Synthesis, characterization, and evaluation of its performance as de novo drug delivery nanosystem.

This paper describes the development of mitoxantrone-loaded PEGylated graphene oxide/magnetite nanoparticles (PEG-GO/Fe3O4-MTX), and investigation of its preliminary drug delivery performance. For this, the GO was synthesized through oxidizing graphite powder, and subsequently carboxylated using a substitution nucleophilic reaction. The carboxylated GO (GO-COOH) was then conjugated with amine end-caped PEG chains by Steglich esterification. Afterward, GO-PEG/Fe3O4 nanocomposite was synthesized through the anchoring of Fe3O4 nanoparticles onto the surface of GO-PEG during the sonication. The biocompatibility and MTX-loading capacity of the synthesized GO-PEG/Fe3O4 nanocomposite were evaluated. The pH dependent drug release behavior and cytotoxicity effect of the MTX-loaded GO-PEG/Fe3O4 nanocomposite were also studied. According to biocompatibility, pH dependent drug release behavior as well as superior physicochemical and biological characteristics of graphene and magnetite nanoparticles, it is expected that the GO-PEG/Fe3O4 nanocomposite may be applied as de novo drug delivery system (DDS) for cancer therapy using both chemo- and photothermal therapy approaches.

Preparation of graphene oxide doped eggshell membrane bioplatform modified Prussian blue nanoparticles as a sensitive hydrogen peroxide sensor.

This study describes the preparation and characterization of graphene oxide doped eggshell membrane (GO-ESM) as a novel electrochemical bioplatform for electroanalytical purposes. The GO-ESM bioplatform was prepared by incorporation of GO nano-sheets into the ESM via a facile sonication procedure. Field emission scanning electron microscopy and X-ray diffraction powder techniques were used to characterize the developed bioplatform. The electrochemistry of GO-ESM was investigated by decorating it on the surface of carbon ceramic electrode (CCE) by an O-ring. The GO-ESM platform was modified with Prussian blue (PB) via a facile dip-coating method. Then the resulted modified electrode (PB|GO-ESM|CCE) was used as a novel hydrogen peroxide electrochemical sensor. The fabricated electrode responds efficiently to H2O2 over the concentration range 125nM-195µM with a detection limit of 31nM (S/N=3) and sensitivity 8.8µAµM(-1)cm(-2). The PB|GO-ESM|CCE has been successfully applied to determination of H2O2 content in spiked milk samples. Due to good stability, environmental friendly, cheapness, nontoxic, well behaved electrochemical properties, and biocompatibility, the fabricated bioplatform has the promising future for practical applications.

D-penicillamine capped cadmium telluride quantum dots as a novel fluorometric sensor of copper(II).

D-penicillamine-capped cadmium telluride quantum dots (DPA-capped CdTe QDs) were synthesized as the new fluorescent semiconductor nanocrystal in aqueous solution. Fourier transmission infrared spectroscopy, X-ray diffraction, transmission electron microscopy, ultraviolet-visible and photoluminescence spectroscopy were used for characterization of the QDs. Based on the quenching effect of Cu(2+) ions on the fluorescence intensity of DPA-capped CdTe QDs, a new fluorometric sensor for copper(II) detection was developed that showed good linearity over the concentration range 5 × 10(-9)-3 × 10(-6) M with the detection limit 0.4 × 10(-9) M. Owing to the strong affinity of the DPA to copper(II), the sensor showed appropriate selectivity for copper(II) compared with conventional QDs. The DPA-capped CdTe QDs was successfully applied for determination of Cu(2+) concentration in river, well and tap waters with satisfactory results.

Graphene quantum dots as a new substrate for immobilization and direct electrochemistry of glucose oxidase: application to sensitive glucose determination.

Graphene quantum dots (GQD) were introduced as a novel and suitable substrate for enzyme immobilization. Glucose oxidase (GOx) was immobilized on GQD modified carbon ceramic electrode (CCE) and well-defined quasi-reversible redox peaks were observed. The UV-vis photoluminescence spectroscopy, transition electron microscopy, field emission scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry techniques were used for characterizing the electrochemical biosensor. The electron transfer coefficient (α) and the heterogeneous electron transfer rate constant (k(s)) for redox reaction of GOx were found to be 0.48 and 1.12 s(-1), respectively. The developed biosensor responds efficiently to glucose presence over the concentration range 5-1270 µM with the detection limit 1.73 µM (S/N=3) and sensitivity 0.085 µA µM(-1) cm(-2). The high value of surface coverage GOx-GQD|CCE (1.8×10(-9) mol/cm(2)) and the small value of Michaelis-Menten constant (0.76 mM) confirmed an excellent loading of the enzyme and a high affinity of biosensor to glucose. High performance of the biosensor is attributed to the large surface-to-volume ratio, excellent biocompatibility of GQD, porosity of GQD|CCE, and the abundance of hydrophilic edges as well as hydrophobic plane in GQD which enhances the enzyme absorption on the electrode surface.