Evaluation of the oxygen reduction reaction electrocatalytic activity of postsynthetically modified covalent organic frameworks

The pyrolysis of organic precursors to produce heteroatomic-doped carbonaceous materials has emerged as a powerful tool to construct metal-free heterogeneous electrocatalysts due to their low cost and their environmental friendliness. However, the lack of control in the atomic positions or the location of the chemical functionalities makes it difficult to establish structure-property relationships. Herein, we report an easy strategy to compare the electrocatalytic oxygen reduction reaction (ORR) performance of metal-free and nonpyrolyzed materials by postsynthetic modification of covalent organic frameworks (COFs) via click-chemistry. This method facilitates the evaluation of different active centers using materials with the same morphology and prevents active site agglomeration by covalently anchoring these moieties inside of a porous and crystalline framework. In this study we developed a series of diimide-based materials (XDI0.17-COFs) with a loading of 7.65 × 10-4 mol of active site/mg of host COF. The bulk COFs have been delaminated to perform electrode modification by drop-casting. The electrocatalytic response toward the ORR has been studied in alkaline media obtaining the best results for the NDI0.17-COF with an onset potential of 0.77 V (vs reversible hydrogen electrode, RHE) and a limiting current of 4.2 mA/cm2 by a preferred pathway toward water electroreduction. Finally, an adequate combination of density functional theory with the thermochemical Gibbs free energy formalism has been used to theoretically rationalize the ORR mechanism in these metal-free and nonpyrolyzed materials. We have obtained theoretical ORR overpotentials for each COF system agreeing with the experimental observation, which correlate with the ability of the NDI, BzDI, and PDI molecular blocks to accommodate electrons. Our work provides a guideline on how to study the electrocatalytic performance of different organic moieties in metal-free and non-pyrolyzed COFs avoiding their de novo synthesis by using the click postsynthetic methodologyTED2021-129886B-C43, PID2019-106268GB-C32, RED2018-102412-T, PID2020-116728RB-I00, PID2020-113142RB-C21, PLEC2021-007906, 2018/NMT-4349TRANSNANOAVANSENS, S2018/NMT-4367, Y2020/NMT646

Sensitive glyphosate electrochemiluminescence immunosensor based on electrografted carbon nanodots

A novel electrochemiluminescence (ECL) immunosensor based on electrografted carbon nanodots (CND) is developed for the sensitive determination of glyphosate in soy milk and tea. Nitrogen rich CND were synthesized by microwave radiations using mild conditions and following the principles of green chemistry. L-Arginine and 3,3′-diamino-N-methyldipropylamine were selected as precursors. CND were exhaustively characterized as well as the resulting nanostructured electrodes after CND electrografting. The high stability of CND nanostructured electrode together with the high electrical conductivity and the improvement of the electrochemiluminescent properties from the luminophore [Ru(bpy)3]2+ makes it an excellent electrochemiluminescence detection platform for biosensing assays. The application to biosensors was assessed by combination with an immunoassay based on magnetic nanoparticles, in which anti-glyphosate-IgG coupled magnetic particles (MP-Ab) was used as recognition element of the analyte, glyphosate. The developed ECL immunosensor was successfully applied for the detection of glyphosate in a wide linear range from 28.9 to 200 pg/mL, a sensitivity of 3.38 × 10−3 mL/pg and a detection limit of 8.66 pg/mL. The immunosensor response is stable and reproducible and it has been applied to the determination of glyphosate in tea and soy milk, with results that agree with those provided by an ELISA kit involving the same immunoreagentsThis work has been supported by the Spanish Ministerio de Ciencia, Innovación y Universidades (CTQ2017-84309-C2-1-R; RED2018-102412-T) and Comunidad Autónoma de Madrid (P2018/NMT-4349 TRANSNANOAVANSENS Program and 2017-T1/BIO-5435 Atracción de Talento Project

Insulin sensor based on nanoparticle-decorated multiwalled carbon nanotubes modified electrodes

