Covalent organic frameworks (COFs) as carrier for improved drug delivery and biosensing applications.

Porous organic frameworks (POFs) represent a significant subclass of nanoporous materials in the field of materials science, offering exceptional characteristics for advanced applications. Covalent organic frameworks (COFs), as a novel and intriguing type of porous material, have garnered considerable attention due to their unique design capabilities, diverse nature, and wide-ranging applications. The unique structural features of COFs, such as high surface area, tuneable pore size, and chemical stability, render them highly attractive for various applications, including targeted and controlled drug release, as well as improving the sensitivity and selectivity of electrochemical biosensors. Therefore, it is crucial to comprehend the methods employed in creating COFs with specific properties that can be effectively utilized in biomedical applications. To address this indispensable fact, this review paper commences with a concise summary of the different methods and classifications utilized in synthesizing COFs. Second, it highlights the recent advancements in COFs for drug delivery, including drug carriers as well as the classification of drug delivery systems and biosensing, encompassing drugs, biomacromolecules, small biomolecules and the detection of biomarkers. While exploring the potential of COFs in the biomedical field, it is important to acknowledge the limitations that researchers may encounter, which could impact the practicality of their applications. Third, this paper concludes with a thought-provoking discussion that thoroughly addresses the challenges and opportunities associated with leveraging COFs for biomedical applications. This review paper aims to contribute to the scientific community's understanding of the immense potential of COFs in improving drug delivery systems and enhancing the performance of biosensors in biomedical applications.

Fabrication of polydopamine decorated carbon cloth as support material to anchor CeO2 nanoparticles for electrochemical detection of ethanol.

A flexible CeO2 nanostructured polydopamine-modified carbon cloth (CeO2/PDA/CC) interface was fabricated via electrodeposition for ethanol detection. The fabrication method involved two consecutive electrochemical steps in which dopamine was firstly electrodeposited on carbon fibers, followed by the electrochemical growth of CeO2 nanoparticles. The CeO2/PDA-based electroactive interface exerts an impressive electrochemical performance on the flexible sensor due to strong synergistic effect of the PDA functionalization with more active sites. Moreover, catalytic activity of CeO2 nanostructures anchored on highly conductive CC incorporate superior electrocatalytic performance of the fabricated interface. The designed electrochemical sensor showed a wide response to ethanol in the linear range 1 to 25 mM with a detection limit of 0.22 mM. The CeO2/PDA/CC flexible sensor showed good anti-interference ability and excellent repeatability and reproducibility (RSD = 1.67%). The fabricated interface performed well in saliva samples with satisfactory recoveries, corroborating the viability of CeO2/PDA/CC integrated interface for practical implementation.

DNA-templated electrodeposition of silver nanoparticles for direct and label-free aptasensing of ochratoxin A.

We present in this work, an aptasensing strategy based on the DNA-templated electrodeposition of silver nanoparticles (AgNPs). The homogeneous electro-deposition of AgNPs on screen printed carbon electrode (SPCE) surface was achieved based on a unique aptamer scaffold. This was constructed by immobilizing a DNA aptamer on SPCE by electrochemical oxidation of its amine groups. The electrodeposition of AgNPs was investigated before and after the addition of the aptamer's specific target; the mycotoxin, ochratoxin A (OTA). Electrochemical characterization by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) showed the effect of the scaffold layer on the electrodeposition of AgNPs. The conformational change induced by aptamer after binding its targeted molecule affects AgNPs electrodeposition and the electron transfer thus allowing OTA detection by cyclic voltammetry. The voltammograms showed a good proportionality between the analyte concentration and the current response. The constructed platform allowed the quantitative aptasensing of OTA within the range of (1.56-400 ng/mL) and the detection limit of 0.6 ng/mL. In term of aptasensor applicability, the proposed strategy showed excellent performance in rice samples.

Black phosphorus nanosheets/poly(allylamine hydrochloride) based electrochemical immunosensor for the selective detection of human epididymis protein 4.

