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1.  A Comprehensive Review of Glucose Biosensors Based on Nanostructured Metal-Oxides 
Sensors (Basel, Switzerland)  2010;10(5):4855-4886.
Nanotechnology has opened new and exhilarating opportunities for exploring glucose biosensing applications of the newly prepared nanostructured materials. Nanostructured metal-oxides have been extensively explored to develop biosensors with high sensitivity, fast response times, and stability for the determination of glucose by electrochemical oxidation. This article concentrates mainly on the development of different nanostructured metal-oxide [such as ZnO, Cu(I)/(II) oxides, MnO2, TiO2, CeO2, SiO2, ZrO2, and other metal-oxides] based glucose biosensors. Additionally, we devote our attention to the operating principles (i.e., potentiometric, amperometric, impedimetric and conductometric) of these nanostructured metal-oxide based glucose sensors. Finally, this review concludes with a personal prospective and some challenges of these nanoscaled sensors.
doi:10.3390/s100504855
PMCID: PMC3292151  PMID: 22399911
nanostructured metal-oxides; glucose biosensor; electrochemical principles; enzymatic sensor; nonenzymatic sensor
2.  Gold nanoparticles-immobilized, hierarchically ordered, porous TiO2 nanotubes for biosensing of glutathione 
International Journal of Nanomedicine  2015;10(Suppl 1):171-182.
Glutathione (GSH) is vital for several functions of our human body such as neutralization of free radicals and reactive oxygen compounds, maintaining the active forms of vitamin C and E, regulation of nitric oxide cycle, iron metabolism, etc. It is also an endogenous antioxidant in most of the biological reactions. Given the importance of GSH, a simple strategy is proposed in this work to develop a biosensor for quantitative detection of GSH. This particular biosensor comprises of gold nanoparticles (Au NPs)-immobilized, hierarchically ordered titanium dioxide (TiO2) porous nanotubes. Hexagonally arranged, honeycomb-like nanoporous tubular TiO2 electrodes are prepared by using a simple electrochemical anodization process by applying a constant potential of 30 V for 24 hours using ethylene glycol consisting of ammonium fluoride as an electrolytic medium. Structural morphology and crystalline nature of such TiO2 nanotubes are analyzed using field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). Interestingly, nanocomposites of TiO2 with Au NPs is prepared in an effort to alter the intrinsic properties of TiO2, especially tuning of its band gap. Au NPs are prepared by a well-known Brust and Schiffrin method and are immobilized onto TiO2 electrodes which act as a perfect electrochemical sensing platform for GSH detection. Structural characterization and analysis of these modified electrodes are performed using FESEM, XRD, and UV-visible spectroscopic studies. GSH binding events on Au NPs-immobilized porous TiO2 electrodes are monitored by electrochemical techniques, namely, cyclic voltammetry (CV) and chronoamperometry (CA). Several parameters such as sensitivity, selectivity, stability, limit of detection, etc are investigated. In addition, Au NPs dispersed in aqueous medium are also explored for naked-eye detection of GSH using UV-visible spectroscopy in order to compare the performance of the proposed sensor. Our studies clearly indicate that these materials could potentially be used for GSH sensing applications.
doi:10.2147/IJN.S80054
PMCID: PMC4599607  PMID: 26491318
biosensor; electrochemistry; glutathione; gold nanoparticles; TiO2 nanotubes
3.  Chemo-sensors development based on low-dimensional codoped Mn2O3-ZnO nanoparticles using flat-silver electrodes 
Background
Semiconductor doped nanostructure materials have attained considerable attention owing to their electronic, opto-electronic, para-magnetic, photo-catalysis, electro-chemical, mechanical behaviors and their potential applications in different research areas. Doped nanomaterials might be a promising owing to their high-specific surface-area, low-resistances, high-catalytic activity, attractive electro-chemical and optical properties. Nanomaterials are also scientifically significant transition metal-doped nanostructure materials owing to their extraordinary mechanical, optical, electrical, electronic, thermal, and magnetic characteristics. Recently, it has gained significant interest in manganese oxide doped-semiconductor materials in order to develop their physico-chemical behaviors and extend their efficient applications. It has not only investigated the basic of magnetism, but also has huge potential in scientific features such as magnetic materials, bio- & chemi-sensors, photo-catalysts, and absorbent nanomaterials.