Insulin sensors based on glassy carbon electrodes modified with nafion-multiwalled carbon nanotubes decorated with nickel hydroxide nanoparticles (Ni(OH)<inf>2</inf>NPs/Nafion-MWCNTs/GC), were prepared by electrochemical deposition of Ni(OH)<inf>2</inf>NPs from a dinuclear paddle-wheel Ni monothiocarboxylate complex on the MWCNTs/GC surface. The size and distribution of the Ni(OH)<inf>2</inf>NPs/Nafion-MWCNTs were characterized by transmission electron microscopy (TEM). The results show that Ni(OH)<inf>2</inf> nanoparticles were electrodeposited on the surface of carbon nanotubes. Moreover, the electrochemical behavior of the modified electrodes in aqueous alkaline solutions of insulin was studied by cyclic voltammetry and chronoamperometry. It was found that the as-prepared nanoparticles have excellent electrocatalytic activity towards insulin oxidation due to their special properties, reducing the overpotential and improving the electrochemical behavior, compared to the bare GC electrode. Amperometry was used to evaluate the analytical performance of modified electrode in the determination of insulin. Excellent analytical features, including high sensitivity (5.0 A mol cm<sup>-2</sup> μM<sup>-1</sup>), low detection limit (85 nM) and wide dynamic range (up to 10.00 μM), were achieved under optimum conditions. Moreover, these insulin sensors show good repeatability and a high stability after successive potential cycling. Common substances such as ascorbic acid, uric acid and acetaminophen do not interfere. Finally, the developed sensors have been applied to the determination of insulin in pharmaceuticals and in human plasma. Efficient recoveries for pharmaceuticals and human plasma demonstrate that the proposed methodology can be satisfactorily applied to these types of samplesThe authors acknowledge Ministerio de Economía y Competitividad (project No. CTQ2014-53334-C2-1-R and MAT2013-46753-C2-1-P) and Comunidad de Madrid (NANOAVANSENS Program) for financial support. E.M.P. gratefully acknowledges the FPU-2010 Grant from the Ministerio de Educació

Spectroelectrochemical operando method for monitoring a phenothiazine electrografting process on amide functionalized C-nanodots/Au hybrid electrodes

Phenothiazine derivatives are extensively explored dye molecules, which present interesting electrochemical and optical properties. In recent years, the possibility of transforming some phenothiazines in their aryl diazonium salt derivatives has been proved, what allows them to be electrochemically reduced and electrografted onto conductive surfaces. This is a smart way to modify these surfaces and enable them with specific functionalities. In order to better comprehend the electrografting process and consequently have a higher control of it, in this work we have carried out an exhaustive study by operando UV–Vis spectroelectrochemistry of the electrografting of a phenothiazine aryl diazonium salt onto amide carbon nanodots. As a model of phenothiazine dye we have chosen Azure A. The electrografting onto carbon nanodots has been stablished by comparison with the results obtained on bare gold electrodes in this novel study. The presence of carbon dots improves the reversibility of the electrochemical process as derived from the results obtained by operando UV–Vis spectroelectrochemistry. In addition, to asses that the electrochemical process studied corresponds to the electrografting, the results have been compared to those obtained for the simple Azure A adsorption. This study shows the advantages of obtaining simultaneously the electrochemical and the spectroscopic evolution of an electron-transfer process in a single experiment, in a particular electrochemical reaction. This work could be the starting point for the study of the electrografting on other nanomaterialsFunding from the Spanish Ministerio de Ciencia, Innovación y Universidades (project: CTQ2017-84309-C2-1-R) and Comunidad Autónoma de Madrid (NANOAVANSENS Program) is acknowledged. IMDEA Nanociencia acknowledges support from the 'Severo Ochoa' Programme for Centres of Excellence in R&D (Ministerio de Ciencia, Innovación y Universidades, Grant SEV-2016-0686

Oxygen reduction using a metal-free naphthalene diimide-based covalent organic framework electrocatalyst

A novel naphthalene diimide-based covalent organic framework (NDI-COF) has been synthesized and successfully exfoliated into COF nanosheets (CONs). Electrochemical measurements reveal that the naphthalene diimide units incorporated into NDI-CONs act as efficient electrocatalyst for oxygen reduction in alkaline media, showing its potential for the development of metal-free fuel cellsFinancial support from the Spanish Government (projects MAT2016-77608-C3-1-P, MAT2016-77608-C3-2-P, CTQ2017-84309-C2-1-R, MAT2017-85089-C2-1-R, FJCI-2017-33536 and RYC-2015-17730), the UCM (INV.GR.00.1819.10759) and the Madrid Regional Government (TRANSNANOAVANSENS-CM (S2018/NMT-4349)) is acknowledge

Azure A embedded in carbon dots as NADH electrocatalyst: Development of a glutamate electrochemical biosensor

