Advanced Uranium Removal with Pure, Nonfluorinated Ionic Liquids: Fine-Tuning Hydrophilic and Hydrophobic Properties for Enhanced Selectivity.

Ionic liquids (ILs) have significant potential for eco-friendly extraction of uranium from aqueous solutions, which is critical for nuclear technology, fuel cycle management, and environmental protection. This study examines the impact of the adjustable hydrophobic/hydrophilic properties of ILs on the removal of uranium(VI) (UO22+) from aqueous solutions utilizing both a novel hydrophilic IL (1-butoxyethyl-1-methylmorpholinium butoxyethylphosphite - Mor1-2O4-BOEP) and 1-heptyl-1-methylmorpholinium heptylphosphite (Mor1-7-HP) as an example of a hydrophobic IL with a similar structure. The transfer mechanism of uranyl ions from water to organic or solid phases closely depends on the physicochemical properties of ILs, especially their hydrophobicity. The hydrophobic Mor1-7-HP extracts uranyl via neutral complex formation as UO2(NO3)2-(Mor1-7-HP)2. Conversely, hydrophilic Mor1-2O4-BOEP induced selective precipitation as UO2(NO3)-(BOEP), transferring uranyl to the solid phase. Optimization of the working parameters, in terms of acidity of the aqueous solution and amount of ILs used, allowed the extraction of over 98% of U(VI). The stoichiometry of the organic complex and the precipitate was determined using physicochemical techniques. These tunable H-phosphonate-based ILs have advantages over traditional solvent extraction and conventional ILs, allowing easier handling, improved selectivity, and lower environmental impact. This work advances uranium separation techniques with applications in hydrometallurgy, particularly in the treatment of wastewater and radioactive waste for sustainable uranium recovery.

Covalent surface modification of single-layer graphene-like BC6N nanosheets with reactive nitrenes for selective ammonia sensing via DFT modeling.

Novel graphene-like nanomaterials with a non-zero bandgap are important for the design of gas sensors. The selectivity toward specific targets can be tuned by introducing appropriate functional groups on their surfaces. In this study, we use first-principles simulations, in the form of density functional theory (DFT), to investigate the covalent functionalization of a single-layer graphitized BC6N with azides to yield aziridine-functionalized adducts and explore their possible use to realize ammonia sensors. First, we determine the most favorable sites for physical adsorption and chemical reaction of methylnitrene, arising from the decomposition of methylazide, onto a BC6N monolayer. Then, we examine the thermodynamics of the [1 + 2]-cycloaddition reaction of various phenylnitrenes and perfluorinated phenylnitrenes para-substituted with (R = CO2H, SO3H) groups, demonstrating favorable energetics. We also monitor the effect of the functionalization on the electronic properties of the nanosheets via density of states and band structure analyses. Finally, we test four dBC6N to gBC6N substrates in the sensing of ammonia. We show that, thanks to their hydrogen bonding capabilities, the functionalized BC6N can selectively detect ammonia, with interaction energies varying from -0.54 eV to -1.37 eV, even in presence of competing gas such as CO2and H2O, as also confirmed by analyzing the change in the electronic properties and the values of recovery times near ambient temperature. Importantly, we model the conductance of a selected substrate alone and in presence of NH3to determine its effect on the integrated current, showing that humidity and coverage conditions should be properly tuned to use HO2C-functionalized BC6N-based nanomaterials to develop selective gas sensors for ammonia.

σ-Hole intermolecular interactions between carbon oxides and dihalogens: Ab-initio investigations.

Recently, halogen bonding (XB) has received increased attention as a new type of non-covalent interaction widely present in nature. In this work, quantum chemical calculations at DFT level have been carried out to investigate halogen bonding interactions between COn (n = 1 or 2) and dihalogen molecules XY (X = F, Cl, Br, I and Y = Cl, Br, I). Highly accurate all-electron data, estimated by CCSD(T) calculations, were used to benchmark the different levels of computational methods with the objective of finding the best accuracy/computational cost. Molecular electrostatic potential, interaction energy values, charge transfer, UV spectra, and natural bond orbital (NBO) analysis were determined to better understand the nature of the XB interaction. Density of states (DOS) and projected DOS were also computed. Hence, according to these results, the magnitude of the halogen bonding is affected by the halogen polarizability and electronegativity, where for the more polarizable and less electronegative halogen atoms, the σ-hole is bigger. Furthermore, for the halogen-bonded complexes involving CO and XY, the OC∙∙∙XY interaction is stronger than the CO∙∙∙XY interaction. Thus, the results presented here can establish fundamental characteristics of halogen bonding in media, which would be very helpful for applying this noncovalent interaction for the sustainable capture of carbon oxides.