In this work, an electrochemical immunosensor based on black phosphorus nanosheets (BPNS)/poly(allylamine hydrochloride) (PAH) nanocomposite modified glassy carbon electrode was developed for the detection of ovarian cancer biomarker HE4. PAH has been applied to retain BPNS in its original honeycomb structure and to anchor biomolecules electrostatically on the transducer surface. The as synthesized nanocomposite was characterized by zeta potential analysis, scanning electron microscopy, x-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy. Subsequently, the performance of the electrochemical immunosensor was evaluated through cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy. Under the optimal condition, the developed electrochemical immunosensor permitted to detect HE4 with a linear range of 0.1-300 ng ml-1and a detection limit of 0.01 ng ml-1. The developed sensor exhibited good selectivity and specificity to HE4 with negligible interference effect from common biomolecules like bovine serum albumin, lysozyme, protamine, glucose, fructose, hemoglobin and fetal bovine serum. Further, practical application of developed electrochemical immunosensor was demonstrated in spiked human serum which showed satisfactory recovery percentages.

Non-enzymatic electrochemical sensing of dopamine from COVID-19 quarantine person.

The worldwide outbreak of COVID-19 pandemic, is not only a great threat to the victim life but it is leaving invisible devastating negative affect on mental health of quarantined individual because of isolation, depression, bereavement, and loss of income. Therefore, the precise monitoring catecholamine neurotransmitters specifically of dopamine (DA) is of great importance to assess the mental health. Thus, herein we have synthesized Co-based zeolitic imidazolate framework (ZIF-67) through solvothermal method for precise monitoring of DA. To facilitate the fast transportation of ions, highly conductive polymer, poly(3,4-ethylenedioxythiophene; PEDOT) has been integrated on the surface of ZIF-67 which not only provides the smooth pathway for ions/electrons transportation but also saves the electrode from pulverization. The fabricated ZIF-67/PEDOT electrode shows a significant sensing performance towards DA detection in terms of short diffusion pathways by expositing more active sites, over good linear range (15-240 µM) and a low detection limit of (0.04 µM) even in the coexistence of the potentially interfering molecules. The developed ZIF-67/PEDOT sensor was successfully employed for sensitive and selective monitoring of DA from COVID-19 quarantined person blood, thus suggesting reliability of the developed electrode.

Fabrication of ionic liquid stabilized MXene interface for electrochemical dopamine detection.

Development of MXene (Ti3C2Cl2)-based sensing platforms by exploiting their inherent active electrochemistry is highly challenging due to their characteristic poor stability in air and water. Herein, we report a cost-effective methodology to deposit MXene on a conductive graphitic pencil electrode (GPE). MXenes can provide active surface area due to their clever morphology of accordion-like sheets; however, the disposition to stack together limits their potential applications. A task-specific ionic liquid (1-methyl imidazolium acetate) is utilized as a multiplex host material to engineer MXene interface via π-π interactions as well as to act as a selective binding site for biomolecules. The resulting IL-MXene/GPE interface proved to be a highly stable interface owing to good interactions between MXene and IL that inhibited electrode leaching and boosted electron transfer at the electrode-electrolyte interface. It resulted in robust dopamine (DA) oxidation with amplified faradaic response and enhanced sensitivity (9.61 µA µM-1 cm-2) for DA detection. This fabricated sensor demonstrated large linear range (10 µM - 2000 µM), low detection limit (702 nM), high reproducibility, and good selectivity. We anticipate that such platform will pave the way for the development of stable and economically viable MXene-based sensors without sacrificing their inherent properties. Scheme 1 Schematic illustration of the IL-MXene/GPE fabrication and oxidative process towards non-enzymatic dopamine sensor.

Perylene diimide/MXene-modified graphitic pencil electrode-based electrochemical sensor for dopamine detection.

The synthesis of novel architecture comprising perylene diimide (PDI)-MXene (Ti3C2TX)-integrated graphitic pencil electrode for electrochemical detection of dopamine (DA) is reported. The good electron passage between PDI-MXene resulted in an unprecedented nano-adduct bearing enhanced electrocatalytic activity with low-energy electronic transitions. The anionic groups of PDI corroborated enhanced active surface area for selective binding and robust oxidation of DA, thereby decreasing the applied potential. Meanwhile, the MXene layers acted as functional conducive support for PDI absorption via strong H-bonding. The considerable conductivity of MXene enhanced electron transportation thus increasing the sensitivity of sensing interface. The inclusively engineered nano-adduct resulted in robust DA oxidation with ultra-sensitivity (38.1 µAµM-1cm-2), and low detection limit (240 nM) at very low oxidation potential (-0.135 V). Moreover, it selectively signaled DA in the presence of physiological interferents with wide linearity (100-1000 µM). The developed transducing interface performed well in human serum samples with RSD (0.1 to 0.4%) and recovery (98.6 to 100.2%) corroborating the viability of the practical implementation of this integrated system. Graphical abstract Schematic illustration of the oxidative process involved on constructed sensing interface for the development of a non-enzymatic dopamine sensor.