Carbon nanodots modified with azure A (AA-CDs) have been synthesized and applied as redox mediator of bioelectrocatalytic reactions. A deep characterization of AA-CDs nanomaterial has been carried out, proving the covalent attachment of azure A molecules into the carbon dots nanostructure. Disposable screen-printed carbon electrodes (SPCE) have been modified with AA-CDs, through the action of chitosan polymer (Chit-AA-CDs/SPCE). The Chit-AA-CDs/SPCE electrocatalytic activity towards the oxidation of NADH has been proved, obtaining excellent results regarding the low oxidation potential achieved (−0.15 V vs. Ag) and low detection and quantification limits (LOD and LOQ) for NADH, 16 and 53 µM, respectively. The developed electrochemical platform has been applied for the construction of a glutamate biosensor by immobilizing L-glutamic dehydrogenase (GLDH/Chit-AA-CDs/SPCE). The morphology of GLDH/Chit-AA-CDs/SPCE platform was analysed by AFM at each different step of the electrode modification process. The resulting biosensing platform is capable of detect NADH enzymatically generated by GLDH in the presence of glutamate and NAD+. Good analytical parameters were obtained for glutamate analysis using GLDH/Chit-AA-CDs/SPCE, as LOD and LOQ of 3.3 and 11 µM, respectively. The biosensor has been successfully applied to the analysis of food and biological samplesThis work has been supported by the Spanish Ministerio de Ciencia e Innovacion (PID2020–116728RB-I00) and Comunidad Autonoma de Madrid (SI3/PJI/2021–00341, P2018/NMT-4349 TRANSNANOAVANSENS Program

Carbon nanodots modified-electrode for peroxide-free cholesterol biosensing and biofuel cell design

The determination of cholesterol is greatly important because high concentrations of this biomarker are associated to heart disease. Moreover, cholesterol can be used as a fuel in enzymatic fuel cells operating under physiological conditions. Here, we present a cholesterol biosensor and a peroxide-free biofuel cell based on the electrocatalytic oxidation of the NADH generated during the enzymatic reaction of cholesterol dehydrogenase (ChDH) as an alternative to the H2O2 biosensing strategies used with cholesterol oxidase-bioelectrodes. Azure A functionalized-carbon nanodots were used as NADH oxidation electrocatalysts and for ChDH covalent immobilization. The biosensor responded linearly to cholesterol concentrations up to 1.7 mM with good sensitivity (4.50 mA cm−2 M−1) and at a low potential. The ChDH bioelectrode was combined with an O2-reducing bilirubin oxidase cathode to produce electrical energy using cholesterol as fuel and O2 as oxidant. Furthermore, the resulting enzymatic fuel cell was tested in human serum naturally containing free cholesterolA.L.DL. and M.P. thank MCIU/AEI/FEDER, EU for funding project RTI2018–095090-B-I00. M.B. acknowledges funding from the European Union’s Horizon 2020 Research and Innovation Program under the Marie Skłodowska-Curie grant agreement No. 713366. This work was also supported by Talent Attraction Project from CAM (SI3/PJI/ 2021–00341 and 2021–5A/BIO-20943), Spanish Ministerio de Ciencia e Innovacion (PID2020–116728RB-I00) and TRANSNANOAVANSENSCAM Program (S2018/NMT-4349

A MoS2 platform and thionine-carbon nanodots for sensitive and selective detection of pathogens

This work focuses on the combination of molybdenum disulfide (MoS2) and à la carte functionalized carbon nanodots (CNDs) for the development of DNA biosensors for selective and sensitive detection of pathogens. MoS2 flakes prepared through liquid-phase exfoliation, serves as platform for thiolated DNA probe immobilization, while thionine functionalized carbon nanodots (Thi-CNDs) are used as electrochemical indicator of the hybridization event. Spectroscopic and electrochemical studies confirmed the interaction of Thi-CNDs with DNA. As an illustration of the pathogen biosensor functioning, DNA sequences from InIA gen of Listeria monocytogenes bacteria and open reading frame sequence (ORF1ab) of SARS-CoV-2 virus were detected and quantified with a detection limit of 67.0 fM and 1.01 pM, respectively. Given the paradigmatic selectivity of the DNA hybridization, this approach allows pathogen detection in the presence of other pathogens, demonstrated by the detection of Listeria monocytogenes in presence of Escherichia coli. We note that this design is in principle amenable to any pathogen for which the DNA has been sequenced, including other viruses and bacteria. As example of the application of the method in real samples it has been used to directly detect Listeria monocytogenes in cultures without any DNA Polymerase Chain Reaction (PCR) amplification processAuthors thank the financial support from the Comunidad de Madrid (NANOAVANSENS, S2013/MIT-3029, MAD2D-CM Program, S2013/ MIT-3007 and 2017-T1/BIO-5435), Ministerio de Economía, Industria y Competitividad (CTQ 2015-71955-REDT (ELECTROBIONET), CTQ2014-53334-C2-1-R. and MAT 2015-71879-P). EMP acknowledges the European Research Council (ERC-PoC-842606), MINECO (CTQ 2017- 86060-P), Comunidad de Madrid (MAD2D-CM S2013/MIT-3007). IMDEA Nanociencia acknowledges support from the ‘Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016–0686). RdC acknowledges support from UAM, Banco Santander, Fundacion ´ IMDEA (convocatoria CRUE–CSIC–SANTANDER, fondo supera 2020, project with reference 10.01.03.02.41). Authors also acknowledge BAT unit of CIA

