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An automatic titration method is reported to resolve ternary mixtures of transition metals (Pb2+, Cd2+ and Cu2+) employing electronic tongue detection and a reduced number of pre-defined additions of EDTA titrant. Sensors used were PVC membrane selective electrodes with generic response to heavy-metals, plus an artificial neural network response model. Detection limits obtained were ca. 1 mg L−1 for the three target ions and reproducibilities 3.0 % for Pb2+, 4.1 % for Cd2+ and 5.2 % for Cu2+. The system was applied to contaminated soil samples and high accuracy was obtained for the determination of Pb2+. In the determination Cd2+ and Cu2+, sample matrix showed a significant effect.

The detection of pollutant traces in the public water supply and aquifers is essential for the safety of the population. In this article, we demonstrate that a simple electrochemical procedure in acidic solution can be employed for enhancing the sensitivity of flexible screen-printed carbon electrodes (SPEs) to detect bisphenol-A (BPA), hydroquinone, and catechol, simultaneously. The SPEs were pretreated electrochemically in a H2SO4 solution, which did not affect their morphology, yielding high current signals with well separated oxidation peaks. The sensitivity values were 0.28, 0.230, and 0.056 &micro, A L &micro, mol&minus, 1 with detection limits of 0.12, 0.82, and 0.95 &micro, mol L&minus, 1 for hydroquinone, catechol, and BPA, respectively. The sensors were reproducible and selective for detecting BPA in plastic cups, and with adequate specificity not to be affected by interferents from water samples. The simple, inexpensive, and flexible SPE may thus be used to detect emerging pollutants and monitor the water quality.

Made available in DSpace on 2020-12-12T02:06:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-10-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The pursuit of biocompatible, breathable and skin-conformable wearable sensors has predominantly focused on synthetic stretchable hydrophobic polymers. Microbial nanocellulose (MNC) is an exceptional skin-substitute natural polymer routinely used for wound dressing and offers unprecedented potential as substrate for wearable sensors. A versatile strategy for engineering wearable sensing platforms is reported, with sensing units made of screen-printed carbon electrodes (SPCEs) on MNC. As-prepared SPCEs were used to detect the toxic metals cadmium (Cd2+) and lead (Pb2+) with limits of detection of 1.01 and 0.43 μM, respectively, which are sufficient to detect these metal ions in human sweat and urine. SPCEs functionalized through anodic pre-treatments were used for detecting uric acid and 17β-estradiol in artificial sweat, with detection limits of 1.8 μM and 0.58 μM, respectively. The electrochemical treatment created oxygen groups on the carbon surfaces, thus improving wettability and hydrophilicity. MNC was herein exploited as an adhesive-free, yet highly skin-adherent platform for wearable sensing devices that also benefit from the semi-permeable, non-allergenic, and renewable features that make MNC unique within the pool of materials that have been used for such a purpose. Our findings have clear implications for the developments on greener and more biocompatible but still efficient substrates and may pave the route for combining immunosensing devices with drug delivery therapies. São Carlos Institute of Physics University of São Paulo (USP) São Carlos Institute of Chemistry University of São Paulo (USP) Institute of Chemistry University of Campinas (UNICAMP), P.O. Box 6154 Biopolymers and Biomaterials Laboratory (BIOPOLMAT) University Center of Araraquara (UNIARA) Brazilian Nanotechnology National Laboratory (LNNano) Brazilian Center for Research in Energy and Materials (CNPEM) São Paulo State University (UNESP) Department of General and Inorganic Chemistry Rua Professor Francisco Degni, 55, Araraquara14800-060 São Paulo State University (UNESP) Department of General and Inorganic Chemistry Rua Professor Francisco Degni, 55, Araraquara14800-060 FAPESP: 2013/14262–7 FAPESP: 2015/01770–0 FAPESP: 2016/01919–6 FAPESP: 2016/06612–6 CNPq: 423952/2018-8

