Nantao Li, Bin Zhao, Robert Stavins, Ana Sol Peinetti, Neha Chauhan, Rashid Bashir, Brian T. Cunningham, William P. King, Yi Lu, Xing Wang, Enrique Valera
Current Opinion in Solid State and Materials Science 26 (2022) 100966
The COVID-19 pandemic revealed fundamental limitations in the current model for infectious disease diagnosis and serology, based upon complex assay workflows, laboratory-based instrumentation, and expensive materials for managing samples and reagents. The lengthy time delays required to obtain test results, the high cost of goldstandard PCR tests, and poor sensitivity of rapid point-of-care tests contributed directly to society’s inability to efficiently identify COVID-19-positive individuals for quarantine, which in turn continues to impact return to normal activities throughout the economy. Over the past year, enormous resources have been invested to develop more effective rapid tests and laboratory tests with greater throughput, yet the vast majority of engineering and chemistry approaches are merely incremental improvements to existing methods for nucleic acid amplification, lateral flow test strips, and enzymatic amplification assays for protein-based biomarkers. Meanwhile, widespread commercial availability of new test kits continues to be hampered by the cost and time required to develop single-use disposable microfluidic plastic cartridges manufactured by injection molding
Lucy L Coria-Oriundo, M Lorena Cortez, Omar Azzaroni, Fernando Battaglini
Soft Matter, 2021, 17, 5240-5247
Redox mediators are pivotal players in the electron transfer process between enzymes and electrodes. We present an alternative approach for redox mediation based on branched polyethyleneimine (BPEI) modified with an osmium complex. This redox polyelectrolyte is crosslinked with phosphate to produce colloidal particles with a diameter of ca. 1 μm, which, combined with glucose oxidase (GOx), can form electroactive assemblies through either layer by layer assembly (LbL) or one-pot drop-casting (OPDC). The addition of NaCl to these colloidal systems induces the formation of films that otherwise poorly grow, presenting an outstanding catalytic current. The system was tested as a bioanode delivering a power output of 148 μW per nmol of mediator. These results are explained in terms of the interactions of the ions with the polyelectrolyte and represent a new route for the development of bioelectrochemical devices involving redox mediators and enzymes.
Lucy L Coria-Oriundo, Fernando Battaglini, Sonia Wirth
Ecotoxicology and Environmental Safety, 217, 112237 (2021)
Laccases and laccase-mediator systems (LMS) are versatile catalysts that can oxidize a broad range of substrates coupled to the sole reduction of dioxygen to water. They possess many biotechnological applications in paper, textile, and food industries, bioethanol production, organic synthesis, detection and degradation of pollutants, and biofuel cell development. In particular, bacterial laccases are getting relevance due to their activity in a wide range of pH and temperature and their robustness under harsh conditions. However, the enzyme and the redox mediator's availability and costs limit their large-scale commercial use. Here we demonstrate that β-(10-phenothiazyl)-propionic acid can be used as an efficient and low-cost redox mediator for decolorizing synthetic dyes by the recombinant laccase SilA from Streptomyces ipomoeae produced in E. coli. This new LMS can decolorize more than 80% indigo carmine and malachite green in 1 h at pH = 8.0 and 2 h in tap water (pH = 6.8). Furthermore, it decolorized more than 40% of anthraquinone dye remazol brilliant blue R and 80% of azo dye xylidine ponceau in 5 h at 50 °C, pH 8.0. It supported at least 3 decolorization cycles without losing activity, representing an attractive candidate for a cost-effective and environmentally friendly LMS functional at neutral to alkaline pH.