Laser-induced graphene electrodes on polyimide membranes modified with gold nanoparticles for the simultaneous detection of dopamine and uric acid in human serum.

The level control of biological active molecules in human body fluids is important for the surveillance of several human diseases. Dopamine (DA) and uric acid (UA) are two important biomarkers of neurological and bone diseases, respectively. Design of sensitive and cost-effective sensors for their detection is an effervescent research field. We report on the straightforward design of laser-induced graphene electrodes (LIGEs) from the laser ablation of a polyimide substrate and their modification by electrochemical deposition of gold nanoparticles (AuNPs/LIGE) and their uses as chemosensors. Electrochemical investigations showed that the presence of gold nanoclusters onto the electrode surface improved the electrochemical surface area (ECSA) and the heterogenous electron transfer (HET) rate. Furthermore, the AuNPs/LIGEs can be used to detect simultaneously low concentrations of DA and UA in presence of ascorbic acid (AA) as an potentially interfering substance at redox potentials of 300 mV, 230 mV and 450 mV and 91 mV, respectively, compared with the Ag/AgCl (3 M KCl) reference electrode in cyclic voltametric. The method displayed linear ranges varying from 2 to 20 µM and 5 to 50 µM, led to limits of detection of 0.37 µM and 0.71 µM for DA and UA, respectively. The AuNPs/LIGE was applied to simultaneously detect both analytes in scarcely diluted human serum with good recoveries. The data show that the recovery percentages ranged from 94% ± 2.1 to 102 % ± 0.5 and from 94% ±0.3 to 112% ± 1.4 for dopamine and uric acid, respectively. Thus, the AuNPs/LIGEs are promising candidates for the detection of other biologically active molecules such as drugs, pesticides, and metabolites.

Sub-femtomolar capacitance-based biosensing of kanamycin using screen-printed electrodes coated with redox-active polymeric films.

An ultrasensitive capacitance-based biosensor has been developed capable of detecting the kanamycin (KAN) antibiotic at sub-femtomolar levels. The biosensor was constructed using a potential-pulse-assisted method, allowing for the layer-by-layer deposition of a melanin-like polymeric film (MLPF) on an electrode surface modified with gold nanoparticles (AuNPs). The MLPF was formed through the electrochemical polymerization of dopamine and the specific kanamycin aptamer. By optimizing the operating parameters, we achieved a label-free detection of kanamycin by monitoring the variation of pseudocapacitive properties of the MLPF-modified electrode using electrochemical impedance spectroscopy. The developed biosensor demonstrated a wide linear response ranging from 1 fM to 100 pM, with a remarkable limit of detection of 0.3 fM (S/N = 3) for kanamycin. Furthermore, the biosensor was successfully applied to detect kanamycin in milk samples, exhibiting good recovery. These findings highlight the promising potential of the aptasensor for determination of antibiotic residues and ensuring food safety. In conclusion, our ultrasensitive capacitance-based biosensor provides a reliable and efficient method for detecting trace amounts of kanamycin in dairy products. This technology can contribute to safeguarding consumer health and maintaining high food safety standards.

Sensitive electrochemical detection of polymorphisms in IL6 and TGFß1 genes from ovarian cancer DNA patients using EcoRI and DNA hairpin-modified gold electrodes.