Electrochemical immunosensors have been developed to determine the carbohydrate antigen 19-9 (CA19-9). They are based on screen-printed carbon electrodes (SPCEs) coated with layer-by-layer (LbL) films of carbon black (CB) and polyelectrolytes. Owing to a suitable choice of LbL film architecture, the procedures for immobilization of anti-CA19-9 antibodies on the electrode surfaces were straightforward. Mechanically flexible immunosensors were capable of detecting CA19-9 within a dynamic range of 0.01 to 40 U mL−1 and a limit of detection of 0.07 U mL−1 using differential pulse voltammetry. In addition to detecting CA19-9 at clinically relevant concentrations for pancreatic cancer in standard solutions, the immunosensors provide the determination of CA19-9 on cell lysate and human serum samples. Using LbL films led to immunosensors with superior performance compared to similar systems obtained by drop casting. The fabrication of this relatively simple, inexpensive platform is a demonstration that SPCEs modified with cost-effective materials are able to detect cancer biomarkers and may be adapted to other disposable immunosensors.

A disposable electrochemical immunosensors is presented suitable to detect cancer biomarker p53 using screen-printed carbon electrodes modified with a layer-by-layer (LbL) matrix of carboxylated NiFe

A disposable electrochemical immunosensors is presented suitable to detect cancer biomarker p53 using screen-printed carbon electrodes modified with a layer-by-layer (LbL) matrix of carboxylated NiFe2O4 nanoparticles and polyethyleneimine, onto which anti-p53 antibodies were adsorbed. Under optimized conditions, the immunosensors exhibited high surface coverage and high concentration of immobilized antibodies, which allowed for detection of p53 in a wide dynamic range from 1.0 to 10 × 103 pg mL−1, with a limit of detection of 5.0 fg mL−1 at a working potential of 100 mV vs. Ag/AgCl. The immunosensors also exhibited good selectivity with negligible interference upon incubation in complex matrices containing high concentrations of proteins (i.e., fetal bovine serum and cell lysate). The immunosensor performance is among the best reported in the literature for determination of p53, with the additional advantage of being disposable and operating with low-volume solutions. Graphical abstract

A green approach for the preparation of carbon black (CB) and electrochemically reduced graphene oxide composite (ERGO) is described based on screen printed carbon electrodes (SPCEs) fabricated on poly(ethylene terephthalate) (PET) as electrochemical sensors. This approach leads to a heterogeneous hydrophilic surface with high concentration of defect sites according to scanning electron microscopy, contact angle and Raman spectroscopy measurements. The SPCE/CB-ERGO sensor was tested with dopamine (DA), epinephrine (EP) and paracetamol (PCM), exhibiting an enhanced electrocatalytic performance compared to the bare SPCE. It displayed a wider linear range, lower limit of detection and a remarkably higher analytical sensitivity, viz. 1.5, 0.13 and 0.028 A L mol−1 for DA, EP and PCM, respectively, being also capable of simultaneous determination of the three analytes. Such high performance is demonstration that SPCE/CB-ERGO may serve as generic platform for cost-effective flexible electrochemical sensors.

Quick-response (QR) codes are gaining much consideration in recent years due to their simple and fast readability compared with conventional barcodes. QR codes provide increased storage capacity and safer access to information, fostering the development of optical or printed smart tags as preferred tools for the Internet of Things (IoT). Herein, the combination of Yb3+/Er3+-doped NaGdF4 upconverting nanoparticles (UCNPs) with recovered plastic for the fabrication of sustainable screen-printed QR codes is reported. Their photothermal response under distinct power densities of the 980 nm laser irradiation (15���115 W cm���2) induces color-tuning and temperature sensing. This power dependence is exploited to design a double key molecular keylock accessed by a smartphone camera through the red (R), green (G), and blue (B) (RGB) additive color model and upconversion thermometry. The latter is based on the integrated areas of the 2H11/2���4I15/2 and 4S3/2���4I15/2 Er3+ transitions using the interconnectivity and integration into the IoT network of the mobile phone to download the temperature calibration curve of the UCNPs from a remote server. These findings illustrate the potential of QR codes-bearing UCNPs toward the design of smart tags for mobile optical sensing and anticounterfeiting., This project has received funding from the European Union's Horizon 2020 FET Open programme under grant agreement No 801305 (NanoTBTech). This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Grant Agreement No. 823941.

