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Functional Materials and Proteins for Bio-Sensing Applications

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (30 November 2013) | Viewed by 84353

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Special Issue Editors

Prof. Dr. Jun-ichi Anzai

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Guest Editor

Graduate School of Pharmaceutical Sciences, Tohoku University Aramaki, Aoba-ku, Sendai 980-8578, Japan
Interests: biosensor; polymer materials; stimuli-sensitive materials; LbL films
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Yasushi Hasebe

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Guest Editor

Department of Applied Chemistry, Graduate School of Engineering, Saitama Institute of Technology 1650 Fusaiji, Fukaya, Saitama 369-0293, Japan
Interests: biosensor; carbon materials; protein immobilization; DNA film

Special Issue Information

Dear Colleague,

This special issue focuses on the recent development in functional materials and proteins for bio-sensing applications. The functional materials include synthetic smart polymers, biopolymers such as polysaccharide and DNA, carbon fibers and felts, carbon nanotube and graphene, as well as metal or semiconductor nano-particles. Papers dealing with bio-sensing systems constructed by using the nano-materials coupled with enzymes and antibodies are welcome. The synthesis of self-assembled architectures and thin films comprising these materials and their use for bio-sensing is also within the scope of this special issue. Submission of papers on the construction of high-performance electrochemical and optical bio-sensing systems is particularly encouraged.

This special issue aims to promote exchange of ideas and knowledge of scientists and engineers working in the communities of materials science and bio-sensing.

Prof. Dr. Yasushi Hasebe
Prof. Dr. Jun-ichi Anzai
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

smart polymer
polysaccharide and DNA
carbon fiber and carbon felt
carbon nanotube and graphene
metal and semiconductor nanoparticles
enzyme
antibody
electrochemical biosensor
optical biosensor

Published Papers (11 papers)

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Research

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534 KiB

Open AccessArticle

Carbon Felt-Based Bioelectrocatalytic Flow-Through Detectors: 2,6-Dichlorophenol Indophenol and Peroxidase Coadsorbed Carbon-Felt for Flow-Amperometric Determination of Hydrogen Peroxide

by Yue Wang and Yasushi Hasebe

Materials 2014, 7(2), 1142-1154; https://doi.org/10.3390/ma7021142 - 12 Feb 2014

Cited by 6 | Viewed by 5875

Abstract

2,6-dichlorophenol indophenol (DCIP) and horseradish peroxidase (HRP) were coadsorbed on a porous carbon felt (CF) from their mixed aqueous solution under ultrasound irradiation for 5 min. The resulting DCIP and HRP-coadsorbed CF (DCIP/HRP-CF) showed an excellent bioelectrocatalytic activity for the reduction of H₂O₂. The coadsorption of DCIP together with HRP was essential to obtain larger bioelectrocatalytic current to H₂O₂. The DCIP/HRP-CF was successfully used as a working electrode unit of a bioelectrocatalytic flow-through detector for highly sensitive and continuous amperometric determination of H₂O₂. Under the optimized operational conditions (i.e., applied potential, +0.2 V versus Ag/AgCl; carrier pH 5.0, and carrier flow rate, 1.9 mL/min), the cathodic peak current of H₂O₂ linearly increased over the concentration range from 0.1 to 30 µM (the sensitivity, 0.88 µA/µM (slope of linear part); the limit of detection, 0.1 µM (S/N = 3) current noise level, 30 nA) with a sample through-put of ca. 40–90 samples/h. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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1071 KiB

Open AccessArticle

Direct Electrochemistry and Electrocatalysis of Horseradish Peroxidase Immobilized in a DNA/Chitosan-Fe₃O₄ Magnetic Nanoparticle Bio-Complex Film

by Tingting Gu, Jianli Wang, Hongqi Xia, Si Wang and Xiaoting Yu

Materials 2014, 7(2), 1069-1083; https://doi.org/10.3390/ma7021069 - 11 Feb 2014

Cited by 29 | Viewed by 7951

Abstract

A DNA/chitosan-Fe₃O₄ magnetic nanoparticle bio-complex film was constructed for the immobilization of horseradish peroxidase (HRP) on a glassy carbon electrode. HRP was simply mixed with DNA, chitosan and Fe₃O₄ nanoparticles, and then applied to the electrode surface to form an enzyme-incorporated polyion complex film. Scanning electron microscopy (SEM) was used to study the surface features of DNA/chitosan/Fe₃O₄/HRP layer. The results of electrochemical impedance spectroscopy (EIS) show that Fe₃O₄ and enzyme were successfully immobilized on the electrode surface by the DNA/chitosan bio-polyion complex membrane. Direct electron transfer (DET) and bioelectrocatalysis of HRP in the DNA/chitosan/Fe₃O₄ film were investigated by cyclic voltammetry (CV) and constant potential amperometry. The HRP-immobilized electrode was found to undergo DET and exhibited a fast electron transfer rate constant of 3.7 s⁻¹. The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP(Fe^(III⁾) and HRP(Fe^(II)). The obtained electrode also displayed an electrocatalytic reduction behavior towards H₂O₂. The resulting DNA/chitosan/Fe₃O₄/HRP/glassy carbon electrode (GCE) shows a high sensitivity (20.8 A·cm⁻²·M⁻¹) toward H₂O₂. A linear response to H₂O₂ measurement was obtained over the range from 2 µM to 100 µM (R² = 0.99) and an amperometric detection limit of 1 µM (S/N = 3). The apparent Michaelis-Menten constant of HRP immobilized on the electrode was 0.28 mM. Furthermore, the electrode exhibits both good operational stability and storage stability. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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763 KiB

