Celina Massumi Miyazaki

Recent advances in electronic tongues

This minireview describes the main developments of electronic tongues (e-tongues) and taste sensors in recent years, with a summary of the principles of detection and materials used in the sensing units. E-tongues are sensor arrays capable of distinguishing very similar liquids employing the concept of global selectivity, where the difference in the electrical response of different materials serves as a fingerprint for the analysed sample. They have been widely used for the analysis of wines, fruit juices, coffee, milk and beverages, in addition to the detection of trace amounts of impurities or pollutants in waters. Among the various principles of detection, electrochemical measurements and impedance spectroscopy are the most prominent. With regard to the materials for the sensing units, in most cases use is made of ultrathin films produced in a layer-by-layer fashion to yield higher sensitivity with the advantage of control of the film molecular architecture. The concept of e-tongues has been extended to biosensing by using sensing units capable of molecular recognition, as in films with immobilized antigens or enzymes with specific recognition for clinical diagnosis. Because the identification of samples is basically a classification task, there has been a trend to use artificial intelligence and information visualization methods to enhance the performance of e-tongues.

Layer-by-layer assembly of functionalized reduced graphene oxide for direct electrochemistry and glucose detection

We report an electrochemical glucose biosensor made with layer-by-layer (LbL) films of functionalized reduced graphene oxide (rGO) and glucose oxidase (GOx). The LbL assembly using positively and negatively charged rGO multilayers represents a simple approach to develop enzymatic biosensors. The electron transport properties of graphene were combined with the specificity provided by the enzyme. rGO was obtained and functionalized using chemical methods, being positively charged with poly(diallyldimethylammonium chloride) to form GPDDA, and negatively charged with poly(styrene sulfonate) to form GPSS. Stable aqueous dispersions of GPDDA and GPSS are easily obtained, enabling the growth of LbL films on various solid supports. The use of graphene in the immobilization of GOx promoted Direct Electron Transfer, which was evaluated by Cyclic Voltammetry. Amperometric measurements indicated a detection limit of 13.4μmol·L(-1) and sensitivity of 2.47μA·cm(-2)·mmol(-1)·L for glucose with the (GPDDA/GPSS)1/(GPDDA/GOx)2 architecture, whose thickness was 19.80±0.28nm, as determined by Surface Plasmon Resonance (SPR). The sensor may be useful for clinical analysis since glucose could be detected even in the presence of typical interfering agents and in real samples of a lactose-free milk and an electrolyte solution to prevent dehydration.

Bending of Layer-by-Layer Films Driven by an External Magnetic Field

We report on optimized architectures containing layer-by-layer (LbL) films of natural rubber latex (NRL), carboxymethyl-chitosan (CMC) and magnetite (Fe3O4) nanoparticles (MNPs) deposited on flexible substrates, which could be easily bent by an external magnetic field. The mechanical response depended on the number of deposited layers and was explained semi-quantitatively with a fully atomistic model, where the LbL film was represented as superposing layers of hexagonal graphene-like atomic arrangements deposited on a stiffer substrate. The bending with no direct current or voltage being applied to a supramolecular structure containing biocompatible and antimicrobial materials represents a proof-of-principle experiment that is promising for tissue engineering applications in biomedicine.

Monoamine oxidase B layer-by-layer film fabrication and characterization toward dopamine detection

In this work nanostructured film composites of the monoamine oxidase B (MAO-B) enzyme, free or encapsulated in liposomes, were fabricated by the layer-by-layer (LbL) self-assembly technique, employing polyethylene imine (PEI) as polycation. Initially, the MAO-B enzyme was incorporated into liposomes in order to preserve its enzymatic structure ensuring their activity and catalytic stability. The LbL film growth was monitored by surface plasmon resonance (SPR) by gold resonance angle shift analysis after each bilayer deposition. Subsequently, the films were applied as amperometric biosensors for dopamine detection using Prussian Blue (PB) as the electron mediator. The biosensor fabricated by MAO-B incorporated into liposomes composed of DPPG:POPG in the ratio (1:4) (w/w) showed the best performance with a sensitivity of 0.86 (μA cm(-2))/(mmol L(-1)) and a detection limit of 0.33 mmol L(-1).

