Unconventional active biosensor made of piezoelectric BaTiO3 nanoparticles for biomolecule detection

doi:10.1016/j.snb.2017.07.159

Sensors and Actuators B: Chemical

Volume 253, December 2017, Pages 1180-1187

https://doi.org/10.1016/j.snb.2017.07.159 Get rights and content

Highlights

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First report on BaTiO₃ NPs film based nanogenerator as one-stop active glucose sensor.
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Multifunctional and biocompatible BaTiO₃ NPs with piezoelectric and semiconducting properties.
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Device with dual functions, as both an energy source and a biosensing signal.
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Proposed sensor has good selectivity and detection limits down to 10 μM.
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Prototype for smart/intelligent implantable nanosystems for theranostic applications.

Abstract

A smart biosensor based on piezoelectric and semiconducting properties of Barium titanate nanoparticles (BT NPs) by means of a piezoelectric nanogenerator (PNG) is reported for the first time. An Al/BT/ITO NG (Aluminum (Al)/Barium titanate (BT)/Indium Tin Oxide (ITO) nanogenerator) was devised as a self-powered biosensor for actively detecting glucose. The piezoelectric output generated from this NG has dual functions, as both an energy source and a biosensing signal. The biomolecule alters device conductance (charge-carrier density), providing a gate potential, and can vary the local work function and band alignment due to its adsorption on the surface of BT NPs (interfacial contact effect). Here, we tailored the piezoelectric and semiconducting properties of BT NPs using glucose molecules. The glucose molecules (lewis base) on the surface of BT NPs film (lewis acid) act as a gate potential, and the field effect eventually influence the charge carrier density (electrons) of BT NPs film, which varies the screening effect of free-carriers on the piezoelectric output. The novel self-powered glucose biosensor has good selectivity (∼6-fold increase in response vs. interferents) and the approach demonstrated here can serve as a prototype for the development of next-generation smart/self-powered nanosystems for theranostic applications.

Graphical abstract

Introduction

Multi-functional, self-powered, piezoelectric-based active sensors have potential in the development of medical devices for health-monitoring purpose. The realization of such a smart nanosystem is quite challenging, but highly desirable for next-generation diagnostic and theranostic applications. Such unconventional diagnostic tools can be realized from conventional principles existing in everyday applications, such as piezoelectricity. Piezoelectric nanogenerators (PNG) are among the older, more established energy harvesters converting mechanical energy into electrical energy [1]. Much research has been focused on harvesting mechanical energy in living environments, and scavenging biomechanical energy, and their conversion to electrical power for powering low-power electronic gadgets and sensors [2], [3], [4]. Few reports on PNGs as implantable devices for health monitoring are available [5], [6]. With limitations in the operational lifetime of the conventional batteries used for powering implantable devices, continuous monitoring over long periods is almost impossible. Surgeries are needed to replace batteries, leading to complications and morbidity. Implantation of both an energy harvester and a monitoring system could be a solution but it would occupy more space inside the recipient animal or patient, involving complex surgical procedures. Thus, developing a stand-alone, fully integrated, one-stop device (an active biosensor) is a desirable solution.

The BaTiO₃ nanoparticle (BT NP) is a well-known piezoelectric, ferroelectric material, similar to lead zirconate titanate (PZT), the piezoelectric harvesting properties of which have been described and investigated by many researchers [7], [8], [9], [10]. Although research on enhancing the piezo properties of the BT NP by composite technologies and bio-based template-assisted self-assembling technology [11], have been reported, it remains unexploited with respect to biosensing and theranostic applications. Unlike PZT, BT NPs are biocompatible, making them suitable candidates for drug delivery, in vivo imaging [12], cancer therapy [13], and self-powered nanosystems [14]. This background prompted us to investigate BT NPs in the field of biosensing for developing self-powered sensors, as reported by our group previously [15], [16]. Instead of harvesting energy separately and integrating it externally with a sensor, a one-stop device having dual functions may be possible. Moreover, vital biomedical information could be determined from the piezoelectric output of a nanogenerator by tailoring its piezoelectric properties for monitoring or sensing biologically important molecules. This suggests a new era of piezo-based biosensing where piezoelectric, piezotronic, and semiconducting properties of BT NPs could play a major role [16], [17], [18]. Thus, tailoring these properties by means of biomolecules can result in a novel biosensing mechanism [17], [19], [20].