Two electrochemical bioplatforms were prepared based on thiolated hairpin DNA probes tethered to AuNP-modified screen-printed electrodes to detect T > G and T > C polymorphisms, namely rs1880269 and rs1800469, present the interleukin-6 (IL6) and transforming growth factor ß1 (TGFß1) genes. The electrochemical readout was ensured by the detection of the double-stranded DNA using methylene blue as a redox probe after treatment by EcoRI restrictase. The main parameters influencing the analytical response such as the thiolated DNA probe concentration, incubation time with electrode, DNA hybridization time, EcoRI enzyme load, and its cleavage time were optimized based on the current intensity and signal-to-blank (S/B) ratio as selection criteria. Using spiked buffer solutions, the IL6 and TGFß1 E-bioplatforms display wide ranges of linearity (1 × 102-1 × 108 fM and 5 × 101-1 × 105 fM, respectively) and limits of detection (47.9 fM and 16.6 fM, respectively). The two bioelectrodes have also good discrimination toward 1-mismatched, two mismatched, and non-complementary sequences, when they were used 30-fold higher than the target sequences. More importantly, the two bioplatforms successfully detected the single nucleotide polymorphisms (SNPs) in scarcely diluted genomic DNA, collected from 52 donors, and showed they can reliably distinguish between heterozygous (TG and TC genotypes) and homozygous (GG and CC genotypes) patients with  respect to the control subjects (TT genotype), where the differences are statistically highly significant (p-value < 0.0001). Thus, the designed devices could be used to conduct large cohort studies targeting these mutations or extended to other SNPs.

Sandwich-Based Immunosensor for Dual-Mode Detection of Pathogenic F17-Positive Escherichia coli Strains.

Bacterial diseases cause tremendous economic losses due to high morbidity and mortality in livestock animals. F17A protein, the major subunit of F17 fimbriae, is one of the most prevalent and crucial virulence factors among the pathogenic Escherichia coli (E. coli) isolated from diarrheic and septicemic animals of various species. Purification and detection of this protein is regarded as an interesting field of investigation due to its important role as a therapeutic target, such as vaccines, and as a diagnostic tool. In this context, polyclonal rabbit antibodies recognizing F17A protein (anti-F17A antibody) were developed and used for its detection. In fact, sandwich biosensor using anti-F17A/gold nanoparticles conjugates as capture probe and anti-F17A antibody labelled with horseradish peroxidase as signal amplification probe was developed for electrochemical and fluorescent detection of purified F17A protein and live F17-positive E. coli bacteria. Good specificity and sensitivity for detection of F17-positive E. coli strains were obtained. The dynamic range for the biosensor varies from 1 × 102 to 1 × 109 CFU·mL-1 (R2 = 0.998) and the detection limit (LOD) and the IC50 value were estimated to be 37 CFU·mL-1 and 75 CFU·mL-1, respectively.

Multiplexed Magnetofluorescent Bioplatform for the Sensitive Detection of SARS-CoV-2 Viral RNA without Nucleic Acid Amplification.

Rapid and sensitive detection of SARS-CoV-2 virus genetic material is of paramount importance to mitigate the COVID-19 pandemic outbreak and lower the death toll. Herein, we report the design of a magnetofluorescent bioplatform for the direct and specific detection of the viral RNA of SARS-CoV-2 in the total RNA extracted from nasopharyngeal swabs of COVID-19-positive patients. A higher fluorescence response was achieved using two capture probes tethered to magnetic beads using a biotin/streptavidin linkage, targeting two specific sites in the ORF1a and S genes. Two horseradish peroxidase (HRP)-conjugated reporter sequences, complementary to the loci of the S and N genes, were used to reveal the presence of the viral RNA through the oxidation of o-phenylenediamine to fluorescent 2,3-diaminophenazine. Under optimal conditions, the bioplatform showed high selectivity and sensitivity and was able to detect as low as 0.01 ng of viral RNA (1 × 103 copies/µL) with a linear dynamic range varying from 0.01 to 3.0 ng (1 × 103 to 9 × 107 copies/µL). The bioplatform was also able to discriminate the SARS-CoV-2 RNA from those of other related viruses such as hepatitis C, West Nile, measles, and non-polio viruses. Furthermore, the developed biosensor was validated in 46 clinical samples (36 COVID-19-positive patients and 10 COVID-19-negative subjects, as assessed with the gold standard RT-qPCR method). Both sensitivity and specificity of the developed method reached 100%. Finally, making such a simple and specific method available in the field, at a primary point of care, can better help the detection of SARS-CoV-2 infection in low-resource settings.

Impedimetric DNA E-biosensor for multiplexed sensing of Escherichia coli and its virulent f17 strains.