Results
The chemical sensor also displays the higher-sensitivity, reproducibility, long-term stability, and enhanced electrochemical responses. The calibration plot is linear (r2 = 0.977) over the 0.1 nM to 50.0 μM 4-nitrophenol concentration ranges. The sensitivity and detection limit is ~4.6667 μA cm-2 μM-1 and ~0.83 ± 0.2 nM (at a Signal-to-Noise-Ratio, SNR of 3) respectively. To best of our knowledge, this is the first report for detection of 4-nitrophenol chemical with doped Mn2O3-ZnO NPs using easy and reliable I-V technique in short response time.
Conclusions
As for the doped nanostructures, NPs are introduced a route to a new generation of toxic chemo-sensors, but a premeditate effort has to be applied for doped Mn2O3-ZnO NPs to be taken comprehensively for large-scale applications, and to achieve higher-potential density with accessible to individual chemo-sensors. In this report, it is also discussed the prospective utilization of Mn2O3-ZnO NPs on the basis of carcinogenic chemical sensing, which could also be applied for the detection of hazardous chemicals in ecological, environmental, and health care fields.
doi:10.1186/1752-153X-7-60
PMCID: PMC3630067  PMID: 23537000
Doped Mn2O3-ZnO nanoparticles; Wet-chemical method; Powder X-ray diffraction; 4-nitrophenol; I-V technique; X-ray photoelectron spectroscopy; Sensitivity
4.  Schottky junction/ohmic contact behavior of a nanoporous TiO2 thin film photoanode in contact with redox electrolyte solutions 
Summary
The nature and photoelectrochemical reactivity of nanoporous semiconductor electrodes have attracted a great deal of attention. Nanostructured materials have promising capabilities applicable for the construction of various photonic and electronic devices. In this paper, a mesoporous TiO2 thin film photoanode was soaked in an aqueous methanol solution using an O2-reducing Pt-based cathode in contact with atmospheric air on the back side. It was shown from distinct photocurrents in the cyclic voltammogram (CV) that the nanosurface of the mesoporous n-TiO2 film forms a Schottky junction with water containing a strong electron donor such as methanol. Formation of a Schottky junction (liquid junction) was also proved by Mott–Schottky plots at the mesoporous TiO2 thin film photoanode, and the thickness of the space charge layer was estimated to be very thin, i.e., only 3.1 nm at −0.1 V vs Ag/AgCl. On the other hand, the presence of [Fe(CN)6]4− and the absence of methanol brought about ohmic contact behavior on the TiO2 film and exhibited reversible redox waves in the dark due to the [Fe(CN)6]4−/3− couple. Further studies showed that multiple Schottky junctions/ohmic contact behavior inducing simultaneously both photocurrent and overlapped reversible redox waves was found in the CV of a nanoporous TiO2 photoanode soaked in an aqueous redox electrolyte solution containing methanol and [Fe(CN)6]4−. That is, the TiO2 nanosurface responds to [Fe(CN)6]4− to give ohmic redox waves overlapped simultaneously with photocurrents due to the Schottky junction. Additionally, a second step photocurrent generation was observed in the presence of both MeOH and [Fe(CN)6]4− around the redox potential of the iron complex. It was suggested that the iron complex forms a second Schottky junction for which the flat band potential (E fb) lies near the redox potential of the iron complex.
doi:10.3762/bjnano.2.15
PMCID: PMC3148041  PMID: 21977423
cyclic voltammogram of titanium dioxide photoanode; flat band potential; nanoporous TiO2 thin film; photocurrent; Schottky junction and ohmic contact
5.  Fast synthesis of platinum nanopetals and nanospheres for highly-sensitive non-enzymatic detection of glucose and selective sensing of ions 
Scientific Reports  2015;5:15277.
Novel methods to obtain Pt nanostructured electrodes have raised particular interest due to their high performance in electrochemistry. Several nanostructuration methods proposed in the literature use costly and bulky equipment or are time-consuming due to the numerous steps they involve. Here, Pt nanostructures were produced for the first time by one-step template-free electrodeposition on Pt bare electrodes. The change in size and shape of the nanostructures is proven to be dependent on the deposition parameters and on the ratio between sulphuric acid and chloride-complexes (i.e., hexachloroplatinate or tetrachloroplatinate). To further improve the electrochemical properties of electrodes, depositions of Pt nanostructures on previously synthesised Pt nanostructures are also performed. The electroactive surface areas exhibit a two order of magnitude improvement when Pt nanostructures with the smallest size are used. All the biosensors based on Pt nanostructures and immobilised glucose oxidase display higher sensitivity as compared to bare Pt electrodes. Pt nanostructures retained an excellent electrocatalytic activity towards the direct oxidation of glucose. Finally, the nanodeposits were proven to be an excellent solid contact for ion measurements, significantly improving the time-stability of the potential. The use of these new nanostructured coatings in electrochemical sensors opens new perspectives for multipanel monitoring of human metabolism.
doi:10.1038/srep15277
PMCID: PMC4626773  PMID: 26515434
6.  Promises and Challenges of Nanoplasmonic Devices for Refractometric Biosensing 
Nanophotonics  2013;2(2):83-101.
