Portable and Autonomous PEDOT-Modified Flexible Paper-Based Methanol Fuel Cell Sensing Platform Applied to L1CAM Recombinant Protein Detection.

This work describes first a 5-stack direct methanol fuel cell (DMFC) based on poly(3,4-ethylenedioxythiophene)-modified paper (PEDOT/PB-DMFC), which acts as an energy source and biosensor, coupled to an electrochromic cell (EC). It is autonomous and monitors the biosensor response by color change, as appropriate for point-of-care (POC) applications. In detail, DMFC strips were developed from square Whatman paper, and the EC was made on baking paper treated with polydimethylsiloxane (PDMS). The PEDOT/PB-DMFCs operate in a passive mode with a few microliters of diluted methanol. The biosensor layer was obtained on the anode ink (a composite of EDOT, oxidized multiwalled carbon nanotubes, and carbon black with platinum and ruthenium) by electropolymerizing 3,4-ethylenedioxythiophene (EDOT), in situ, in the presence of L1CAM. Each PEDOT/PB-DMFC single cell generates a voltage in the range of 0.3-0.35 V depending on the cell, and a five-cell stack delivers a 1.5-1.6 V voltage range when fed with 0.5 M methanol. The fabricated PEDOT/PB-DMFC/biosensor was calibrated against L1CAM, showing linear responses from 1.0 × 10-12 to 1.0 × 10-8 M with a detection limit of 1.17 × 10-13 M (single cell mode). When the EC was connected to the PEDOT/PB-DMFC device, a color gradient was observed. Overall, this work opens horizons to the use of biosensors even in places with energy scarcity and offers an alternative to reducing the current energy demand.

New autonomous and self-signaling biosensing device for sarcosine detection.

An early diagnosis is the gold standard for cancer survival. Biosensors have proven their effectiveness in monitoring cancer biomarkers but are still limited to a series of requirements. This work proposes an integrated power solution, with an autonomous and self-signaling biosensing device. The biorecognition element is produced in situ by molecular imprinting to detect sarcosine, a known biomarker for prostate cancer. The biosensor was assembled on the counter-electrode of a dye-sensitized solar cell (DSSC), simultaneously using EDOT and Pyrrole as monomers for the biomimetic process and the catalytic reduction of triiodide in the DSSC. After the rebinding assays, the hybrid DSSC/biosensor displayed a linear behavior when plotting the power conversion efficiency (PCE) and the charge transfer resistance (RCT) against the logarithm of the concentration of sarcosine. The latter obtained a sensitivity of 0.468 Ω/decade of sarcosine concentration, with a linear range between 1 ng/mL and 10 µg/mL, and a limit of detection of 0.32 ng/mL. When interfacing an electrochromic cell, consisting of a PEDOT-based material, with the hybrid device, a color gradient between 1 ng/mL and 10 µg/mL of sarcosine was observed. Thus, the device can be used anywhere with access to a light source, completely equipment-free, suitable for point-of-care analysis and capable of detecting sarcosine within a range of clinical interest.

Water Peel-Off Transfer of Electronically Enhanced, Paper-Based Laser-Induced Graphene for Wearable Electronics.

Laser-induced graphene (LIG) has gained preponderance in recent years, as a very attractive material for the fabrication and patterning of graphitic structures and electrodes, for multiple applications in electronics. Typically, polymeric substrates, such as polyimide, have been used as precursor materials, but other organic, more sustainable, and accessible precursor materials have emerged as viable alternatives, including cellulose substrates. However, these substrates have lacked the conductive and chemical properties achieved by conventional LIG precursor substrates and have not been translated into fully flexible, wearable scenarios. In this work, we expand the conductive properties of paper-based LIG, by boosting the graphitization potential of paper, through the introduction of external aromatic moieties and meticulous control of laser fluence. Colored wax printing over the paper substrates introduces aromatic chemical structures, allowing for the synthesis of LIG chemical structures with sheet resistances as low as 5 Ω·sq-1, translating to an apparent conductivity as high as 28.2 S·cm-1. Regarding chemical properties, ID/IG ratios of 0.28 showcase low defect densities of LIG chemical structures and improve on previous reports on paper-based LIG, where sheet resistance has been limited to values around 30 Ω·sq-1, with more defect dense and less crystalline chemical structures. With these improved properties, a simple transfer methodology was developed, based on a water-induced peel-off process that efficiently separates patterned LIG structures from the native paper substrates to conformable, flexible substrates, harnessing the multifunctional capabilities of LIG toward multiple applications in wearable electronics. Proof-of concept electrodes for electrochemical sensors, strain sensors, and in-plane microsupercapacitors were patterned, transferred, and characterized, using paper as a high-value LIG precursor for multiples scenarios in wearable technologies, for improved sustainability and accessibility of such applications.