The role of band structure in Co- and Fe-co-doped Ba0.5Sr0.5Zr0.1Y0.1O3-δ perovskite semiconductor to design an electrochemical aptasensing platform: application in label-free detection of ochratoxin A using voltammetry.

Nanocomposites can offer a platform to conjugate biorecognition features of aptamer with unique size-dependent properties of a given material, which can autoprobe the binding event based on their electroactive characteristics. Herein, we design electroactive switchable aptamer probes based on co-doped single-phase semiconducting materials employing the cyclic voltammetry method to record the current signal at each step of electrochemical characterization. To do so, we utilized a facile hydrothermal method assisted by co-precipitation method such as Co-Fe-co-doped Ba0.5Sr0.5Zr0.1Y0.1O3-δ (CF-BSZY) and tuned the alignment of the energy band structure of the material to amplify the output of the electrochemical signal. At various steps, changes occurred in the electrochemical properties at the surface of CF-BSZY. The binding of the ssDNA with prepared materials enhances the current signal by the interaction with the target (ochratoxin A (OTA)) depressing the current signal and facilitating the construction of a novel design of electrochemical aptasensor. As a proof of concept, an electrochemical aptasensor for the detection of ochratoxin A (OTA) in rice samples has been developed. The electrochemical aptasensor provides a limit of detection (LOD) of 0.00012 µM (0.12 nM), with a linear range from 0.000247 to 0.74 µM and sound OTA recovery in real samples. The developed aptasensor is simply designed and is free of oligonucleotide labeling or decorative nanoparticle modifications. The proposed mechanism is generic in principle with the potential to translate any type of aptamer and target binding event into a detectable signal; hence, it can be largely applied to various bioreceptor recognition phenomena for subsequent applications.

Two-Dimensional Nanostructures for Electrochemical Biosensor.

Current advancements in the development of functional nanomaterials and precisely designed nanostructures have created new opportunities for the fabrication of practical biosensors for field analysis. Two-dimensional (2D) and three-dimensional (3D) nanomaterials provide unique hierarchical structures, high surface area, and layered configurations with multiple length scales and porosity, and the possibility to create functionalities for targeted recognition at their surface. Such hierarchical structures offer prospects to tune the characteristics of materials-e.g., the electronic properties, performance, and mechanical flexibility-and they provide additional functions such as structural color, organized morphological features, and the ability to recognize and respond to external stimuli. Combining these unique features of the different types of nanostructures and using them as support for bimolecular assemblies can provide biosensing platforms with targeted recognition and transduction properties, and increased robustness, sensitivity, and selectivity for detection of a variety of analytes that can positively impact many fields. Herein, we first provide an overview of the recently developed 2D nanostructures focusing on the characteristics that are most relevant for the design of practical biosensors. Then, we discuss the integration of these materials with bio-elements such as bacteriophages, antibodies, nucleic acids, enzymes, and proteins, and we provide examples of applications in the environmental, food, and clinical fields. We conclude with a discussion of the manufacturing challenges of these devices and opportunities for the future development and exploration of these nanomaterials to design field-deployable biosensors.

Nitrogen-doped graphene oxide as a catalyst for the oxidation of Rhodamine B by hydrogen peroxide: application to a sensitive fluorometric assay for hydrogen peroxide.