Nanostructured capacitive biosensors, combined with inexpensive fabrication technologies, may provide simple, sensitive devices for detecting clinically relevant cancer biomarkers. Herein, we report a novel platform for detecting the pancreatic cancer biomarker CA19-9 using low-cost screen-printed interdigitated electrodes (SPIDEs). The SPIDEs were modified by carbon nano-onions (CNOs) and graphene oxide (GO) films, on which a layer of anti-CA19-9 antibodies was immobilized. The modification with CNOs and GO significantly improved the analytical performance of the biosensor, which displayed superior results to those prepared only with GO. The biossensor exhibited high reproducibility and a relatively low limit of detection of 0.12 U mL-1. Using these devices in combination with information visualization methods we were able to detect CA19-9 in whole cell lysates of colorectal adenocarcinoma. The fabrication of these low-cost, disposable immunosensors is a successful attempt to explore CNOs in capacitive biosensors, which may be extended for detection of different cancer biomarkers., CAPES (001), CNPq, INEO and FAPESP (2012/15543-7, 2013/14262-7, 2015/01770-0, 2016/00991-5 and 2017/12096-3). M.N.C is grateful for the economic support from Vicerrectoria de Investigaciones and the Centro de Excelencia en Nuevos Materiales (CENM) from the Universidad del Valle.

Outbreaks of foodborne diseases demand simple, rapid techniques for detecting pathogenic bacteria beyond the standard methods that are not applicable to routine analysis in the food industry and in the points of food consumption. In this work, we developed a sensitive, rapid and low-cost assay for detecting Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Salmonella typhimurium (S. typhi) in potable water and apple juice. The assay is based on electrical impedance spectroscopy measurements with screen-printed interdigitated electrodes coupled with magnetite nanoparticles functionalized with the antimicrobial peptide melittin (MLT). The data were analyzed with the information visualization methods Sammon's Mapping and Interactive Document Map to distinguish samples at two levels of contamination from food suitable for consumption. With this approach it has been possible to detect E. coli concentration down to 1 CFU mL−1 in potable water and 3.5 CFU mL−1 in apple juice without sample preparation, within only 25 min. This approach may serve as a low-cost, quick screening procedure to detect bacteria-related food poisoning, especially if the impedance data of several sensing units are combined.

In this communication, a new methodology for the simultaneous and automated monitoring of biosorption processes of multimetal mixtures of polluting heavy metals on vegetable wastes based on flow-injection potentiometry (FIP) and electronic tongue detection (ET) is presented. A fixed-bed column filled with grape stalks from wine industry wastes is used as the biosorption setup to remove the metal mixtures from the influent solution. The monitoring system consists in a computer controlled-FIP prototype with the ET based on an array of 9 flow-through ion-selective electrodes and electrodes with generic response to divalent ions placed in series, plus an artificial neural network response model. The cross-response to Cu(2+), Cd(2+), Zn(2+), Pb(2+) and Ca(2+) (as target ions) is used, and only when dynamic treatment of the kinetic components of the transient signal is incorporated, a correct operation of the system is achieved. For this purpose, the FIA peaks are transformed via use of Fourier treatment, and selected coefficients are used to feed an artificial neural network response model. Real-time monitoring of different binary (Cu(2+)/ Pb(2+)), (Cu(2+)/ Zn(2+)) and ternary mixtures (Cu(2+)/ Pb(2+)/ Zn(2+)), (Cu(2+)/ Zn(2+)/ Cd(2+)), simultaneous to the release of Ca(2+) in the effluent solution, are achieved satisfactorily using the reported system, obtaining the corresponding breakthrough curves, and showing the ion-exchange mechanism among the different metals. Analytical performance is verified against conventional spectroscopic techniques, with good concordance of the obtained breakthrough curves and modeled adsorption parameters.