Natural Materials Modified and Applied to the Detection of Drugs In Situ: Modification of Eggshell and Quantification of Oxytetracycline.

This work describes a novel sensing system using eggshells as substrate for the first time, targeting the detection and semiquantitative determination of antibiotics in waters from aquaculture, enabling simple, inexpensive, and in situ drug monitoring. Eggshell was ground and the resulting powder was modified by adsorption of suitable reagents, and it takes a typical colour after contact with the antibiotic. The colour intensity is correlated with the concentration of the antibiotic. This novel approach was applied to oxytetracycline, one of the antibiotics commonly used in aquaculture. The chemical changes on the eggshell powder were evaluated and optimised to produce an intense colour change as a function of the concentration of the antibiotic. The colour changes were evaluated by visual comparison with images taken with a digital camera, applying an appropriate mathematical treatment to the colour coordinates of the HSL system used by Windows. The selectivity of the response was tested against other antibiotic drugs. The materials were also used in the analysis of a spiked environmental water sample. Overall, this work presents a rapid, inexpensive, simple and equipment-free method for screening and discrimination of tetracycline drugs in aquaculture. The method is a green approach by reusing eggshells and decreasing the level of contamination correlated to analytical methods, thus being a promising tool for local, rapid, and cost-effective antibiotic monitoring.

Wine astringent compounds monitored by an electrochemical biosensor.

An innovative approach for monitoring astringent polyphenols in beverages (wines) is described, consisting of an electrochemical biosensor constructed by adsorbing salivary α-amylase or proline-rich protein (PRP) onto amined gold screen-printed electrodes. Interaction with polyphenols was tested using pentagalloyl glucose (PGG) as a standard, an important representative element for astringency. The analytical properties of the resulting biosensors were evaluated by electrochemical impedance spectroscopy at different pHs. The PRP-biosensor was able to bind to PGG with higher sensitivity, displaying lower limit of the linear range of 0.6 µM. Wine samples were tested to prove the concept and the concentrations obtained ranged from 0.17 to 4.7 µM, as expressed in PGG units. The effects of side-compounds on PRP and on α-amylase binding to PGG were tested (gallic acid, catechin, ethanol, glucose, fructose and glycerol) and considered negligible. Overall, concentrations > 1.0 µM in PGG units are signaling electrochemical impedance, providing a quantitative monitoring of astringent compounds.

An ultra-sensitive electrochemical biosensor using the Spike protein for capturing antibodies against SARS-CoV-2 in point-of-care.

This work presents an innovative ultra-sensitive biosensor having the Spike protein on carbon-based screen-printed electrodes (SPEs), for monitoring in point-of-care antibodies against SARS-CoV-2, a very important tool for epidemiological monitoring of COVID-19 infection and establishing vaccination schemes. In an innovative and simple approach, a highly conductive support is combined with the direct adsorption of Spike protein to enable an extensive antibody capture. The high conductivity was ensured by using carboxylated carbon nanotubes on the carbon electrode, by means of a simple and quick approach, which also increased the surface area. These were then modified with EDC/NHS chemistry to produce an amine layer and undergo Spike protein adsorption, to generate a stable layer capable of capturing the antibodies against SARS-CoV-2 in serum with great sensitivity. Electrochemical impedance spectroscopy was used to evaluate the analytical performance of this biosensor in serum. It displayed a linear response between 1.0 â€‹pg/mL and 10 â€‹ng/mL, with a detection limit of ∼0.7 â€‹pg/mL. The analysis of human positive sera containing antibody in a wide range of concentrations yielded accurate data, correlating well with the reference method. It also offered the unique ability of discriminating antibody concentrations in sera below 2.3 â€‹µg/mL, the lowest value detected by the commercial method. In addition, a proof-of-concept study was performed by labelling anti-IgG antibodies with quantum dots to explore a new electrochemical readout based on the signal generated upon binding to the anti-S protein antibodies recognised on the surface of the biosensor. Overall, the alternative serologic assay presented is a promising tool for assessing protective immunity to SARS-CoV-2 and a potential guide for revaccination.