The authors report that nitrogen-doped graphene oxide (NGO) catalyzes the oxidative decomposition of the fluorophore Rhodamine B (RhB) by hydrogen peroxide. The catalytic decomposition of hydrogen peroxide yields free hydroxyl radicals that destroy RhB so that the intensity of the yellow fluorescence is reduced. Nitrogen doping enhances the electronic and optical properties and surface chemical reactivities of GO such as widening of bandgap, increase in conductivity, enhanced quenching and adsorbing capabilities etc. The catalytic properties of NGO are attributed to its large specific surface and high electron affinity of nitrogen atoms. The chemical and structural properties of GO and NGO were characterized by XRD, FTIR, SEM, UV-visible and Raman spectroscopies. The method was optimized by varying the concentration of RhB, nitrogen dopant and hydrogen peroxide. The fluorescent probe, best operated at excitation/emission wavelengths of 554/577 nm, allows hydrogen peroxide to be determined in concentrations as low as 94 pM with a linear range spanning from 1 nM to 1 µM. Graphical abstract Schematic illustration of a fluorescence quenching method for the determination of H2O2. Upon addition of H2O2, nitrogen-doped graphene oxide (NGO) catalyzes the oxidation of Rhodamine B dye due to hydroxyl radical generation, which leads to a sensitive quenchometric methd for H2 O2.

Polymer scaffold layers of screen-printed electrodes for homogeneous deposition of silver nanoparticles: application to the amperometric detection of hydrogen peroxide.

A method is described for electrochemical oxidation of polymers on the surface of screen-printed electrodes (SPCE). These act as scaffold layers for homogeneous deposition of silver nanoparticles (AgNPs). Hexamethylenediamine (HMDA) and poly(ethylene glycol) were immobilized on the SPCE surface via electrochemical oxidation. AgNPs were then electrodeposited on the scaffolds on the SPCE. This type of different carbon chain containing materials like PEG and HMDA act as big tunnels for electron mobility and are useful for the homogenous deposition of AgNPs on the SPCE surface without agglomeration. The resulting sensor was applied to the determination of hydrogen peroxide (H2O2) as a model analyte. It is found to display favorable catalytic and conductive properties towards the reduction of H2O2. Cyclic voltammetry and amperometry revealed that the modified electrode performs better than other modified SPCEs. Best operated at a potential of around -0.61 V (vs Ag|AgCl), the amperometric response is linear in the 10-180 µM H2O2 concentration range and the detection limit is 1.5 µM. The sensor is stable and reproducible. The resultant sensor was appplied to toothpaste analysis, and good recovery values were gained. Graphical abstractSchematic representation of electropolymerization of poly(ethylene glycol) and hexamethylenediamine scaffold layers on screen-printed electrodes for homogeneous electrodeposition of silver nanoparticles. This electrode was applied for the amperometric determination of hydrogen peroxide.

A nanocomposite prepared from magnetite nanoparticles, polyaniline and carboxy-modified graphene oxide for non-enzymatic sensing of glucose.

The authors report on the synthesis of carboxy functionalized graphene oxide (fGO) decorated with magnetite (Fe3O4) nanoparticles. The resulting nanomaterial was used to prepare a composite with polyaniline (PANI) which was characterized by UV-vis, Fourier transform-infrared and Raman spectroscopies. Its surface morphologies were characterized by atomic force and scanning electron microscopies. A screen-printed carbon electrode was then modified with the nanocomposite to obtain an enzyme-free glucose sensor. The large surface of fGO and Fe3O4 along with the enhanced charge transfer capability of PANI warrant a pronounced electrochemical response (typically measured at 0.18 V versus Ag/AgCl) which is suppressed in the presence of glucose. This reduction of current by glucose was used to design a sensitive method for quantification of glucose. The response of the modified SPCE is linear in the 0.05 µM - 5 mM glucose concentration range, and the lower detection limit is 0.01 µM. Graphical abstract Schematic illustration of in-situ anchoring of Iron oxide on functionalized graphene oxide and synthesis of its polymeric nanocomposite for non-enzymatic detection of Glucose. The nanocomposite modified screen printed interface enabled monitoring of glucose at lower potential with higher precision. GO (graphene oxide), fGO (functionalized graphene oxide), PANI (polyaniline).

Development of an Impedimetric Aptasensor for Label Free Detection of Patulin in Apple Juice.