Scalable Synthesis and Electrocatalytic Performance of Highly Fluorinated Covalent Organic Frameworks for Oxygen Reduction

In this study, we present a novel approach for the synthesis of covalent organic frameworks (COFs) that overcomes the common limitations of non-scalable solvothermal procedures. Our method allows for the room-temperature and scalable synthesis of a highly fluorinated DFTAPB-TFTA-COF, which exhibits intrinsic hydrophobicity. We used DFT-based calculations to elucidate the role of the fluorine atoms in enhancing the crystallinity of the material through corrugation effects, resulting in maximized interlayer interactions, as disclosed both from PXRD structural resolution and theoretical simulations. We further investigated the electrocatalytic properties of this material towards the oxygen reduction reaction (ORR). Our results show that the fluorinated COF produces hydrogen peroxide selectively with low overpotential (0.062 V) and high turnover frequency (0.0757 s−1) without the addition of any conductive additives. These values are among the best reported for non-pyrolyzed and metal-free electrocatalysts. Finally, we employed DFT-based calculations to analyse the reaction mechanism, highlighting the crucial role of the fluorine atom in the active site assembly. Our findings shed light on the potential of fluorinated COFs as promising electrocatalysts for the ORR, as well as their potential applications in other fieldsThis work was financially supported by Ministerio de Ciencia e Innovación of Spain MICINN (TED2021-129886B-C41, TED2021-129886BC42; TED2021-129886BC43; PID2019-106268GB-C32; PID2019-106268GB C33, PID2020-113608RB-I00; PID2022-138908NB-C33, PID2022-138470NB-100, RED2018-102412-T; PID2020-116728RB-I00). Comunidad de Madrid (P2018/NMT-4349 TRANSNANOAVANSENS Program; SI3/PJI/2021-0034). F.Z. acknowledge financial support from the Spanish Ministry of Science and Innovation, through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M). R.V. acknowledges “Programa Juan de la Cierva Formación” (FJC2020-045043-I). R.V. and J.A.R.N. acknowledge MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR

Methylene Blue functionalized carbon nanodots combined with different shape gold nanostructures for sensitive and selective SARS-CoV-2 sensing

The development of DNA-sensing platforms based on new synthetized Methylene Blue functionalized carbon nanodots combined with different shape gold nanostructures (AuNs), as a new pathway to develop a selective and sensitive methodology for SARS-CoV-2 detection is presented. A mixture of gold nanoparticles and gold nanotriangles have been synthetized to modify disposable electrodes that act as an enhanced nanostructured electrochemical surface for DNA probe immobilization. On the other hand, modified carbon nanodots prepared a la carte to contain Methylene Blue (MB-CDs) are used as electrochemical indicators of the hybridization event. These MB-CDs, due to their structure, are able to interact differently with double and single-stranded DNA molecules. Based on this strategy, target sequences of the SARS-CoV-2 virus have been detected in a straightforward way and rapidly with a detection limit of 2.00 aM. Moreover, this platform allows the detection of the SARS-CoV-2 sequence in the presence of other viruses, and also a single nucleotide polymorphism (SNPs). The developed approach has been tested directly on RNA obtained from nasopharyngeal samples from COVID-19 patients, avoiding any amplification process. The results agree well with those obtained by RT-qPCR or reverse transcription quantitative polymerase chain reaction technique.We acknowledge the support from the Comunidad de Madrid (TRANSNANOAVANSENS-CM, S2018/NMT-4349, NANOCOV-CM, SI3/PJI/2021–00341) and Ministerio de economia y competitividad de España (PID2020–116728RB-100, CTQ2015–71955-REDT (ELECTROBIONET)). IMDEA Nanociencia acknowledges support from the Programme for Centres of Excellence in R&D ‘Severo Ochoa’ (CEX2020–001039-S, MINECO). Authors also acknowledge REACT EU NANOCOV-CM project. RdC acknowledges support from Fundación IMDEA Nanociencia, Banco Santander, UAM (convocatoria CRUE- SANTANDER-CSIC, reference 10.01.03.02.41).Peer reviewe