A molecularly imprinted photonic polymer based on an inverse opal structure for sensing D-dimer at the point-of-care.

Accurate and timely diagnosis of venous thromboembolism (VTE) is crucial to prevent related morbidity and mortality. This work reports a label-free sensor for D-dimer, a biomarker of VTE. The sensor is based on the synergy between the colloidal crystal templating method and the molecular imprinting technique. The design of the photonic molecularly imprinted polymer (PMIP) is focused on the preparation of an inverse opal structure, resulting from silica infiltration in a poly(methyl methacrylate) photonic crystal template, followed by a calcination stage that removes the sacrificial colloidal crystal. The molecularly imprinted polymer in the inverse opal structure is then synthesized in the presence of the template molecule, the peptide D-dimer. After D-Dimer removal, the PMIP consists in a three-dimensional highly ordered structure, where nanocavities complementary to the D-dimer in shape and binding features are distributed. The PMIP showed a linear response to D-dimer in synthetic urine, exhibiting a decrease in the reflectance intensity with increasing D-dimer concentrations, ranging from 22.5 ng mL-1 to 1450.0 ng mL-1. The PMIP material demonstrated a limit of detection of 15.5 ng mL-1 and was selective for D-dimer in the presence of fibrinopeptide B, another prospective VTE biomarker in urine. Moreover, the sensor was reusable up to five times without losing its recognition ability. Overall, a novel PMIP material is described for successful recognition of D-Dimer. Considering the clinical relevance of D-dimer detection, the sensor is envisioned as a promising low-cost test for urinalysis.

The modulatory role of internet-supported mindfulness-based cognitive therapy on extracellular vesicles and psychological distress in people who have had cancer: a protocol for a two-armed randomized controlled study.

BACKGROUND: Mindfulness-based interventions (MBIs) have been used in oncology contexts as a promising tool with numerous benefits for various health-related and psychosocial outcomes. Despite the increasing popularity of MBIs, few randomized controlled trials (RCTs) have examined their effects upon biological parameters. Specifically, no previous study has examined the effects of MBIs on extracellular vesicles (EVs), which are potentially important markers of health, disease, and stress. Moreover, the lack of RCTs is even more limited within the context of technology-mediated MBIs and long-term effects. METHODS: The current study protocol presents a two-arm, parallel, randomized controlled study investigating the effects of internet-supported mindfulness-based cognitive therapy (MBCT) compared with treatment as usual (TAU). Primary outcomes are psychological distress and EV cargo of distressed participants with previous breast, colorectal, or prostate cancer diagnoses. Secondary outcomes are self-reported psychosocial and health-related measures, and additional biological markers. Outcomes will be assessed at baseline, 4 weeks after baseline (mid-point of the intervention), 8 weeks after baseline (immediately post-intervention), 24 weeks after baseline (after booster sessions), and 52 weeks after baseline. Our goal is to recruit at least 111 participants who have been diagnosed with breast, prostate, or colorectal cancer (cancer stage I to III), are between 18 and 65 years old, and have had primary cancer treatments completed between 3 months and 5 years ago. Half of the participants will be randomized to the TAU group, and the other half will participate in an 8-week online MBCT intervention with weekly group sessions via videoconference. The intervention also includes asynchronous homework, an online retreat after the fifth week, and 4 monthly booster sessions after completion of the 8-week programme. DISCUSSION: This study will allow characterizing the effects of internet-based MBCT on psychosocial and biological indicators in the context of cancer. The effects on circulating EVs will also be investigated, as a possible neurobiological pathway underlying mind-body intervention effects. TRIAL REGISTRATION: ClinicalTrials.gov NCT04727593 (date of registration: 27 January 2021; date of record verification: 6 October 2021).

Paper-based aptasensor for colorimetric detection of osteopontin.