In the present work, an aptasensing platform was developed for the detection of a carcinogenic mycotoxin termed patulin (PAT) using a label-free approach. The detection was mainly based on a specific interaction of an aptamer immobilized on carbon-based electrode. A long linear spacer of carboxy-amine polyethylene glycol chain (PEG) was chemically grafted on screen-printed carbon electrodes (SPCEs) via diazonium salt in the aptasensor design. The NH2-modified aptamer was then attached covalently to carboxylic acid groups of previously immobilized bifunctional PEG to build a diblock macromolecule. The immobilized diblocked molecules resulted in the formation of long tunnels on a carbon interface, while the aptamer was assumed as the gate of these tunnels. Upon target analyte binding, the gates were assumed to be closed due to conformational changes in the structure of the aptamer, increasing the resistance to the charge transfer. This increase in resistance was measured by electrochemical impedance spectroscopy, the main analytical technique for the quantitative detection of PAT. Encouragingly, a good linear range between 1 and 25 ng was obtained. The limit of detection and limit of quantification was 2.8 ng L-1 and 4.0 ng L-1, respectively. Selectivity of the aptasensor was confirmed with mycotoxins commonly occurring in food. The developed apta-assay was also applied to a real sample, i.e., fresh apple juice spiked with PAT, and toxin recovery up to 99% was observed. The results obtained validated the suitability and selectivity of the developed apta-assay for the identification and quantification of PAT in real food samples.

Carboxylic group riched graphene oxide based disposable electrochemical immunosensor for cancer biomarker detection.

In this work, we have developed for the first time a carboxylic group riched graphene oxide based disposable electrochemical immunosensor for cancer biomarker detection using methylene blue (MB). The developed immunosensor is highly sensitive for detection of biomarker Mucin1 (MUC1) in human serum samples. Development of this disposable electrochemical immunosensor was premeditated by applying specific monoclonal antibodies against MUC1. In this method, we explored highly conductive surface of carboxylic group (-COOH-) rich graphene oxide (GO) on screen-printed carbon electrodes (SPCE). This modified GO-COOH-SPCE was employed for the detection of MUC1 protein based on the reaction with methylene blue (MB) redox probe using differential pulse voltammetry (DPV) technique. Developed immunosensor exhibited good detection range for MUC1 with excellent linearity (0.1 U/mL- 2 U/mL), with a limit of detection of 0.04 U/mL. Upon potential application of developed biosensor, good recoveries were recorded in the range of 96-96.67% with % R.S.D 4.2. Analytical performance of the developed immunosensor assures the applicability in clinical diagnostic applications.

Ionic liquid coated iron nanoparticles are promising peroxidase mimics for optical determination of H2O2.

Ionic liquid coated nanoparticles (IL-NPs) consisting of zero-valent iron are shown to display intrinsic peroxidase-like activity with enhanced potential to catalyze the oxidation of the chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. This results in the formation of a blue green colored product that can be detected with bare eyes and quantified by photometry at 652 nm. The IL-NPs were further doped with bismuth to enhance its catalytic properties. The Bi-doped IL-NPs were characterized by FTIR, X-ray diffraction and scanning electron microscopy. A colorimetric assay was worked out for hydrogen peroxide that is simple, sensitive and selective. Response is linear in the 30-300 µM H2O2 concentration range, and the detection limit is 0.15 µM. Graphical abstract Schematic of ionic liquid coated iron nanoparticles that display intrinsic peroxidase-like activity. They are capable of oxidizing the chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. This catalytic oxidation generated blue-green color can be measured by colorimetry. Response is linear in the range of 30-300 µM H2O2 concentration, and the detection limit is 0.15 µM.

Photoinduced discharge of electrons stored in a TiO2-MWCNT composite to an analyte: application to the fluorometric determination of hydrogen peroxide, glucose and aflatoxin B1.