Keyla M Fuentes, Lucy L Coria-Oriundo, Sonia Wirth, Sara A Bilmes
Journal of Porous Materials 28, 261-269 (2021)
Functionalized mesoporous SiO2 are common supports for some enzymes of industrial interest, such as laccases. However, the incorporation of specific functionalities and the loading of enzymes with dimensions close to the diameters of the pores obstructs the porous system. For biotechnological applications, tailored porous supports are still needed to enhance the laccase loading. The hierarchical meso/macroporous system in wrinkled-SiO2 spheres (w-SiO2) is a suitable option to overcome this issue. Herein, (3-aminopropyl) triethoxysilane and glutaraldehyde were use as functionalizing agents for the immobilization of laccase on w-SiO2. The functionalization occurs in the mesopores of the wrinkled walls and the preservation of the macroporous entries facilitates the diffusion of the laccase inside the particle. The enzyme performance was evaluated by means of the crystal violet bleaching. The enzyme is stabilized through the imine groups provided by glutaraldehyde, allowing the retention of the activity after several reaction cycles. The bleaching can be boosted by acetosyringone, highlighting the possibility of using redox mediators to expand the range of oxidizable substrates. Understanding the effect of w-SiO2 functionalization on laccases loading and performance could be extrapolated to other enzymes with biotechnological interest that requires this type of hierarchical porous silica.
Esteban Piccinini, Graciela A González, Omar Azzaroni, Fernando Battaglini
Journal of Colloid and Interface Science 581, 595-607,2021
The assembly of polyacrylic acid and different combinations of redox-modified and unmodified hexadecyltrimethylammonium bromide yields highly structured and electroactive thin films. The growth, viscoelastic properties, mass, and electron transport of these films were studied by combining electrochemical and quartz crystal balance with dissipation experiments.
Lucy L Coria-Oriundo, Helena Ceretti, Yoann Roupioz, Fernando Battaglini
ChemistrySelect, 5(36), 11391-11398
We present an electrochemical sandwich-type assay based on the splitting of an aptamer into two fragments. Gold nanoparticles are modified with one of the fragments and a redox polyelectrolyte. The first is used as the recognition element, while the other for the electrochemical signal generation. The split-aptamer used here can detect adenosine, used as a model system for recognizing small molecules. The multiple binding sites on the nanoparticle, along with the high number of redox probes, yield a selective and sensitive assay for adenosine, achieving a limit of detection of 3.1 nM and a linear range up to 75 nM. The obtained results are analyzed in terms of the nanoparticle and electrode architectures. The assay can be easily extended to other small molecules and sandwich assays, representing a promising tool for detecting metabolites at the nanomolar level.
Esteban Piccinini, Marcelo Ceolín, Fernando Battaglini, Omar Azzaroni
The layer‐by‐layer assembly of polyelectroIMlytes and surfactants enables structural control of multilayers displaying meso‐organized 3D redox‐active domains. The approach exploits the dual role of surfactants as functional units, i. e.: redox active centers, and structural units, such as structure‐directing agents. The population of redox centers hosted into the film can be manipulated by co‐assembling electroactive and non‐electroactive surfactants. This strategy constitutes a straightforward technique to produce electroactive films with precise control over the spatial organization of their redox domains, even under dynamic electrochemical conditions.
Juliana Scotto, Esteban Piccinini, Catalina von Bilderling, Lucy L Coria-Oriundo, Fernando Battaglini, Wolfgang Knoll, Waldemar A Marmisolle, Omar Azzaroni
Applied Surface Science, 146440, 2020
In this work, we present a novel strategy for producing graphite nanosheets (GNS) dispersed in the solvent employed then for the chemical synthesis of PEDOT, which allows producing composite nanofilms on plastic substrates for the construction of transparent and flexible all-polymer electrodes. By an optimized experimental procedure, we achieved a proper integration of PEDOT and GNS within ultrathin (<100 nm) composite films and good enough conductivity to ensure adequate electrochemical response without the requirement of conducting base electrodes. We tested the performance of these platforms for real applications by developing glucose biosensors by molecular integration of supramolecular assembly of glucose oxidase and an electroactive polyelectrolyte on top of the PEDOT-GNS coatings.
Ignacio Boron, Angela Juarez, Fernando Battaglini
biosensor composed by unicellular microalgae hosted in a mechanically stable and electrochemically sensitive material is cast on a screen‐printed electrode and mounted in a flow‐cell system. The biosensor presents a limit of detection of 24 ppb to atrazine and a long‐term stability, making this system suitable for remote sensing.