An impedance-based DNA multiplexed biosensor was designed to simultaneously detect Escherichia coli (yaiO gene) and its virulent f17 variant. The thiolated DNA dual probe was self-assembled onto the surface of the gold nanoparticle-modified screen-printed carbon electrode (AuNPs/SPCE) to recognize selected sequences from yaiO and f17 genes. The optimal conditions to prepare the bioelectrode were determined based on the monitoring of the impedimetric response fitted to an equivalent electrical circuit model. The charge transfer resistance of the bioelectrode increased by recognizing the target DNA sequences. The limit of detection was 0.8 fM and 1.0 fM for yaiO and f17 target DNA, respectively, and the linearity ranged from 1 × 10-15 to 1 × 10-7 M with a linear regression coefficient R ≥ 0.995. The nanodevice provided a novel strategy for simultaneous detection of E. coli and its virulence f17 gene with excellent discrimination with a single-base mismatch, two-base mismatch, and non-complementary sequences. Moreover, genomic DNA extracted from E. coli bacteria isolated from diarrheic camel calves and control animals in Tunisia was successfully detected using the as-prepared biosensor with minimal treatment of the extracted DNA samples.Graphical abstract.

Determination of miRNAs in serum of cancer patients with a label- and enzyme-free voltammetric biosensor in a single 30-min step.

The preparation of an integrated biosensor for the easy, fast, and sensitive determination of miRNAs is described based on a direct hybridization format and a label-free voltammetric detection. The biosensor involves a disposable carbon electrode substrate doubly nanostructured with reduced graphene oxide (rGO) and AuNPs modified with pyrene carboxylic acid (PCA) and 6-ferrocenylhexanethiol (Fc-SH), respectively. A synthetic amino terminated DNA capture probe was covalently immobilized on the CO2H moieties of PCA/rGO, while Fc-SH was used as a signaling molecule. Differential pulse voltammetry was employed to record the decrease in the oxidation peak current of Fc after the hybridization due to the hindering of the electron transfer upon the formation of the DNA-RNA duplex on the electrode surface. The stepwise biosensor preparation was characterized by surface and electrochemical techniques showing the role played by each biosensor component as well as the reliability of the target miRNA determination. The determination of the oncogene miRNA-21 synthetic target allowed quantification in the low femtomolar range (LOD of 5 fM) with a high discrimination of single-base mismatched sequences in a single 30-min incubation step. The bioplatform allowed the determination of the target miRNA in a small amount of total RNA extracted from breast cancer (BC) cells or directly in serum samples collected from BC patients without the need for prior extraction, purification, amplification, or reverse transcription of the genetic material and with no matrix effect. Graphical abstract.

Electrochemical immunoassay for lactalbumin based on the use of ferrocene-modified gold nanoparticles and lysozyme-modified magnetic beads.

The authors describe a method for electrochemical determination of the breast cancer biomarker α-lactalbumin (α-LA) using disposable screen-printed carbon electrodes (SPCEs). Lysozyme-conjugated Fe3O4 nanoparticles (Lys-Fe3O4NPs) were used to capture α-LA on the surface of the SPCEs which then is trapped in an immunosandwich using secondary antibodies labeled with ferrocene-modified gold nanoparticles. The amperometric response of ferrocene (recorded at +0.1 V vs. silver pseudo-reference electrode) as well as the electrocatalytic activity of gold nanoparticles on the hydrogen evolution reaction (recorded at -1.0 V Vs Ag pseudo-reference electrode) was exploited to sense α-LA. A sensitive voltammetric response is observed, with (a) a sensitivity of 0.8789 µA·nM-1.cm-2, (b) a detection limit (LOD, at S/N = 3) as low as 0.07 ng·mL-1, and (c) linear response in the 0.75 to 630 ng mL-1 α-LA concentration range. The assay is selective and reproducible, and the SPCEs have good storage stability. The SPCEs were applied (a) to the analysis of (spiked) maternal milk, (b) of spiked serum from healthy and pregnant persons, and (c) of serum of patients suffering from breast cancer. Graphical abstract Schematic presentation of a sensitive electrochemical immunoassay platform based on ferrocene modified gold nanoparticles and lysozyme modified magnetic beads for the determination of alpha lactalbumin in human sera and breast milk by the amperometric response of ferrocene and hydrogen evolution reaction.

Single-Step Incubation Determination of miRNAs in Cancer Cells Using an Amperometric Biosensor Based on Competitive Hybridization onto Magnetic Beads.