The authors describe an analytical detection scheme based on the use of multiwalled carbon nanotubes (MWCNTs) that accept and store electrons upon contact with photo-irradiated TiO2 nanoparticles (TiO2-NPs). The Fermi level equilibration with photo-irradiated TiO2-NPs has a storage value of 0.35 mM of electrons per 120 mg·L-1 of MWCNTs. The stored electrons can be discharged on demand upon addition of electron acceptors to the TiO2-NP/MWCNT composite. These findings are applied to detect the quencher hydrogen peroxide. H2O2 also is produced on enzymatic action of glucose oxidase on glucose, and this enables glucose also to be quantified by using the TiO2-NP/MWCNT fluorescent nanoprobe. The wide scope of the method also is demonstrated by an assay for aflatoxin B1 that is making use of an FAM-labeled aptamer where the FAM fluorophore on the aptamer quenches the emission of the nanoprobe. The following analytical linear ranges and limits of detection are found: H2O2: 0.1-100 µM and 15 nM; glucose: 5-200 µM and 0.5 µM; aflatoxin: 0.1-40 ng·mL-1 and 0.02 ng·mL-1. The method was applied to the determination of glucose in human serum. Graphical abstract The assays demonstrated in (b) and (c) are based on the fluorescence quenching ability of MWCNTs-TiO2. In the presence of the target (analyte), the fluorescence is restored and the target concentration is determined from the percentage of fluorescence recovery.

An Overview on Recent Progress in Electrochemical Biosensors for Antimicrobial Drug Residues in Animal-Derived Food.

Anti-microbial drugs are widely employed for the treatment and cure of diseases in animals, promotion of animal growth, and feed efficiency. However, the scientific literature has indicated the possible presence of antimicrobial drug residues in animal-derived food, making it one of the key public concerns for food safety. Therefore, it is highly desirable to design fast and accurate methodologies to monitor antimicrobial drug residues in animal-derived food. Legislation is in place in many countries to ensure antimicrobial drug residue quantities are less than the maximum residue limits (MRL) defined on the basis of food safety. In this context, the recent years have witnessed a special interest in the field of electrochemical biosensors for food safety, based on their unique analytical features. This review article is focused on the recent progress in the domain of electrochemical biosensors to monitor antimicrobial drug residues in animal-derived food.

Tetramethyl-6-carboxyrhodamine quenching-based aptasensing platform for aflatoxin B1: Analytical performance comparison of two aptamers.

In this study, a simple TAMRA (tetramethyl-6-carboxyrhodamine) quenching-based aptasensing platform was designed for the detection of aflatoxin B1 (AFB1). Here, we compared the analytical performance of two aptamer sequences: seqA and seqB. The AFB1 detection was based on the interactions of FAM (carboxyfluorescein)-labeled aptamer with TAMRA-labeled DNA complementary strand in the presence and absence of target analyte. Under optimized experimental conditions, TAMRA-labeled strand quenched the fluorescence response of FAM-labeled aptamer due to the noncovalent interaction between the two DNA strands. The binding of AFB1 induced the complex formation and weakened the interaction between FAM-labeled aptamer and TAMRA-labeled complementary strand, resulting in the fluorescence recovery. By using this principle concept, an assay was constructed for the detection of AFB1. The method exhibited good sensitivity, good selectivity with a limit of detection of 0.2 ng ml(-1), and a wide linear range from 0.25 to 32 ng ml(-1). For real sample application, the aptasensors were tested in beer and wine samples, with good recovery rates obtained for AFB1 detection.

Ligand Assisted Stabilization of Fluorescence Nanoparticles; an Insight on the Fluorescence Characteristics, Dispersion Stability and DNA Loading Efficiency of Nanoparticles.

This work reports on the ligand assisted stabilization of Fluospheres® carboxylate modified nanoparticles (FCMNPs), and subsequently investigation on the DNA loading capacity and fluorescence response of the modified particles. The designed fluorescence bioconjugate was characterized with enhanced fluorescence characteristics, good stability and large surface area with high DNA loading efficiency. For comparison purpose, bovine serum albumin (BSA) and polyethylene glycol (PEG) with three different length strands were used as cross linkers to modify the particles, and their DNA loading capacity and fluorescence characteristics were investigated. By comparing the performance of the particles, we found that the most improved fluorescence characteristics, enhanced DNA loading and high dispersion stability were obtained, when employing PEG of long spacer arm length. The designed fluorescence bioconjugate was observed to maintain all its characteristics under varying pH over an extended period of time. These types of bioconjugates are in great demand for fluorescence imaging and in vivo fluorescence biomedical application, especially when most of the as synthesized fluorescence particles cannot withstand to varying in vivo physiological conditions with decreases in fluorescence response and DNA loading efficiency.