Optical biosensors based on surface plasmon resonance (SPR) in metallic thin films are currently standard tools for measuring molecular binding kinetics and affinities – an important task for biophysical studies and pharmaceutical development. Motivated by recent progress in the design and fabrication of metallic nanostructures, such as nanoparticles or nanoholes of various shapes, researchers have been pursuing a new generation of biosensors harnessing tailored plasmonic effects in these engineered nanostructures. Nanoplasmonic devices, while demanding nanofabrication, offer tunability with respect to sensor dimension and physical properties, thereby enabling novel biological interfacing opportunities and extreme miniaturization. Here we provide an integrated overview of refractometric biosensing with nanoplasmonic devices and highlight some recent examples of nanoplasmonic sensors capable of unique functions that are difficult to accomplish with conventional SPR. For example, since the local field strength and spatial distribution can be readily tuned by varying the shape and arrangement of nanostructures, biomolecular interactions can be controlled to occur in regions of high field strength. This may improve signal-to-noise and also enable sensing a small number of molecules. Furthermore, the nanoscale plasmonic sensor elements may, in combination with nanofabrication and materials-selective surface-modifications, make it possible to merge affinity biosensing with nanofluidic liquid handling.
doi:10.1515/nanoph-2012-0026
PMCID: PMC3804425  PMID: 24159429
Optical biosensors; refractometric sensors; surface plasmon resonance; plasmonics; figure of merit; single molecule detection; enzyme-linked biosensing; site-specific chemistry; supported lipid bilayer; pore-spanning lipid membrane; nanoparticle; nanohole; optofluidics
7.  A Nonoxidative Electrochemical Sensor Based on a Self-Doped Polyaniline/Carbon Nanotube Composite for Sensitive and Selective Detection of the Neurotransmitter Dopamine: A Review 
Sensors (Basel, Switzerland)  2008;8(12):8423-8452.
Most of the current techniques for in vivo detection of dopamine exploit the ease of oxidation of this compound. The major problem during the detection is the presence of a high concentration of ascorbic acid that is oxidized at nearly the same potential as dopamine on bare electrodes. Furthermore, the oxidation product of dopamine reacts with ascorbic acid present in samples and regenerates dopamine again, which severely limits the accuracy of the detection. Meanwhile, the product could also form a melanin-like insulating film on the electrode surface, which decreases the sensitivity of the electrode. Various surface modifications on the electrode, new materials for making the electrodes, and new electrochemical techniques have been exploited to solve these problems. Recently we developed a new electrochemical detection method that did not rely on direct oxidation of dopamine on electrodes, which may naturally solve these problems. This approach takes advantage of the high performance of our newly developed poly(anilineboronic acid)/carbon nanotube composite and the excellent permselectivity of the ion-exchange polymer Nafion. The high affinity binding of dopamine to the boronic acid groups of the polymer affects the electrochemical properties of the polyaniline backbone, which act as the basis for the transduction mechanism of this non-oxidative dopamine sensor. The unique reduction capability and high conductivity of single-stranded DNA functionalized single-walled carbon nanotubes greatly improved the electrochemical activity of the polymer in a physiologically-relevant buffer, and the large surface area of the carbon nanotubes increased the density of the boronic acid receptors. The high sensitivity and selectivity of the sensor show excellent promise toward molecular diagnosis of Parkinson's disease. In this review, we will focus on the discussion of this novel detection approach, the new interferences in this detection approach, and how to eliminate these interferences toward in vivo and in vitro detection of the neurotransmitter dopamine.
doi:10.3390/s8128423
PMCID: PMC3791025
Boronic Acid; Dopamine Detection; Nonoxidative Sensor; Polyaniline; Carbon Nanotube; Parkinson's disease
8.  A Macroporous TiO2 Oxygen Sensor Fabricated Using Anodic Aluminium Oxide as an Etching Mask 
Sensors (Basel, Switzerland)  2010;10(1):670-683.