Surface plasmon resonance biosensor for enzymatic detection of small analytes

Surface plasmon resonance (SPR) biosensing is based on the detection of small changes in the refractive index on a gold surface modified with molecular recognition materials, thus being mostly limited to detecting large molecules. In this paper, we report on a SPR biosensing platform suitable to detect small molecules by making use of the mediator-type enzyme microperoxidase-11 (MP11) in layer-by-layer films. By depositing a top layer of glucose oxidase or uricase, we were able to detect glucose or uric acid with limits of detection of 3.4 and 0.27 μmol l-1, respectively. Measurable SPR signals could be achieved because of the changes in polarizability of MP11, as it is oxidized upon interaction with the analyte. Confirmation of this hypothesis was obtained with finite difference time domain simulations, which also allowed us to discard the possible effects from film roughness changes observed in atomic force microscopy images. The main advantage of this mediator-type enzyme approach is in the simplicity of the experimental method that does not require an external potential, unlike similar approaches for SPR biosensing of small molecules. The detection limits reported here were achieved without optimizing the film architecture, and therefore the performance can in principle be further enhanced, while the proposed SPR platform may be extended to any system where hydrogen peroxide is generated in enzymatic reactions.

Ultra-Thin Films of Reduced Graphene Oxide (RGO) Nanoplatelets Functionalized with Different Organic Materials

This work aims the functionalization of reduced graphene oxide nanoplatelets with chitosan (G-chitosan) and also with poly(styrenesulfonic acid) (GPSS), thus forming stable, dispersed aqueous solut ...

Experimental and computational investigation of reduced graphene oxide nanoplatelets stabilized in poly(styrene sulfonate) sodium salt

The production of large-area interfaces and the use of scalable methods to build up designed nanostructures generating advanced functional properties are of high interest for many materials science applications. Nevertheless, large-area coverage remains a major problem even for pristine graphene, and here we present a hybrid, composite graphene-like material soluble in water that can be exploited in many areas such as energy storage, electrodes fabrication, selective membranes and biosensing. Graphene oxide (GO) was produced by the traditional Hummers’ method being further reduced in the presence of poly(styrene sulfonate) sodium salt (PSS), thus creating stable reduced graphene oxide (rGO) nanoplatelets wrapped by PSS (GPSS). Molecular dynamics simulations were carried out to further clarify the interactions between PSS molecules and rGO nanoplatelets, with calculations supported by Fourier transform infrared spectroscopy analysis. The intermolecular forces between rGO nanoplatelets and PSS lead to the formation of a hybrid material (GPSS) stabilized by van der Waals forces, allowing the fabrication of high-quality layer-by-layer (LbL) films with poly(allylamine hydrochloride) (PAH). Raman and electrical characterizations corroborated the successful modifications in the electronic structures from GO to GPSS after the chemical treatment, resulting in (PAH/GPSS) LbL films four orders of magnitude more conductive than (PAH/GO).

Surface Plasmon Resonance (SPR) for Sensors and Biosensors

Surface plasmon resonance (SPR) is an optical technique that exploits the generation of electromagnetic waves (plasmons). The propagation of the surface plasmons at the metal–dielectric interface is very sensitive to the variations in the refractive index of the surface allowing the monitoring of ultrathin films grown very close to the metal interface. Sensor development and studies about kinetics of interaction between biomolecules are the most investigated applications in the field. The main advantage over other currently used techniques is the possibility of label-free and real-time analysis with high sensitivity and specificity. In this chapter, we discuss briefly the theory of surface plasmon generation; the SPR-based sensor fundamentals and the main applications of the technique are also remarked on.

Self-assembly Thin Films for Sensing

The ability to control properties of nanomaterials by immobilization on a substrate of interest through Layer-by-Layer (LbL) and Langmuir-Blodgett (LB) techniques have drawn attention among many researchers. The molecular level control achieved by the LB and LbL techniques in coating surfaces can be explored in different areas, as energy generation and storage, environmental, clinical analysis, among others. We focus on three materials of great importance in the development of sensors in recent decades: metallic nanoparticles, graphene and carbon nanotubes based materials. In this chapter, the LB and LbL techniques are briefly discussed. The state-of-the-art of metal nanoparticles, graphene, and carbon nanotubes based materials in such films focusing sensing applications are summarized in this chapter.

SISTEMAS DE BAIXA DIMENSIONALIDADE: NANOPARTÍCULAS

As nanoparticulas vem exercendo importante funcao no desenvolvimento de diversas areas como em catalise, biotecnologia e desenvolvimento de sensores, entre outros. Este capitulo ira introduzir um conhecimento basico sobre as principais tecnicas de obtencao das nanoparticulas, descrevendo processos de sintese top-down (de cima para baixo) e bottom-up (de baixo para cima), e, para este ultimo, discutir aspectos fisico-quimicos e processos de estabilizacao. As propriedades que tornam esse tipo de material tao interessante sao discutidas na sequencia, com a descricao sucinta das principais tecnicas de caracterizacao, como difracao de raios X, microscopia eletronica de transmissao e microscopia de forca atomica. As nanoparticulas sao amplamente aplicadas nas mais diversas areas e neste capitulo serao apresentados alguns avancos na literatura em relacao a biossensores, catalise e aplicacoes biomedicas.