All-solid-state sensors with polyvinyl chloride (PVC)-based membranes using off-the-shelf N-hydroxysuccinimide (NHS) and succinimide (Succ) ionophores were prepared using DOP (dioctyl phthalate) and NPOE (ortho-nitrophenyloctyl ether) as plasticizers. Good responses were obtained when NHS was used. The potentiometric response of the proposed electrode is independent of pH over the range 2-6. The electrode shows a fast response time of 0.25 s. The electrode exhibits a Super-Nernstian response, with 37.5 mV/decade, with a potentiometric detection limit of 4.4 μM. The proposed sensor revealed good selectivity towards a group of transition metal ions.

A sensor array of 9 potentiometric PVC sensors has been employed for the simultaneous determination of heavy metals in soil. Sensors were firstly characterized in their response: Nernstian behavior, a concentration range from ca. 10 6 to 10 2 M and selectivity coefficients confirming that all sensors had cross-response for the target ions. The mixed response system was modeled employing Artificial Neural Networks. The proposed tool was applied to the determination of Pb 2 + ,C d 2 + ,C u 2 + and Zn 2 + in soils at the mg kg 1 level with satisfactory performance. Results were compared and validated against AAS reference methodology, with correlations R 2 > 0.948 for the four heavy metals considered.

Two PVC membrane ion selective electrodes for Pb(II) ion based on two bis-thioureas: 1,3-bis(N'-benzoylthioureido)benzene and 1,3-bis(N'-furoylthioureido)benzene as ionophores, are reported. A first membrane formulated using 1,3-bis(N'-benzoylthioureido)benzene as carrier exhibited a Nernstian response to Pb(II) over a wide concentration range (4.0x10(-6) to 1.0x10(-2)M) with a slope of 31.5+/-1.6 mV/dec. It showed a fast response time (t(90%)=14 s) and could be used for 10 weeks without any divergence in potentials. The membrane formulated using 1,3-bis(N'-furoylthioureido)benzene as carrier exhibited a Nernstian response in the concentration range (5.0x10(-6) to 1.0x10(-2) M), with a slope of 30.0+/-1.3 mV/dec. Its response time was t(90%)=14 s, and it could be used for 14 weeks without any divergence in potentials. The two proposed potentiometric sensors revealed acceptable selectivities for Pb(II) over a wide variety of other metal ions and could be used in a pH range of 2.2-6.0. Both electrodes were assayed in direct potentiometric determination of lead in soils (10-30 mg/kg range) with very good performance (0.99935 correlation coefficient in the comparison against ICP-MS method).

An automated flow injection potentiometric (FIP) system with electronic tongue detection (ET) is used for the monitoring of biosorption processes of heavy metals on vegetable wastes. Grape stalk wastes are used as biosorbent to remove Cu2+ ions in a fixed-bed column configuration. The ET is formed by a 5-sensor array with Cu2+ and Ca2+-selective electrodes and electrodes with generic response to heavy-metals, plus an artificial neural network response model of the sensor's cross-response. The real-time monitoring of both the Cu2+ and the cation exchanged and released (Ca2+) in the effluent solution is performed by using flow-injection potentiometric electronic tongue system. The coupling of the electronic tongue with automation features of the flow-injection system allows us to accurately characterize the Cu2+ ion-biosorption process, through obtaining its breakthrough curves, and the profile of the Ca2+ ion release. In parallel, fractions of the extract solution are analysed by spectroscopic techniques in order to validate the results obtained with the reported methodology. The sorption performance of grape stalks is also evaluated by means of well-established sorption models.