This work presents a novel cellulose-based aptasensor for the colorimetric detection of a cancer biomarker, osteopontin (OPN), in point-of-care (PoC) analysis. For this purpose, the cellulose paper was chemically modified with (mercaptopropyl)methyldimetoxisilane to attach the thiolated aptamer, which acts as a biological detection layer. The surface modification was checked by Fourier transform infrared spectroscopy and thermogravimetric analysis. Colorimetric detection was performed using a conventional staining solution, Bradford reagent. The color analysis was performed by evaluating the RGB coordinates provided by the ImageJ program from the photographs taken with a smartphone. Overall, the biosensor shows good sensitivity with a wide linear range (R > 0.998) of 5-1000 ng/mL and a detection limit lower than 5 ng/mL in buffer and commercial human serum solution, after 30 min of incubation. In addition, this aptasensor shows good selectivity to some interfering species such as bovine serum albumin and recombinant OPN. Analytical data obtained from spiked serum samples confirm the accuracy of the method. Importantly, it is a broad-spectrum method that tends to meet the criteria of REASSURED (real-time connectivity, ease of sampling, affordability, specificity, ease of use, speed and robustness, device freedom, and deliverability) for global testing.

Paper-Based Biosensors for COVID-19: A Review of Innovative Tools for Controlling the Pandemic.

The appearance and quick spread of the new severe acute respiratory syndrome coronavirus disease, COVID-19, brought major societal challenges. Importantly, suitable medical diagnosis procedures and smooth clinical management of the disease are an emergent need, which must be anchored on novel diagnostic methods and devices. Novel molecular diagnostic tools relying on nucleic acid amplification testing have emerged globally and are the current gold standard in COVID-19 diagnosis. However, the need for widespread testing methodologies for fast, effective testing in multiple epidemiological scenarios remains a crucial step in the fight against the COVID-19 pandemic. Biosensors have previously shown the potential for cost-effective and accessible diagnostics, finding applications in settings where conventional, laboratorial techniques may not be readily employed. Paper- and cellulose-based biosensors can be particularly relevant in pandemic times, for the renewability, possibility of mass production with sustainable methodologies, and safe environmental disposal. In this review, paper-based devices and platforms targeting SARS-CoV-2 are showcased and discussed, as a means to achieve quick and low-cost PoC diagnosis, including detection methodologies for viral genomic material, viral antigen detection, and serological antibody testing. Devices targeting inflammatory markers relevant for COVID-19 are also discussed, as fast, reliable bedside diagnostic tools for patient treatment and follow-up.

Plastic Antibody of Polypyrrole/Multiwall Carbon Nanotubes on Screen-Printed Electrodes for Cystatin C Detection.

This work reports the design of a novel plastic antibody for cystatin C (Cys-C), an acute kidney injury biomarker, and its application in point-of-care (PoC) testing. The synthetic antibody was obtained by tailoring a molecularly imprinted polymer (MIP) on a carbon screen-printed electrode (SPE). The MIP was obtained by electropolymerizing pyrrole (Py) with carboxylated Py (Py-COOH) in the presence of Cys-C and multiwall carbon nanotubes (MWCNTs). Cys-C was removed from the molecularly imprinted poly(Py) matrix (MPPy) by urea treatment. As a control, a non-imprinted poly(Py) matrix (NPPy) was obtained by the same procedure, but without Cys-C. The assembly of the MIP material was evaluated in situ by Raman spectroscopy and the binding ability of Cys-C was evaluated by the cyclic voltammetry (CV) and differential pulse voltammetry (DPV) electrochemical techniques. The MIP sensor responses were measured by the DPV anodic peaks obtained in the presence of ferro/ferricyanide. The peak currents decreased linearly from 0.5 to 20.0 ng/mL of Cys-C at each 20 min successive incubation and a limit of detection below 0.5 ng/mL was obtained at pH 6.0. The MPPy/SPE was used to analyze Cys-C in spiked serum samples, showing recoveries <3%. This device showed promising features in terms of simplicity, cost and sensitivity for acute kidney injury diagnosis at the point of care.

Fabrication and modification of homemade paper-based electrode systems.