Generally, poling leads to orientation of electrical dipoles in BT NPs in the direction of the external electrical field. During mechanical deformation of a nanogenerator, a piezoelectric potential is induced between the top and bottom electrodes due to the stress of the dipoles. This built-in potential causes the flow of free electrons, thus neutralizing the piezoelectric potential [21]. Thus, tailoring the charge-carrier density can result in the piezopotential containing vital information. Adsorption of biomolecules on a piezoelectric material causes changes in the free electrons, so screening of the piezopotential could have a significant effect on the final output of the NG [20], [22]. The free-carrier density in the conduction band of piezoelectric material tends to flow and screen the positive ionic piezoelectric charges at one end, while leaving the negative ionic piezoelectric charges alone. This principle is called the screening effect which alters the piezoelectric output of the PNG. This output signal then serves both as a biosensor and a source of energy. In this study, the piezoelectric output response of an unpackaged BT film-based NG to glucose was investigated, exploring the screening effect of free carriers on piezo potential due to the presence of glucose molecules. The NG can actively detect glucose molecules as a self-powered sensor without requiring external power (active sensor). This study could provide a prototype for the development of next-generation smart/self-powered nanosystems.

Section snippets

Synthesis of BT NPs

A conventional solid-state reaction method was used for synthesizing pristine, tetragonal-phase BT NPs. The precursors – BaCO₃ (99.95%, High Purity Chemicals) and TiO₂ (98%, Daejung Chemicals) – were mixed well in acetone using a pestle and mortar for 30 min until a homogeneous powder was obtained (precursors were taken according to the atomic ratio of BaTiO₃). The homogeneous mixture was then placed inside a combustion boat (alumina) and heated, at a heating rate of 2.5 °C/min, to 1200 °C for 2 h

Structural characterization

The structural morphology, size, and phase of the as-synthesized BT NPs were confirmed through characterization techniques. The XRD and Raman shift results were used to confirm the phase of the BT NPs. The characteristic peaks of BT NPs at 252 cm⁻¹, 305 cm⁻¹, and 518 cm⁻¹ in the Raman spectrum (Fig. 1a) confirmed the tetragonal phase of BT NPs, indicating the presence of Ti⁴⁺ ions in the parent lattice; the peaks at 305 cm⁻¹ and 518 cm⁻¹ were assigned to the A1 and B1 modes, respectively [23].

Conclusions

In summary, a BT film-based NG was developed for energy harvesting and active biosensing. This is the first report of a BT film-based PNG for actively sensing glucose biomolecules. The simple, novel device structure leads to new dimensions in diagnosis, namely piezoelectric-based biosensing. The piezoelectric output signal from the device contains the biosensing signal, thus having a dual purpose as a generator and biosensor. The active glucose sensor has an LOD of 10 μM and is highly selective

Conflict of interest

The authors declare no competing financial interests.

Acknowledgments

This work was supported by the National Research Foundation of Korea (NRF), funded by the Korean government (2016R1A2B2013831).