An innovative fabrication method to produce a macroporous Si surface by employing an anodic aluminium oxide (AAO) nanopore array layer as an etching template is presented. Combining AAO with a reactive ion etching (RIE) processes, a homogeneous and macroporous silicon surface can be effectively configured by modulating AAO process parameters and alumina film thickness, thus hopefully replacing conventional photolithography and electrochemical etch methods. The hybrid process integration is considered fully CMOS compatible thanks to the low-temperature AAO and CMOS processes. The gas-sensing characteristics of 50 nm TiO2 nanofilms deposited on the macroporous surface are compared with those of conventional plain (or non-porous) nanofilms to verify reduced response noise and improved sensitivity as a result of their macroporosity. Our experimental results reveal that macroporous geometry of the TiO2 chemoresistive gas sensor demonstrates 2-fold higher (∼33%) improved sensitivity than a non-porous sensor at different levels of oxygen exposure. In addition, the macroporous device exhibits excellent discrimination capability and significantly lessened response noise at 500 °C. Experimental results indicate that the hybrid process of such miniature and macroporous devices are compatible as well as applicable to integrated next generation bio-chemical sensors.
doi:10.3390/s100100670
PMCID: PMC3270862  PMID: 22315561
anodic aluminium oxide (AAO); macroporous; MEMS; TiO2 gas sensor
9.  Self-Assembled Films of Dendrimers and Metallophthalocyanines as FET-Based Glucose Biosensors 
Sensors (Basel, Switzerland)  2011;11(10):9442-9449.
Separative extended gate field effect transistor (SEGFET) type devices have been used as an ion sensor or biosensor as an alternative to traditional ion sensitive field effect transistors (ISFETs) due to their robustness, ease of fabrication, low cost and possibility of FET isolation from the chemical environment. The layer-by-layer technique allows the combination of different materials with suitable properties for enzyme immobilization on simple platforms such as the extended gate of SEGFET devices enabling the fabrication of biosensors. Here, glucose biosensors based on dendrimers and metallophthalocyanines (MPcs) in the form of layer-by-layer (LbL) films, assembled on indium tin oxide (ITO) as separative extended gate material, has been produced. NH3+ groups in the dendrimer allow electrostatic interactions or covalent bonds with the enzyme (glucose oxidase). Relevant parameters such as optimum pH, buffer concentration and presence of serum bovine albumin (BSA) in the immobilization process were analyzed. The relationship between the output voltage and glucose concentration shows that upon detection of a specific analyte, the sub-products of the enzymatic reaction change the pH locally, affecting the output signal of the FET transducer. In addition, dendritic layers offer a nanoporous environment, which may be permeable to H+ ions, improving the sensibility as modified electrodes for glucose biosensing.
doi:10.3390/s111009442
PMCID: PMC3231248  PMID: 22163704
glucose biosensor; layer by layer; field effect transistor; enzyme immobilization
10.  Biomedical Detection via Macro- and Nano-Sensors Fabricated with Metallic and Semiconducting Oxides 
Originally developed as gas sensors, the benefits of metallic and semiconducting oxide materials are now being realized in other areas of sensing, such as chemical, environmental, and biomedical monitoring and detection. Metallic and semiconducting oxides have continuously expanded their roles to date, and have also established their significance in biosensing by utilizing a variety of modes for signal generation and detection mechanism. These sensors are typically based either on their optical, electrochemical, electrical, gravimetric, acoustic, and magnetic properties for signal transduction. This article reviews such biosensors that employ metallic and semiconducting oxides as active sensing elements to detect nucleic acids, proteins, cells, and a variety of important biomarkers, both in thin film and one-dimensional forms. Specific oxide materials (Mx Oy ) examined comprehensively in this article include M = Fe, Cu, Si, Zn, Sn, In. The derivatives of these oxide materials resulting from incorporation of dopants are examined as well. The crystalline structures and unique properties that may be exploited for various biosensing applications are discussed, and recent efforts investigating the feasibility of using these oxide materials in biosensor technology are described. Key biosensor characteristics resulting from reduced dimensionality are overviewed under the motif of planar and one-dimensional sensors. This article also provides insight into current challenges facing biosensor applications for metallic and semiconducting oxides. In addition, future outlook in this particular field as well as different impacts on biology and medicine are addressed.