This work reports the simple and inexpensive fabrication of homemade paper-based carbon-printed electrodes (HP C-PEs), aiming to produce an alternative way to generate electrochemical biosensors to all and promoting their wide use. This is especially important in times of pandemics, considering the excellent features of electrochemical biosensing, which may ensure portability, low-cost and quick responses. HP C-PEs were fabricated using a standard cellulose filter paper that was first modified with wax, to make it hydrophobic. Then, the electrodes were manually printed on top of this cellulose/wax substrate. The electrodes were designed by having standard configurations for potentiometric and electrochemical readings, combining two or three electrodes. In general, both electrode systems showed excellent electrochemical and mechanical features, which were better in specific cases than commercial devices. The 3-electrode system displayed high current levels with low peak-to-peak potential separation, yielding highly stable signals after consecutive electrode bending that corresponded to high active areas. The possibility of modifying the devices with polymers produced in-situ was also explored and proven successful, providing also advantageous features when compared to other devices. The 2-electrode system was also proven highly stable and capable of subsequent use in potentiometric sensing development. Overall, the fabrication process of the 2- and 3-electode systems described herein may be employed in laboratories to produce successful electrochemical biosensors, with the final devices displaying excellent electrochemical and mechanical features. This procedure offers the advantages of being simple and inexpensive, when compared to other commercial devices, while using materials that are promptly available and that may undergo a worldwide use.

A passive direct methanol fuel cell as transducer of an electrochemical sensor, applied to the detection of carcinoembryonic antigen.

This work describes an electrochemical sensor with a biomimetic plastic antibody film for carcinoembryonic antigen (CEA, an important biomarker in colorectal cancer), integrated in the electrical circuit of a direct methanol fuel cell (DMFC), working in passive mode and used herein as power supply and signal transducer. In detail, the sensing layer for CEA consisted of a Fluorine-doped Tin Oxide (FTO) conductive glass substrate - connected to the negative pole side of the DMFC - with a conductive poly (3,4-ethylenedioxythiophene) (PEDOT) layer and a polypyrrol (PPy) molecularly-imprinted polymer (MIP), assembled in-situ. This sensing element is then closed using a cover FTO-glass, hold in place with a clip, connected to the positive side of the DMFC. When compared with control DMFCs, the power curves of DMFC/Sensor integrated system showed decreased power values due to the MIP layer interfaced in the electrical circuit, also displaying high stability signals. The DMFC/Sensor was further calibrated at room temperature, in different medium (buffer, a synthetic physiological fluid model and Cormay® serum), showing linear responses over a wide concentration range, with a limit of detection of 0.08 ng/mL. The DMFC/Sensor presented sensitive data, with linear responses from 0.1 ng/mL to 100 µg/mL and operating well in the presence of human serum. Overall, the results obtained evidenced the possibility of using a DMFC as a transducing element in an electrochemical sensor, confirming the sensitive and selective readings of the bio (sensing) imprinted film. This integration paves the way towards fully autonomous electrochemical devices, in which the integration of the sensor inside the fuel cell may be a subsequent direction.

Paper-Based Platform with an In Situ Molecularly Imprinted Polymer for ß-Amyloid.

Alzheimer's disease (AD) is one of the most common forms of dementia affecting millions of people worldwide. Currently, an easy and effective form of diagnosis is missing, which significantly hinders a possible improvement of the patient's quality of life. In this context, biosensors emerge as a future solution, opening the doors for preventive medicine and allowing the premature diagnosis of numerous pathologies. This work presents a pioneering biosensor that combines a bottom-up design approach using paper as a platform for the electrochemical recognition of peptide amyloid ß-42 (Aß-42), a biomarker for AD present in blood, associated with visible differences in the brain tissue and responsible for the formation of senile plaques. The sensor layer relies on a molecularly imprinted polymer as a biorecognition element, created on the carbon ink electrode's surface by electropolymerizing a mixture of the target analyte (Aß-42) and a monomer (O-phenylenediamine) at neutral pH 7.2. Next, the template molecule was removed from the polymeric network by enzymatic and acidic treatments. The vacant sites so obtained preserved the shape of the imprinted protein and were able to rebind the target analyte. Morphological and chemical analyses were performed in order to control the surface modification of the materials. The analytical performance of the biosensor was evaluated by an electroanalytical technique, namely, square wave voltammetry. For this purpose, the analytical response of the biosensor was tested with standard solutions ranging from 0.1 ng/mL to 1 µg/mL of Aß-42. The linear response of the biosensor went down to 0.1 ng/mL. Overall, the developed biosensor offered numerous benefits, such as simplicity, low cost, reproducibility, fast response, and repeatability less than 10%. All together, these features may have a strong impact in the early detection of AD.

Photonics in nature and bioinspired designs: sustainable approaches for a colourful world.