Open AccessArticle

Detection of Waterborne and Airborne Formaldehyde: From Amperometric Chemosensing to a Visual Biosensor Based on Alcohol Oxidase

by Sasi Sigawi, Oleh Smutok, Olha Demkiv, Galina Gayda, Bohdan Vus, Yeshayahu Nitzan, Mykhailo Gonchar and Marina Nisnevitch

Materials 2014, 7(2), 1055-1068; https://doi.org/10.3390/ma7021055 - 11 Feb 2014

Cited by 18 | Viewed by 6857

Abstract

A laboratory prototype of a microcomputer-based analyzer was developed for quantitative determination of formaldehyde in liquid samples, based on catalytic chemosensing elements. It was shown that selectivity for the target analyte could be increased by modulating the working electrode potential. Analytical parameters of three variants of the amperometric analyzer that differed in the chemical structure/configuration of the working electrode were studied. The constructed analyzer was tested on wastewater solutions that contained formaldehyde. A simple low-cost biosensor was developed for semi-quantitative detection of airborne formaldehyde in concentrations exceeding the threshold level. This biosensor is based on a change in the color of a solution that contains a mixture of alcohol oxidase from the yeast Hansenula polymorpha, horseradish peroxidase and a chromogen, following exposure to airborne formaldehyde. The solution is enclosed within a membrane device, which is permeable to formaldehyde vapors. The most efficient and sensitive biosensor for detecting formaldehyde was the one that contained alcohol oxidase with an activity of 1.2 U·mL⁻¹. The biosensor requires no special instrumentation and enables rapid visual detection of airborne formaldehyde at concentrations, which are hazardous to human health. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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330 KiB

Open AccessArticle

Vascular Endothelial Growth Factor (VEGF) Detection Using an Aptamer and PNA-Based Bound/Free Separation System

by Chifuku Mita, Koichi Abe, Takahiro Fukaya and Kazunori Ikebukuro

Materials 2014, 7(2), 1046-1054; https://doi.org/10.3390/ma7021046 - 11 Feb 2014

Cited by 17 | Viewed by 7468

Abstract

We have developed a bound/free separation system using a vascular endothelial growth factor (VEGF) aptamer and a peptide nucleic acid (PNA) to detect VEGF. In this system, we designed capture PNA (CaPNA), which hybridizes with the aptamer in the absence of the target protein, but does not hybridize with the aptamer in the presence of the target protein due to steric hindrance and/or stabilization of the aptamer’s structure. By removing the aptamers not bound to the target protein using CaPNA immobilized beads, we can detect the target protein by measuring signals labeled with the aptamer in the supernatant. In this study, we detected VEGF using CaPNA-immobilized beads without the time-consuming washing step. This simple and rapid system can detect 25 nM of VEGF in 15 min. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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244 KiB

Open AccessCommunication

Long-Term Stability of a Cellulose-Based Glucose Oxidase Membrane

by Soichi Yabuki, Miho Iwamoto and Yoshiki Hirata

Materials 2014, 7(2), 899-905; https://doi.org/10.3390/ma7020899 - 28 Jan 2014

Cited by 13 | Viewed by 5181

Abstract

A cellulose-based glucose oxidase membrane was prepared on a glassy carbon (GC) electrode. The current response of the electrode to glucose was measured by applying a potential of 1.0 V vs. Ag/AgCl on the base GC and was proportional to the concentration of glucose up to 1 mM. The long-term stability of the electrode was examined by measuring the daily glucose response. Over four months, the response magnitude was maintained and then gradually decreased. After 11 months, though the response magnitude decreased to 50% of the initial value, the linear response range did not change. Therefore, the electrode could be used as a glucose biosensor even after 11 months of use. The entrapment of the enzyme in the cellulose matrix promoted the stability of the enzyme, as revealed by data on the enzyme activity after the enzyme electrode was immersed in urea. Therefore, the cellulose matrix may be used to improve the performance of biosensors, bioreactors and bio-fuel cells. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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314 KiB