Nitya Sai Reddy Satyavolu, Ana Sol Peinetti, Yiming Wang, Arzeena Sultana Ali, Jeffrey Wayjer Lin, Yi Lu
Chemistry of Materials 31 (8), 2923-2929, 2019
This study establishes a synthetic procedure that is scalable and is both chemically and economically more accessible than the existing protocols for Pd THH nanoparticles, making it possible for much wider applications of the Pd THH nanoparticles and its variants. Finally, these particles displayed higher electrocatalytic activity for ethanol oxidation reaction compared to low-indexed faceted Pd nanoparticles and commercially available Pd catalysts.
Noor Zaouri, Zhengfang Cui, Ana Sol Peinetti, Yi Lu, Pei-Ying Hong
Environmental Science: Water Research & Technology 5 (12), 2260-2268, 2019
This study aimed to achieve rapid verification test of E. coli using DNAzyme-based biosensor. The biosensor was first tested for four E. coli strains against more than 90 non-E. coli strains routinely causing false positive results and showed high specificity towards E. coli strains. The biosensor was then determined for its detection sensitivity. It was observed that a single E. coli colony would generate a robust fluorescence signal after 2 h of sub-culturing. With this short incubation time, non-E. coli strains were unable to generate any apparent fluorescence signal, hence further improving the detection specificity of biosensor. Lastly, we further demonstrate that the biosensor can be applied to different commercial brands of simultaneous enzyme-based agar to consistently identify the presence of E. coli. The biosensor was able to rapidly denote presence of discrete E. coli colonies by binding on to protein targets possibly of DNA replication or motility functions that were predominantly specific to E. coli.
Daniele Zappi, Lucy L Coria-Oriundo, Esteban Piccinini, Marcos Gramajo, Catalina von Bilderling, Lía I Pietrasanta, Omar Azzaroni, Fernando Battaglini
Physical Chemistry Chemical Physics 21 (41), 22947-22954, 2019
Our results show that the environment from which the assembly is constructed has a significant effect on the electrochemical response. Notably, the polyelectrolyte dissolved in the presence of phosphate at high ionic strength presents a globular structure which is preserved after adsorption with substantial effects on the buildup of the multilayer system, improving the electron transfer process through the film.
Ignacio Pedre, Fernando Battaglini, Graciela A González
Electroanalysis 30 (11), 2589-2596, 2019
A simple and reliable method is presented for the direct monitoring of xanthate in flotation baths and their effluents, as a tool for their reconditioning, and reducing their environmental impact. For this purpose, screen‐printed graphite electrodes (SPE) were modified with a polyelectrolyte‐surfactant matrix which was able to adsorb the xanthate, whose concentration is determined by electrochemical impedance spectroscopy (EIS) following the change in the electron transfer resistance of ferrocyanide after a pre‐oxidation treatment.
Ana S Peinetti, Helena Ceretti, Martín Mizrahi, Graciela A González, Silvana A Ramírez, Félix G Requejo, Javier M Montserrat, Fernando Battaglini
Bioelectrochemistry 121, 169-175, 2018
Our results prove that low DNA coverages on the confined nanoparticles prompt to a more sensitive response, showing the relevance in avoiding the DNA strand overcrowding. The system was able to determine a concentration as low as 100 pM of the complementary strand, thus introducing the foundations for the construction of label-free genosensors at the nanometer scale.
Gonzalo Pérez-Mitta, Ana S Peinetti, M Lorena Cortez, María Eugenia Toimil-Molares, Christina Trautmann, Omar Azzaroni
Nano Letters 18 (5), 3303-3310, 2018
In this work, we describe the construction of novel ultrasensitive enzymatic nanopore biosensors employing “reactive signal amplifiers” as key elements coupled to the transduction mechanism. The proposed framework offers innovative design concepts not only to amplify the detected ionic signal and develop ultrasensitive nanopore-based sensors but also to construct nanofluidic diodes displaying specific chemo-reversible rectification properties. The integrated approach is demonstrated by electrostatically assembling poly(allylamine) on the anionic pore walls followed by the assembly of urease.