PMCID: PMC3766318  PMID: 23627064
Semiconducting Oxides; Metallic Oxides; Biosensors; Solid-State Biodetection; Nanobiosensors; Nanomaterials; Biomedical Detection
11.  Application of 2D Non-Graphene Materials and 2D Oxide Nanostructures for Biosensing Technology 
The discovery of graphene and its unique properties has inspired researchers to try to invent other two-dimensional (2D) materials. After considerable research effort, a distinct “beyond graphene” domain has been established, comprising the library of non-graphene 2D materials. It is significant that some 2D non-graphene materials possess solid advantages over their predecessor, such as having a direct band gap, and therefore are highly promising for a number of applications. These applications are not limited to nano- and opto-electronics, but have a strong potential in biosensing technologies, as one example. However, since most of the 2D non-graphene materials have been newly discovered, most of the research efforts are concentrated on material synthesis and the investigation of the properties of the material. Applications of 2D non-graphene materials are still at the embryonic stage, and the integration of 2D non-graphene materials into devices is scarcely reported. However, in recent years, numerous reports have blossomed about 2D material-based biosensors, evidencing the growing potential of 2D non-graphene materials for biosensing applications. This review highlights the recent progress in research on the potential of using 2D non-graphene materials and similar oxide nanostructures for different types of biosensors (optical and electrochemical). A wide range of biological targets, such as glucose, dopamine, cortisol, DNA, IgG, bisphenol, ascorbic acid, cytochrome and estradiol, has been reported to be successfully detected by biosensors with transducers made of 2D non-graphene materials.
doi:10.3390/s16020223
PMCID: PMC4801599  PMID: 26861346
two-dimensional materials; beyond graphene; transition metal dichalcogenides; transition metal oxides; two-dimensional oxides; transducers; biosensors
12.  Development of the Wireless Instantaneous Neurotransmitter Concentration System for intraoperative neurochemical monitoring using fast-scan cyclic voltammetry 
Journal of neurosurgery  2009;111(4):712-723.
Object
Emerging evidence supports the hypothesis that modulation of specific central neuronal systems contributes to the clinical efficacy of deep brain stimulation (DBS) and motor cortex stimulation (MCS). Real-time monitoring of the neurochemical output of targeted regions may therefore advance functional neurosurgery by, among other goals, providing a strategy for investigation of mechanisms, identification of new candidate neurotransmitters, and chemically guided placement of the stimulating electrode. The authors report the development of a device called the Wireless Instantaneous Neurotransmitter Concentration System (WINCS) for intraoperative neurochemical monitoring during functional neurosurgery. This device supports fast-scan cyclic voltammetry (FSCV) at a carbon-fiber microelectrode (CFM) for real-time, spatially and chemically resolved neurotransmitter measurements in the brain.
Methods
The FSCV study consisted of a triangle wave scanned between −0.4 and 1 V at a rate of 300 V/second and applied at 10 Hz. All voltages were compared with an Ag/AgCl reference electrode. The CFM was constructed by aspirating a single carbon fiber (r = 2.5 μm) into a glass capillary and pulling the capillary to a microscopic tip by using a pipette puller. The exposed carbon fiber (that is, the sensing region) extended beyond the glass insulation by ~ 100 μm. The neurotransmitter dopamine was selected as the analyte for most trials. Proof-of-principle tests included in vitro flow injection and noise analysis, and in vivo measurements in urethane-anesthetized rats by monitoring dopamine release in the striatum following high-frequency electrical stimulation of the medial forebrain bundle. Direct comparisons were made to a conventional hardwired system.
Results
The WINCS, designed in compliance with FDA-recognized consensus standards for medical electrical device safety, consisted of 4 modules: 1) front-end analog circuit for FSCV (that is, current-to-voltage transducer); 2) Bluetooth transceiver; 3) microprocessor; and 4) direct-current battery. A Windows-XP laptop computer running custom software and equipped with a Universal Serial Bus–connected Bluetooth transceiver served as the base station. Computer software directed wireless data acquisition at 100 kilosamples/second and remote control of FSCV operation and adjustable waveform parameters. The WINCS provided reliable, high-fidelity measurements of dopamine and other neurochemicals such as serotonin, norepinephrine, and ascorbic acid by using FSCV at CFM and by flow injection analysis. In rats, the WINCS detected subsecond striatal dopamine release at the implanted sensor during high-frequency stimulation of ascending dopaminergic fibers. Overall, in vitro and in vivo testing demonstrated comparable signals to a conventional hardwired electrochemical system for FSCV. Importantly, the WINCS reduced susceptibility to electromagnetic noise typically found in an operating room setting.