Open AccessArticle

Fluorescence Sensing of the Interaction between Biomembranes with Different Lipid Composition and Endocrine Disrupting Chemicals

by Yuko Nakane and Izumi Kubo

Materials 2014, 7(1), 170-179; https://doi.org/10.3390/ma7010170 - 31 Dec 2013

Cited by 3 | Viewed by 5518

Abstract

Fluorescence sensing of the interaction between biomembranes with different lipid composition and endocrine disrupting chemicals (EDCs) was carried out by using a liposome-encapsulating fluorescence dye (carboxyfluorescein (CF)-liposome). We detected a significant increase in fluorescence intensity in CF-liposome solutions due to the leakage of fluorescence caused by the interaction of EDCs with the biomembranes of liposomes. The temporal increases in fluorescent were significantly different among the lipid compositions of CF-liposome and the EDCs. Results were considered by summarizing the interactions in radar charts and by showing the pattern of interaction of each EDC. Each chart showed a dissimilar pattern reflecting the complexity of the biomembrane-EDC interaction. The results indicate that this fluorescence sensing could be useful to evaluate the interaction. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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1092 KiB

Open AccessArticle

Development of Conductive Boron-Doped Diamond Electrode: A microscopic, Spectroscopic, and Voltammetric Study

by Kevin E. Bennet, Kendall H. Lee, James N. Kruchowski, Su-Youne Chang, Michael P. Marsh, Alexander A. Van Orsow, Aurelio Paez and Felicia S. Manciu

Materials 2013, 6(12), 5726-5741; https://doi.org/10.3390/ma6125726 - 06 Dec 2013

Cited by 43 | Viewed by 8004

Abstract

Building on diamond characteristics such as hardness, chemical inertness and low electron emission threshold voltage, the current microscopic, spectroscopic and voltammetric investigations are directed towards improving the properties of electrode coating materials for their future use in clinical studies of deep brain stimulation via fast-scan cyclic voltammetry (FSCV). In this study we combine the capabilities of confocal Raman mapping in providing detailed and accurate analysis of local distributions of material constituents in a series of boron-doped polycrystalline diamond films grown by chemical vapor deposition, with information from the more conventional techniques of scanning electron microscopy (SEM) and infrared absorption spectroscopy. Although SEM images show a uniform distribution of film crystallites, they have the limitation of being unable to differentiate the distribution of boron in the diamond. Values of 10¹⁸–10²¹ atoms/cm³ of boron content have been estimated from the absorption coefficient of the 1290 cm⁻¹ infrared absorption band and from the 500 cm⁻¹ Raman vibration. The observed accumulation of boron atoms and carbon sp² impurities at the grain boundaries suggests that very high doping levels do not necessarily contribute to improvement of the material’s conductivity, corroborating with voltammetric data. FSCV results also indicate an enhanced stability of analyte detection. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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Graphical abstract

390 KiB

Open AccessArticle

A Sensitive DNAzyme-Based Chiral Sensor for Lead Detection

by Hua Kuang, Honghong Yin, Changrui Xing and Chuanlai Xu

Materials 2013, 6(11), 5038-5046; https://doi.org/10.3390/ma6115038 - 01 Nov 2013

Cited by 16 | Viewed by 5795

Abstract

A DNAzyme-based sensor for the determination and quantification of lead ions (Pb²⁺) has been established, which combines the recognition and catalysis of DNAzyme with the optical properties of nanomaterials. Circular dichroism (CD) signals were obtained by a DNAzyme-based assembly of asymmetric silver nanoparticle (AgNPs) dimers. A good linear relationship between CD signals and Pb²⁺concentration was obtained ranging from 0.05 ng∙mL⁻¹ to 10 ng∙mL⁻¹ with a limit of detection (LOD) of 0.02 ng∙mL⁻¹. The specificity of this sensor in lead ion detection was excellent, and a satisfactory recovery was obtained in the analysis of tap water samples. The proposed technique possesses both high sensitivity and good specificity, giving it great potential for the analysis of Pb²⁺ in water. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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1102 KiB

Open AccessArticle

Influence of a Thiolate Chemical Layer on GaAs (100) Biofunctionalization: An Original Approach Coupling Atomic Force Microscopy and Mass Spectrometry Methods

by Alex Bienaime, Therese Leblois, Nicolas Gremaud, Maxime-Jean Chaudon, Marven El Osta, Delphine Pecqueur, Patrick Ducoroy and Celine Elie-Caille

Materials 2013, 6(11), 4946-4966; https://doi.org/10.3390/ma6114946 - 25 Oct 2013