Biological systems possess nanoarchitectures that have evolved for specific purposes and whose ability to modulate the flow of light creates an extraordinary diversity of natural photonic structures. In particular, the striking beauty of the structural colouration observed in nature has inspired technological innovation in many fields. Intense research has been devoted to mimicking the unique vivid colours with newly designed photonic structures presenting stimuli-responsive properties, with remarkable applications in health care, safety and security. This review highlights bioinspired photonic approaches in this context, starting by presenting many appealing examples of structural colours in nature, followed by describing the versatility of fabrication methods and designed coloured structures. A particular focus is given to optical sensing for medical diagnosis, food control and environmental monitoring, which has experienced a significant growth, especially considering the advances in obtaining inexpensive miniaturized systems, more reliability, fast responses, and the use of label-free layouts. Additionally, naturally derived biomaterials and synthetic polymers are versatile and fit many different structural designs that are underlined. Progress in bioinspired photonic polymers and their integration in novel devices is discussed since recent developments have emerged to lift the expectations of smart, flexible, wearable and portable sensors. The discussion is expanded to give emphasis on additional functionalities offered to related biomedical applications and the use of structural colours in new sustainable strategies that could meet the needs of technological development.

Dual biorecognition by combining molecularly-imprinted polymer and antibody in SERS detection. Application to carcinoembryonic antigen.

This work reports the innovative combination of a molecularly-imprinted polymer (MIP) and a natural antibody for the accurate surface-enhanced Raman spectroscopy (SERS) detection of carcinoembryonic antigen (CEA). The MIP material acted as a pre-concentration scheme for the target protein, while the natural antibody was responsible to signal the presence of CEA on the MIP platform. Gold-based screen-printed electrodes were used as substrate and gallic acid (GA) was used herein for the first time in the assembly of a MIP film, by electropolymerization, in the presence of CEA. This layer was further covered by a second ultra-thin film of electropolymerized benzoic acid (BA), to avoid non-specific binding. The rebinding features of the MIP film were evaluated by electrochemical impedance spectroscopy (EIS) and a linear response was observed from 1 to 1000 ng/mL. For a sensitive SERS detection, the MIP film was first incubated in sample containing CEA and next incubated in SERS tag. For the SERS tag, gold nanostars (AuNSs) were employed as metal support, coupled to 4-aminothiophenol (4-ATP) as Raman reporter and to a natural antibody for CEA as recognition element. The overall system showed a sensitive response down to 1.0 ng/mL, which was different from the blank signal. Overall, the innovative approach presented herein combines the advantages of using two different targeting elements for CEA. The costs and time of MIP production were substantially low due to selection of electropolymerization approach and the proposal described herein may be extended to other target molecules.

Molecularly imprinted polymer SPE sensor for analysis of CA-125 on serum.

Considering the high incidence level and mortality rate of ovarian cancer, particularly among the European female population, the carbohydrate antigen 125 (CA-125) was selected as the protein target for this study for the development of a MIP-based biosensor. This work presents the development of molecular imprinting polymers (MIPs) on gold electrode surface for CA-125 biomarker recognition. The preparation of the CA-125 imprinting was obtained by electropolymerization of pyrrole (Py) monomer in a gold electrode using cyclic voltammetry (CV) in order to obtain highly selective materials with great molecular recognition capability. The quantification of CA-125 biomarker was made through the comparison of two methods: electrochemical (square wave voltammetry -SWV) and optical transduction (surface plasmon resonance -SPR). SWV has been widely used in biological molecules analysis since it is a fast and sensitive technique. In turn, SPR is a non-destructive optical technique that provides high-quality analytical data of CA-125 biomarker interactions with MIP. Several analytical parameters, such as sensitivity, linear response interval, and detection limit were determined to proceed to the performance evaluation of the electrochemical and optical transduction used in the development of the CA-125 biosensor. The biosensor based in the electrochemical transduction was the one that presented the best analytical parameters, yielding a good selectivity and a detection limit (LOD) of 0.01 U/mL, providing a linear concentration range between 0.01 and 500 U/mL. This electrochemical biosensor was selected for the study and it was successfully applied in the CA-125 analysis in artificial serum samples with recovery rates ranging from 91 to 105% with an average relative error of 5.8%.

An impedimetric molecularly-imprinted biosensor for Interleukin-1ß determination, prepared by in-situ electropolymerization on carbon screen-printed electrodes.