Ana S Peinetti, Martín Mizrahi, Félix G Requejo, David Buceta, M Arturo López-Quintela, Graciela A González, Fernando Battaglini
Journal of colloid and interface science 516, 371-378, 2018
Synthesis of low atomicity Ni nanoclusters is carried out in 10 nm diameter mesoporous alumina allowing the production of zerovalent ligand-free Ni nanoclusters estimated in 13 atoms. The size and shape of the Nickel entities inside the pores can be controlled by the current density applied during the reduction process. The nanoclusters show a superior performance as catalysts for the reduction of methylene blue.
Fernando Battaglini, Ana S Peinetti
Encyclopedia of Interfacial Chemistry. Surface Science and Electrochemistry, 2018
Esteban Piccinini, Jimena S Tuninetti, Joseba Irigoyen Otamendi, Sergio E Moya, Marcelo Ceolín, Fernando Battaglini, Omar Azzaroni
Physical Chemistry Chemical Physics 20 (14), 9298-9308, 2018
. In the present work we demonstrate that the integration of surfactants (as mesogenic agents) into layer-by-layer (LbL) assembled polyelectrolyte multilayers offers a straightforward approach to control the internal film organization at the mesoscale level. The mesostructure of films constituted of hexadecyltrimethylammonium bromide, CTAB, and polyacrylic acid, PAA (of different molecular weights), was characterized as a function of the number of assembled layers.
M Lorena Cortez, Agustín Lorenzo, Waldemar A Marmisollé, Catalina Von Bilderling, Eliana Maza, Lía Pietrasanta, Fernando Battaglini, Marcelo Ceolín, Omar Azzaroni
Soft Matter 14 (10), 1939-1952, 2018
Herein, we report on the facile preparation and application of highly organized stacked multilayers via layer-by-layer assembly of lipid-like surfactants and polyelectrolytes. Polyelectrolyte multilayers with high degree of stratification of the internal structure were constructed through consecutive assembly of polyallylamine and dodecyl phosphate, a lipid-like surfactant that act as a structure-directing agent.
Luciano D Sappia, Esteban Piccinini, Waldemar Marmisollé, Natalia Santilli, Eliana Maza, Sergio Moya, Fernando Battaglini, Rossana E Madrid, Omar Azzaroni
Advanced Materials Interfaces 4 (17), 1700502, 2017
Biorecognizable carbohydrate motifs are integrated onto poly(3,4‐ethylenedioxythiophene) (PEDOT) films through the preparation poly(allylamine)–PEDOT composites via supramolecular interactions. The proposed strategy facilitates the straightforward supramolecular construction of versatile all‐plastic bioelectrochemical platforms. The bioelectrocatalytic detection of glucose is studied. Results reveal that the use of supramolecular PEDOT platforms leads to an enhancement of the bioelectrocatalytic signal.
Esteban Piccinini, Christina Bliem, Ciril Reiner-Rozman, Fernando Battaglini, Omar Azzaroni, Wolfgang Knoll
Biosensors and Bioelectronics 92, 661-667, 2017
We present the construction of layer-by-layer (LbL) assemblies of polyethylenimine and urease onto reduced-graphene-oxide based field-effect transistors (rGO FETs) for the detection of urea. This versatile biosensor platform simultaneously exploits the pH dependency of liquid-gated graphene-based transistors and the change in the local pH produced by the catalyzed hydrolysis of urea.
Ignacio Borón, Sonia Wirth, Fernando Battaglini
Electroanalysis 29 (2), 616-621, 2017
Through adequate laccase immobilization, disposable screen printed electrodes can be used as interphase to build amperometric phenol sensors. In this work three different laccases were studied for the determination of phenol‐like compounds, two of them are isoenzymes from Trametes trogii and the third one from Rhus vernicifera. Their immobilization on screen printed electrodes is presented for the construction of amperometric sensors. The electrode substrate is composed by graphite screen printed electrodes modified with carbon nanotubes and silica microspheres where, depending on the application, one of the three laccases is adsorbed.