This work reports an amperometric biosensor for the determination of miRNA-21, a relevant oncogene. The methodology involves a competitive DNA-target miRNA hybridization assay performed on the surface of magnetic microbeads (MBs) and amperometric transduction at screen-printed carbon electrodes (SPCEs). The target miRNA competes with a synthetic fluorescein isothiocyanate (FITC)-modified miRNA with an identical sequence for hybridization with a biotinylated and complementary DNA probe (b-Cp) immobilized on the surface of streptavidin-modified MBs (b-Cp-MBs). Upon labeling, the FITC-modified miRNA attached to the MBs with horseradish peroxidase (HRP)-conjugated anti-FITC Fab fragments and magnetic capturing of the MBs onto the working electrode surface of SPCEs. The cathodic current measured at -0.20 V (versus the Ag pseudo-reference electrode) was demonstrated to be inversely proportional to the concentration of the target miRNA. This convenient biosensing method provided a linear range between 0.7 and 10.0 nM and a limit of detection (LOD) of 0.2 nM (5 fmol in 25 µL of sample) for the synthetic target miRNA without any amplification step. An acceptable selectivity towards single-base mismatched oligonucleotides, a high storage stability of the b-Cp-MBs, and usefulness for the accurate determination of miRNA-21 in raw total RNA (RNAt) extracted from breast cancer cells (MCF-7) were demonstrated.

Label-free electrochemical genosensor based on mesoporous silica thin film.

A novel label-free electrochemical strategy for nucleic acid detection was developed by using gold electrodes coated with mesoporous silica thin films as sensing interface. The biosensing approach relies on the covalent attachment of a capture DNA probe on the surface of the silica nanopores and further hybridization with its complementary target oligonucleotide sequence, causing a diffusion hindering of an Fe(CN)6 (3-/4-) electrochemical probe through the nanochannels of the mesoporous film. This DNA-mesoporous silica thin film-modified electrodes allowed sensitive (91.7 A/M) and rapid (45 min) detection of low nanomolar levels of synthetic target DNA (25 fmol) and were successfully employed to quantify the endogenous content of Escherichia coli 16S ribosomal RNA (rRNA) directly in raw bacterial lysate samples without isolation or purification steps. Moreover, the 1-month stability demonstrated by these biosensing devices enables their advanced preparation and storage, as desired for practical real-life applications. Graphical abstract Mesoporous silica thin films as scaffolds for the development of novel label-free electrochemical genosensors to perform selective, sensitive and rapid detection of target oligonucleotide sequences. Application towards E. coli determination.

Enhanced sensitivity in electrochemical detection of ochratoxin A within food samples using ferrocene- and aptamer-tethered gold nanoparticles on disposable electrodes.

Ensuring food security is crucial for public health, and the presence of mycotoxins, produced by fungi in improperly stored processed or unprocessed food, poses a significant threat. This research introduces a novel approach - a disposable aptasensing platform designed for the detection of ochratoxin A (OTA). The platform employs gold-nanostructured screen-printed carbon electrodes functionalized with a ferrocene derivative, serving as an integrated faradaic transducing system, and an anti-OTA aptamer as a bioreceptor site. Detection relies on the ferrocene electrochemical signal changes induced by the aptamer folding in the presence of the target molecule. Remarkably sensitive, the platform detects OTA within the range of 0.5 to 70 ng mL-1 and a detection limit of 11 pg mL-1. This limit is approximately 200 times below the levels stipulated by the European Commission for agricultural commodities. Notably, the sensing device exhibits efficacy in detecting OTA in complex media, such as roasted coffee beans and wine, without the need for sample pretreatment, yielding accurate recoveries. Furthermore, while label-free electrochemical aptasensors have proliferated, this study addresses a gap in understanding the binding mechanisms of some aptasensors. To enhance the experimental findings, a theoretical study was conducted to underscore the specificity of the anti-OTA aptamer as a donor for OTA detection. The molecular docking technique was employed to unveil the key binding region of the aptamer, providing valuable insights into the aptasensor specificity.

Smartphone-based device for rapid and single-step detection of piRNA-651 using anti-DNA:RNA hybrid antibody and enzymatic signal amplification.