Sophia Selvarajan is currently pursuing her PhD at the Department of Advanced Convergence Technology and Science in Jeju National University, South Korea as a KGSP grantee (Korean Government Scholarship Program). She did her Master of Technology in Nanotechnology at Karunya University, India (Funded by DST) and her Bachelor of Technology in Biotechnology at Centre for Plant Molecular Biology and Biotechnology, Tamil Nadu Agricultural University, India.H er research areas of interest include

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Alluri Nagamalleswara Rao received Master of Technology in Sensor System Technology (2010) from Vellore Institute of Technology, Vellore and Master of Science in Condensed Mater Physics (2007) from Andhra University, Vishakhapatnam, India. He is currently doing PhD under the supervision of Prof. Kim Sang-Jae at Faculty of Applied Energy systems (Mechanical Engineering) from Jeju National University, South Korea. His research interests include synthesis of piezoelectric nanomaterials, composites, High performance nanogenerators with novel microstructures and self-powered systems for fluid velocity, photo-sensing, biomolecule detection and health monitoring devices like flexion sensors.

Arunkumar Chandrasekhar is currently pursuing his PhD at the Department of Mechatronics Engineering in Jeju National University, Jeju, South Korea where he is a scholarship recipient from the Korean Government Scholarship Program. He has a Master of Science degree in Nanoscience and Nanotechnology from SRM University, India and Bachelor of Engineering degree in Electronics and Communications Engineering from Ranganathan Engineering College, India. He is interested in wearable triboelectric nanogenerator and self-powered devices.

Sang Jae Kim is a professor in the Department of Mechatronics Engineering and the Department of Advanced Convergence Technology and Science in Jeju National University, Republic of Korea. He received his PhD degree in Electrical Communication Engineering from Tohoku University, Japan. He was a visiting research scholar in materials science department at University of Cambridge, UK and at Georgia Institute of Technology, USA as well as a senior researcher at National Institute of Materials Science. His research disciplines are based on nanomaterials and systems for energy and electronics applications, covering Josephson devices, MEMS, supercapacitors, nanogenerators and nanobiosensors.

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Unconventional active biosensor made of piezoelectric BaTiO3 nanoparticles for biomolecule detection

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of BT NPs

Structural characterization

Conclusions

Conflict of interest

Acknowledgments

Biomaterials

Sens. Actuators B Chem.

Biosens. Bioelectron.

Biosens. Bioelectron.

J. Phys. Chem. Solids

Biosens. Bioelectron.

Talanta

Electrochem. Commun.

Highly efficient flexible piezoelectric PZT thin film nanogenerator on plastic substrates

Adv. Mater.

Fabric active transducer stimulated by water motion for self-powered wearable device

ACS Appl. Mater. Interfaces

Conductive fabric based stretchable hybridized nanogenerator for scavenging biomechanical energy conductive fabric based stretchable hybridized nanogenerator for scavenging biomechanical energy

ACS Nano

Enhanced performance of a ZnO nanowire-based self-powered glucose sensor by piezotronic effect

Adv. Funct. Mater.

Native cellulose microfiber based hybrid piezoelectric generator for mechanical energy harvesting utility

ACS Appl. Mater. Interfaces

Self-powered cardiac pacemaker enabled by flexible single crystalline PMN-PT piezoelectric energy harvester

Adv. Mater.

Flexible nanocomposite generator made of BaTiO3 nanoparticles and graphitic carbons

Adv. Mater.

Piezoelectric BaTiO3 thin film nanogenerator on plastic substrates

Nano Lett.

High performance flexible piezoelectric nanogenerators based on BaTiO3 nanofibers in different alignment modes

ACS Appl. Mater. Interfaces

Piezoelectric and triboelectric dual effects in mechanical energy harvesting using BaTiO3/polydimethylsiloxane composite film

ACS Appl. Mater. Interfaces

Unconventional active biosensor made of piezoelectric BaTiO₃ nanoparticles for biomolecule detection

Flexible nanocomposite generator made of BaTiO₃ nanoparticles and graphitic carbons

Piezoelectric BaTiO₃ thin film nanogenerator on plastic substrates

High performance flexible piezoelectric nanogenerators based on BaTiO₃ nanofibers in different alignment modes

Piezoelectric and triboelectric dual effects in mechanical energy harvesting using BaTiO₃/polydimethylsiloxane composite film