This work reports the first electrochemical molecularly imprinted polymer (MIP) sensor for Interleukin-1beta (IL-1ß) detection, based on modified commercial screen-printed carbon electrode (SPCE) was successfully demonstrated. For this purpose, the carbon support was modified with a PEDOT/4-aminothiophenol layer prior to the MIP film to enhance sensitivity and signal stability. The MIP layer was constructed on top of this by electropolymerization of Eriochrome black T (EBT) in the presence of IL-1ß. The several steps of the biosensor assembly was followed by Raman spectroscopy and electroanalytical techniques. Using electrochemical impedance spectroscopy (EIS), a linear response in the range of 60 pM to 600 nM, with a LOD of 1.5 pM with (S/N = 3) was obtained in neutral PBS. Selectivity tests of the MIP biosensor made in spiked synthetic serum samples as well as against other structurally related (Myoglobin, of similar shape and size) or competing compounds (Immunoglobulin G, also present in the human serum) confirmed the good selectivity of the biosensor. Overall, the biosensor described herein has the potential to provide a simple and quick way for on-site screening of IL-1ß, with low sample/reagent consumption and enabling direct serum analysis, which constitutes a valuable alternative to other conventional methods.

Self-powered and self-signalled autonomous electrochemical biosensor applied to cancinoembryonic antigen determination.

This work describes a novel and disruptive electrochemical biosensing device that is self-powered by light and self-signalled by an optical readout. Electrical energy requirements are ensured by a photovoltaic cell that is a dye sensitized solar cell (DSSC), in which one of the electrodes is the biosensing unit. The readout converts electrical energy into colour by an electrochromic cell and signals the concentration dependent event. This device was designed to target a cancer biomarker, cancinoembryonic antigen (CEA). In brief, the sensing unit was assembled on a conductive glass substrate with a highly conductive poly(3,4-ethylenedioxythiophene) (PEDOT) layer, using a molecularly-imprinted polymer of polypyrrol (PPy) as biorecognition element. This sensing unit acted as the counter electrode (CE) of the DSSC, generating a hybrid device with a maximum power conversion efficiency of 3.45% for a photoanode area of 0.7 cm2. The hybrid DSSC/biosensor had an electrical output that was CEA concentration dependent from 100 ng/mL to 100 µg/mL, with a limit detection of 0.14 ng/mL in human urine samples. The electrochromic cell consisted of a PEDOT-based material and showed a colour gradient change for CEA concentrations, ranging from 0.1 ng/mL to 100 µg/mL. Overall, this self-powered and self-signalled set-up is equipment free and particularly suitable for point-of-care analysis (POC), being able to screen CEA in real samples and differentiating critical concentrations for establishing a diagnosis. It holds the potential to provide clinical relevant data anywhere, in a fully independent manner.

Photovoltaics, plasmonics, plastic antibodies and electrochromism combined for a novel generation of self-powered and self-signalled electrochemical biomimetic sensors.

This work describes further developments into the self-powered and self-signalled biosensing system that merges photovoltaic cells, plastic antibodies and electrochromic cells into a single target. Herein, the plasmonic effect is introduced to improve the photoanode features of the photovoltaic cell, a dye sensitized solar cell (DSSC), and better electrocatalytic features are introduced in the electrode containing the sensing element. In brief, the DSSC had a counter-electrode of poly(3,4-ethylenedioxythiophene) on an FTO glass modified by a plastic antibody of 3,4-ethylenedioxythiophene and pyrrol. The photoanode had dye sensitized TiO2 modified with gold nanoparticles (AuNPs) to increase the cell efficiency, aiming to improve the sensitivity of the response of hybrid device for the target biomarker. The target biomarker was carcinoembryonic antigen (CEA). The response of the hybrid device evidenced a linear trend from 0.1 ng/mL to 10 µg/mL, with an anionic slope of 0.1431 per decade concentration. The response of the plastic antibody for CEA revealed great selectivity against other tumour markers (CA 15-3 or CA 125). The colour response of the electrochromic cell was also CEA concentration dependent and more sensitive when the hybrid device was set-up with a photoanode with AuNPs. A more intense blue colour was obtained when higher concentrations of CEA were present. Overall, this improved version of the self-powered and self-signalled set-up has zero-requirements and is particularly suitable for point-of-care analysis (POC). It is capable of screening CEA in real samples and differentiating clinical levels of interest. This concept opens new horizons into the current cancer screening approaches.