P-element-induced wimpy testis (PIWI)-interacting RNAs (piRNAs/piRs) are a class of small noncoding RNAs that play a crucial role in regulating various biological processes, including carcinogenesis. One specific piRNA, piR-651, has been reported to be overexpressed in both human blood serum and solid cancer tissues, that can be used a viable biomarker in cancer diagnosis. Early diagnosis of cancer can help reduce the burden of the disease and improve survival rates. In the present work, we report for the first time a smartphone-based colorimetric biosensor for highly sensitive and specific detection of piR-651 thanks to an enzymatic signal amplification, which yielded high colorimetric intensities. Indeed, a heteroduplex DNA:RNA was formed in the presence of piR-651 with the capture DNA probe immobilized on the magnetic beads for easy magnetic separation. Then, a HRP tethered to anti-DNA:RNA (S9.6) was used to reveal the DNA-RNA heteroduplex formed by catalyzing the oxidation of TMB substrate into colorimetric TMBox, which absorbs at 630 nm. The absorbance is positively proportional to the piR-651 concentrations. On the other hand, the colorimetric product of the assay can be photographed with a smartphone camera and analyzed using ImageJ software. Using a smartphone and under optimal conditions, the biosensor responded linearly to the logarithm of piRNA-651 from 8 fM to 100 pM with a detection limit of 2.3 fM and discriminates against other piRNAs. It was also successfully applied to the determination of piRNA-651 levels in spiked human serum.

Detection of SARS-CoV-2 N protein using AgNPs-modified aligned silicon nanowires BioSERS chip.

The SARS-CoV-2 (COVID-19) pandemic had a strong impact on societies and economies worldwide and tests for high-performance detection of SARS-CoV-2 biomarkers are still needed for potential future outbreaks of the disease. In this paper, we present the different steps for the design of an aptamer-based surface-enhanced Raman scattering (BioSERS) sensing chip capable of detecting the coronavirus nucleocapsid protein (N protein) in spiked phosphate-buffered solutions and real samples of human blood serum. Optimization of the preparation steps in terms of the aptamer concentration used for the functionalization of the silver nanoparticles, time for affixing the aptamer, incubation time with target protein, and insulation of the silver active surface with cysteamine, led to a sensitive BioSERS chip, which was able to detect the N protein in the range from 1 to 75 ng mL-1 in spiked phosphate-buffered solutions with a detection limit of 1 ng mL-1 within 30 min. Furthermore, the BioSERS chip was used to detect the target protein in scarcely spiked human serum. This study demonstrates the possibility of a clinical application that can improve the detection limit and accuracy of the currently commercialized SARS-CoV-2 immunodiagnostic kit. Additionally, the system is modular and can be applied to detect other proteins by only changing the aptamer.

Switching on/off the chemisorption of thioctic-based self-assembled monolayers on gold by applying a moderate cathodic/anodic potential.

An in situ and real-time electrochemical method has been devised for quantitatively monitoring the self-assembly of a ferrocene-labeled cyclic disulfide derivative (i.e., a thioctic acid derivative) on a polycrystalline gold electrode under electrode polarization. Taking advantage of the high sensitivity, specificity, accuracy, and temporal resolution of this method, we were able to demonstrate an unexpectedly facilitated formation of the redox-active SAM when the electrode was held at a moderate cathodic potential (-0.4 V vs SCE in CH3CN), affording a saturated monolayer from only micromolar solutions in less than 10 min, and a totally impeded SAM growth when the electrode was polarized at a slightly anodic potential (+0.5 V vs SCE in CH3CN). This method literally allows for switching on/off the formation of SAMs under "soft" conditions. Moreover the cyclic disulfide-based SAM was completely desorbed at this potential contrary to the facilitated deposition of a ferrocene-labeled alkanethiol. Such a strikingly contrasting behavior could be explained by an energetically favored release of the thioctic-based SAM through homolytic cleavage of the Au-S bond followed by intramolecular cyclization of the generated thiyl diradicals. Moreover, the absence of a discernible transient faradaic current response during the potential-assisted adsorption/desorption of the redox-labeled cyclic disulfide led us to conclude in a potential-dependent reversible surface reaction where no electron is released or consumed. These results provide new insights into the formation of disulfide-based SAMs on gold but also raise some fundamental questions about the intimate mechanism involved in the facilitated adsorption/desorption of SAMs under electrode polarization. Finally, the possibility to easily and selectively address the formation/removal of thioctic-based SAMs on gold by applying a moderate cathodic/anodic potential offers another degree of freedom in tailoring their properties and in controlling their self-assembly, nanostructuration, and/or release.

Novel biomimetic Prussian blue nanocubes-based biosensor for Tau-441 protein detection.