M Lorena Cortez, Marcelo Ceolín, Luis Cuellar Camacho, Edwin Donath, Sergio E Moya, Fernando Battaglini, Omar Azzaroni
ACS applied materials & interfaces 9 (1), 1119-1128, 2017
Our studies reveal that the solvent used in processing the supramolecular films and the presence of metal nanoparticles not only have a substantial influence in determining the mesoscale organization and morphological characteristics of the film but also have a strong influence on the efficiency and performance of the bioelectrochemical system. In particular, a higher bioelectrochemical response is observed when nanocomposite supramolecular films were cast from aqueous solutions. These observations seem to be associated with the fact that the use of aqueous solvents increases the hydrophilicity of the film, thus favoring the access of glucose, particularly at low concentrations.
Ignacio Pedre, L Méndez DeLeo, Maria Guadalupe Sánchez-Loredo, Fernando Battaglini, Graciela Alicia González
Sensors and Actuators B: Chemical 232 ,383-389 ,2016
A simple and reliable device is presented for the direct monitoring of thiourea in copper electrorefinery baths as a tool for reconditioning of industrial baths, and so reducing its environmental impact. For this purpose, a screen-printed graphite electrode is modified with silver nanoparticles (AgNPs) contained in a polyelectrolyte-surfactant matrix.
Ana Sol Peinetti, Rodrigo S Gilardoni, Martín Mizrahi, Felix G Requejo, Graciela A González, Fernando Battaglini
Analytical chemistry 88 (11), 5752-5759, 2016
In this work, we present a computational model able to simulate the electrochemical behavior of arrays working either as the summation of individual electrodes or being affected by the overlapping of the diffusional fields without previous considerations. Our computational model relays in dividing a regular electrode array in cells. In each of them, there is a central electrode surrounded by neighbor electrodes; these neighbor electrodes are transformed in a ring maintaining the same active electrode area than the summation of the closest neighbor electrodes.
Esteban Piccinini, Diego Pallarola, Fernando Battaglini, Omar Azzaroni
Molecular Systems Design & Engineering 1 (2), 155-162 2016
For quite a while, scientists have resorted to colloidal synthesis to mimic complex structural and functional materials found in Nature. In particular, within the past few years, the synthesis of suprastructures with novel properties that emerge from the coupling of diverse nanoscale functional units has defined new boundaries in materials science. In this mini-review, we survey the most recent and outstanding achievements on the rational design of supraparticles based on the self-limited self-assembly of nanoparticles, and their application in fields like biology, medicine and energy.
M.L. Cortez, N. de Matteis, M. Ceolín, W. Knoll, F. Battaglini, O. Azzaroni
Physical Chemistry Chemical Physics 16, 20844-20855, 2014
M Lorena Cortez, Marcelo Ceolín, Omar Azzaroni, Fernando Battaglini
Bioelectrochemistry,105 ,117-122 , 2015
In this work the effects of the self-assembly solvent on the structure and electrochemical behavior of redox-active polyelectrolyte–surfactant complexes cast on electrode supports from aqueous and DMF solutions are presented. The complex studied is formed by complexation of osmium complex-modified polyallylamine (OsPA) with dodecyl sulfate (DS) surfactants.
Ignacio Pedre, Fernando Battaglini, Gladis Judith Labrada Delgado, María Guadalupe Sánchez-Loredo, Graciela A González
Sensors and Actuators B: Chemical 211,515-522,2015
A novel and easy-to-use colorimetric thiourea (TU) sensor based on immobilized polyvinylpyrrolidone-stabilized silver nanoparticles (PVP-AgNPs) is reported. The new sensor is aimed for its direct application in copper electrorefinery baths. Quantitative analysis was carried out by adding different thiourea amounts into a synthetic bath and monitoring the absorption changes of the surface plasmon resonance band (SPRB) by UV–Vis spectrophotometry. A linear correlation between the absorbance change and thiourea concentration was obtained, ranging from 0.125 mg/L to 1 mg/L.
Esteban Piccinini, Diego Pallarola, Fernando Battaglini, Omar Azzaroni
Chemical Communications 51(79),14754-14757,2015
We report the recognition-driven assembly of self-limiting protein nanoparticles displaying enzymatic activity. Solution self-assembly of concanavalin A lectin and glycoenzyme glucose oxidase leads to the spontaneous formation of biocolloids with well-defined dimensions, narrow size distribution and remarkable stability. These biocolloids successfully recognize a glycosylated modified electrode retaining the enzyme activity.