Cited by 8 | Viewed by 5286

Abstract

Widely used in microelectronics and optoelectronics; Gallium Arsenide (GaAs) is a III-V crystal with several interesting properties for microsystem and biosensor applications. Among these; its piezoelectric properties and the ability to directly biofunctionalize the bare surface, offer an opportunity to combine a highly sensitive transducer with a specific bio-interface; which are the two essential parts of a biosensor. To optimize the biorecognition part; it is necessary to control protein coverage and the binding affinity of the protein layer on the GaAs surface. In this paper; we investigate the potential of a specific chemical interface composed of thiolate molecules with different chain lengths; possessing hydroxyl (MUDO; for 11-mercapto-1-undecanol (HS(CH₂)₁₁OH)) or carboxyl (MHDA; for mercaptohexadecanoic acid (HS(CH₂)₁₅CO₂H)) end groups; to reconstitute a dense and homogeneous albumin (Rat Serum Albumin; RSA) protein layer on the GaAs (100) surface. The protein monolayer formation and the covalent binding existing between RSA proteins and carboxyl end groups were characterized by atomic force microscopy (AFM) analysis. Characterization in terms of topography; protein layer thickness and stability lead us to propose the 10% MHDA/MUDO interface as the optimal chemical layer to efficiently graft proteins. This analysis was coupled with in situ MALDI-TOF mass spectrometry measurements; which proved the presence of a dense and uniform grafted protein layer on the 10% MHDA/MUDO interface. We show in this study that a critical number of carboxylic docking sites (10%) is required to obtain homogeneous and dense protein coverage on GaAs. Such a protein bio-interface is of fundamental importance to ensure a highly specific and sensitive biosensor. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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Review

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479 KiB

Open AccessReview

Colorimetric Sugar Sensing Using Boronic Acid-Substituted Azobenzenes

by Yuya Egawa, Ryotaro Miki and Toshinobu Seki

Materials 2014, 7(2), 1201-1220; https://doi.org/10.3390/ma7021201 - 14 Feb 2014

Cited by 66 | Viewed by 15218

Abstract

In association with increasing diabetes prevalence, it is desirable to develop new glucose sensing systems with low cost, ease of use, high stability and good portability. Boronic acid is one of the potential candidates for a future alternative to enzyme-based glucose sensors. Boronic acid derivatives have been widely used for the sugar recognition motif, because boronic acids bind adjacent diols to form cyclic boronate esters. In order to develop colorimetric sugar sensors, boronic acid-conjugated azobenzenes have been synthesized. There are several types of boronic acid azobenzenes, and their characteristics tend to rely on the substitute position of the boronic acid moiety. For example, o-substitution of boronic acid to the azo group gives the advantage of a significant color change upon sugar addition. Nitrogen-15 Nuclear Magnetic Resonance (NMR) studies clearly show a signaling mechanism based on the formation and cleavage of the B–N dative bond between boronic acid and azo moieties in the dye. Some boronic acid-substituted azobenzenes were attached to a polymer or utilized for supramolecular chemistry to produce glucose-selective binding, in which two boronic acid moieties cooperatively bind one glucose molecule. In addition, boronic acid-substituted azobenzenes have been applied not only for glucose monitoring, but also for the sensing of glycated hemoglobin and dopamine. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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640 KiB

Open AccessReview

Recent Progress in Ferrocene-Modified Thin Films and Nanoparticles for Biosensors

by Shigehiro Takahashi and Jun-ichi Anzai

Materials 2013, 6(12), 5742-5762; https://doi.org/10.3390/ma6125742 - 06 Dec 2013

Cited by 78 | Viewed by 10517

Abstract

This article reviews recent progress in the development of ferrocene (Fc)-modified thin films and nanoparticles in relation to their biosensor applications. Redox-active materials in enzyme biosensors commonly use Fc derivatives, which mediate electron transfer between the electrode and enzyme active site. Either voltammetric or amperometric signals originating from redox reactions of Fc are detected or modulated by the binding of analytes on the electrode. Fc-modified thin films have been prepared by a variety of protocols, including in situ polymerization, layer-by-layer (LbL) deposition, host-guest complexation and molecular recognitions. In situ polymerization provides a facile way to form Fc thin films, because the Fc polymers are directly deposited onto the electrode surface. LbL deposition, which can modulate the film thickness and Fc content, is suitable for preparing well-organized thin films. Other techniques, such as host-guest complexation and protein-based molecular recognition, are useful for preparing Fc thin films. Fc-modified Au nanoparticles have been widely used as redox-active materials to fabricate electrochemical biosensors. Fc derivatives are often attached to Au nanoparticles through a thiol-Au linkage. Nanoparticles consisting of inorganic porous materials, such as zeolites and iron oxide, and nanoparticle-based composite materials have also been used to prepare Fc-modified nanoparticles. To construct biosensors, Fc-modified nanoparticles are immobilized on the electrode surface together with enzymes. Full article

(This article belongs to the Special Issue Functional Materials and Proteins for Bio-Sensing Applications)

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