Tau protein is a promising biomarker for early diagnosis of Alzheimer's disease. Therefore, there is an urgent need to develop a simple and effective method for its detection. To this end, an innovative sensing device was developed using a carbon screen-printed electrode (C-SPE) decorated with graphene oxide/Prussian Blue nanocubes (GO/PBNCs) for the selective and sensitive determination of Tau-441 protein. The molecular imprinting polymer (MIP) was built on the GO/PBNCs/C-SPE by electropolymerizing 3-aminophenol (3-AMP) in the presence of the target protein using chronoamperometry, and the template was subsequently removed from the polymer matrix with oxalic acid. In parallel, a non-imprinted material (NIP) was also prepared in the absence of the target for comparison purposes. Scanning electron microscopy and transmission electron microscopy, were used to study the morphology of the modified electrode and electrochemical techniques were used to monitor the stepwise assembly of the sensor. Under optimized conditions, the sensing platform exhibited a linear range within 1.09 and 2.18 nmol/L and a detection limit of 0.01 pmol/L in spiked phosphate buffer solution (PBS). The MIP sensor showed minimal interference with uric acid and bovine albumin. The simplicity of production, affordable cost and promising performance make this sensor a potential strategic sensing platform for the detection of chemical and biological molecules.

A Magnetoelectrochemical Bioassay for Highly Sensitive Sensing of Point Mutations in Interleukin-6 Gene Using TMB as a Hybridization Intercalation Indicator.

Point mutations are common in the human DNA genome and are closely related to higher susceptibility to cancer diseases. Therefore, suitable methods for their sensing are of general interest. In this work, we report on a magnetic electrochemical bioassay using DNA probes tethered to streptavidin magnetic beads (strep-MBs) to detect T > G single nucleotide polymorphism (SNP) within the inteleukin-6 (IL6) gene in human genomic DNA. In the presence of the target DNA fragment and tetramethylbenzidine (TMB), the electrochemical signal related to the oxidation of TMB is observed, which is much higher than the one obtained in the absence of the target. The key parameters affecting the analytical signal, such as the concentration of the biotinylated probe, its incubation time with strep-MBs, DNA hybridization time, and TMB loading, were optimized using the electrochemical signal intensity and signal-to-blank (S/B) ratio as selection criteria. Using spiked buffer solutions, the bioassay can detect the mutated allele in a wide range of concentrations (over six decades) with a low detection limit (7.3 fM). Furthermore, the bioassay displays a high specificity with high concentrations of the major allele (one mismatched), and two mismatched and non-complementary DNA. More importantly, the bioassay can detect the variation in scarcely diluted human DNA, collected from 23 donors, and can reliably distinguish between heterozygous (TG genotype) and homozygous (GG genotype) in respect to the control subjects (TT genotype), where the differences are statistically highly significant (p-value < 0.001). Thus, the bioassay is useful for cohort studies targeting one or more mutations in human DNA.

Laser-induced graphene electrodes scribed onto novel carbon black-doped polyethersulfone membranes for flexible high-performance microsupercapacitors.

A facile and expandable methodology was successfully developed to fabricate laser-induced graphene from novel pristine aminated polyethersulfone (amPES) membranes. The as-prepared materials were applied as flexible electrodes for microsupercapacitors. The doping of amPES membranes with various weight percentages of carbon black (CB) microparticles was then performed to improve their energy storage performance. The lasing process allowed the formation of sulfur- and nitrogen-codoped graphene electrodes. The effect of electrolyte on the electrochemical performance of as-prepared electrodes was investigated and the specific capacitance was significantly enhanced in 0.5 M HClO4. Remarkably, the highest areal capacitance of 47.3 mF·cm-2 was achieved at a current density of 0.25 mA·cm-2. This capacitance is approximately 12.3 times higher than the average value for commonly used polyimide membranes. Furthermore, the energy and power densities were as high as 9.46 µWh·cm-2 and 0.3 mW·cm-2 at 0.25 mA·cm-2, respectively. The galvanostatic charge-discharge experiments confirmed the excellent performance and stability of amPES membranes during 5,000 cycles, where more than 100% of capacitance retention was achieved and the coulombic efficiency was improved up to 96.67%. Consequently, the fabricated CB-doped PES membranes offer several advantages including low carbon fingerprint, cost-effectiveness, high electrochemical performance and potential applications in wearable electronic systems.