Ana S Peinetti, Helena Ceretti, Martín Mizrahi, Graciela A González, Silvana A Ramírez, Felix G Requejo, Javier M Montserrat, Fernando Battaglini
Nanoscale 7 (17), 7763-7769, 2015
Gold nanoparticles with a controlled size (about 2 nm) are electrogenerated in the alumina cavities, showing a fast electron transfer process toward ferrocyanide. These uncapped nanoparticles are easily modified with a thiol-containing aptamer for label-free detection of adenosine monophosphate by electrochemical impedance spectroscopy. Our results show that the use of a limited electrical conducting surface inside an insulating environment can be very sensitive to conformational changes, introducing a new approach to the detection of small molecules, exemplified here by the direct and selective detection of adenosine monophosphate at the nanomolar scale.
M Lorena Cortez, Graciela A González, Marcelo Ceolín, Omar Azzaroni, Fernando Battaglini
Electrochimica Acta 118,124-129, 2014
M Lorena Cortez, Waldemar Marmisollé, Diego Pallarola, Lía I Pietrasanta, Daniel H Murgida, Marcelo Ceolín, Omar Azzaroni, Fernando Battaglini
Chemistry–A European Journal 20 (41),13366-13374,2014
Carina Gaviglio, Fernando Battaglini
Sensors and Actuators B: Chemical 182,53-57, 2013
M Lorena Cortez, Diego Pallarola, Marcelo Ceolín, Omar Azzaroni, Fernando Battaglini
Analytical chemistry 85(4), 2414-2422
Ana Sol Peinetti, Santiago Herrera, Graciela A González, Fernando Battaglini
Chemical Communications 49 (96), 11317-11319, 2013
C. Gaviglio, F. Battaglini
Sensors and Actuators B: Chemical, 182 (2013) 53-57.
Ana Sol Peinetti, Lucila P Méndez De Leo, Graciela A González, Fernando Battaglini
Journal of colloid and interface science 386 (1), 44-50, 2012
M. L. Cortez, D. Pallarola, M. Ceolín, O. Azzaroni, F. Battaglini
Chem. Commun., 48 (2012) 10868–10870
D. Pallarola, C. von Bildering, L. I. Pietrasanta, N. Queralto, W. Knoll, F. Battaglini, O. Azzaroni.
Phys. Chem. Chem. Phys., 14 (2012) 11027–11039.
G. Priano, L.N. Acquaroli, L.C. Lasave, F. Battaglini, R.D. Arce, R.R. Koropecki
Thin Solid Films 520 (2012) 6434–6439.
M. L. Cortez, M. Ceolín, O. Azzaroni, F. Battaglini
Analytical Chemistry, 83 (2011) 8011-8018.
M. L. Cortez, G. A. Gonzalez, F. Battaglini
Electroanalysis, 23 (2011) 156-160
G. González, G. Priano, M. Günther, F. Battaglini
Sensors & Actuators: B. Chemical, 144 (2010) 349-353
D. Pallarola, N. Queralto, W. Knoll, O. Azzaroni, F. Battaglini
Chemistry, a european journal, 16 (2010) .13970-13975
J. Yánez-Heras, G. A. Planes, F. Williams, C. A. Barbero, F. Battaglini.
Electroanalysis, 22 (2010) 2801-2808
J. Yánez Heras, S.D. Rodríguez, R.M. Negri, F. Battaglini.
Sensors & Actuators: B. Chemical, 145 (2010) 726-733.
D. Pallarola, N. Queralto,W. Knoll, M. Ceolín, O. Azzaroni, F. Battaglini
Langmuir, 26 (2010) 13684-13696
D. Pallarola, N. Queralto, F. Battaglini, O. Azzaroni
Phys. Chem. Chem. Phys., 12 (2010) 8071-8083.
J. Yánez Heras, D. Pallarola, F. Battaglini
Biosensors and Bioelectronics, 25 (2010) 2470-2476.
Ana Sol Peinetti, Graciela A González, Fernando Battaglini
Electroanalysis 22 (12), 1329-1336, 2011