Conclusions
Taken together, these results demonstrate that the WINCS is well suited for intraoperative neurochemical monitoring. It is anticipated that neurotransmitter measurements at an implanted chemical sensor will prove useful for advancing functional neurosurgery.
doi:10.3171/2009.3.JNS081348
PMCID: PMC2808191  PMID: 19425890
deep brain stimulation; neuromodulation; neurotransmitter; voltammetry; dopamine
13.  Hot plasmonic electrons for generation of enhanced photocurrent in gold-TiO2 nanocomposites 
In this manuscript, for the first time, we report a combination of electrophoretic and sintering approaches for introducing gold nanoparticles into nanoporous TiO2 films to generate ‘hot’ electrons resulting in a strong enhancement of photocurrent. The Au-TiO2 nanocomposite material was prepared by the electrophoretic deposition of gold nanoparticles into a porous nanoparticulate titanium dioxide film, creating a photoactive electrode. The composite film demonstrates a significant increase in the short circuit current (Isc) compared to unmodified TiO2 when excited at or close to the plasmon resonance of the gold nanoparticles. Then, we employed a thermal ripening process as a method of increasing the Isc of these electrodes and also as a method of tuning the plasmon peak position, with a high degree of selectivity. Photo-electrochemical investigations revealed that the increase in photocurrent is attributed to the generation and separation of plasmonically generated hot electrons at the gold/TiO2 interface and also the inter-band generation of holes in gold nanoparticles by photons with λ < 520 nm. Theoretical modelling outputs perfectly match our results obtained from photo-physical studies of the processes leading to enhanced photocurrent.
Electronic supplementary material
The online version of this article (doi:10.1186/s11671-014-0710-5) contains supplementary material, which is available to authorized users.
doi:10.1186/s11671-014-0710-5
PMCID: PMC4385105  PMID: 25852335
Surface plasmon resonance; Hot electrons; Au-TiO2 nanocomposite; TiO2 films
14.  Protein Biosensors Based on Polymer Nanowires, Carbon Nanotubes and Zinc Oxide Nanorods 
Sensors (Basel, Switzerland)  2011;11(5):5087-5111.
The development of biosensors using electrochemical methods is a promising application in the field of biotechnology. High sensitivity sensors for the bio-detection of proteins have been developed using several kinds of nanomaterials. The performance of the sensors depends on the type of nanostructures with which the biomaterials interact. One dimensional (1-D) structures such as nanowires, nanotubes and nanorods are proven to have high potential for bio-applications. In this paper we review these three different kinds of nanostructures that have attracted much attention at recent times with their great performance as biosensors. Materials such as polymers, carbon and zinc oxide have been widely used for the fabrication of nanostructures because of their enhanced performance in terms of sensitivity, biocompatibility, and ease of preparation. Thus we consider polymer nanowires, carbon nanotubes and zinc oxide nanorods for discussion in this paper. We consider three stages in the development of biosensors: (a) fabrication of biomaterials into nanostructures, (b) alignment of the nanostructures and (c) immobilization of proteins. Two different methods by which the biosensors can be developed at each stage for all the three nanostructures are examined. Finally, we conclude by mentioning some of the major challenges faced by many researchers who seek to fabricate biosensors for real time applications.
doi:10.3390/s110505087
PMCID: PMC3231366  PMID: 22163892
biosensor; nanostructures; electrochemical; immobilization
15.  An In-situ Real-Time Optical Fiber Sensor Based on Surface Plasmon Resonance for Monitoring the Growth of TiO2 Thin Films 
Sensors (Basel, Switzerland)  2013;13(7):9513-9521.
An optical fiber sensor based on surface plasmon resonance (SPR) is proposed for monitoring the thickness of deposited nano-thin films. A side-polished multimode SPR optical fiber sensor with an 850 nm-LD is used as the transducing element for real-time monitoring of the deposited TiO2 thin films. The SPR optical fiber sensor was installed in the TiO2 sputtering system in order to measure the thickness of the deposited sample during TiO2 deposition. The SPR response declined in real-time in relation to the growth of the thickness of the TiO2 thin film. Our results show the same trend of the SPR response in real-time and in spectra taken before and after deposition. The SPR transmitted intensity changes by approximately 18.76% corresponding to 50 nm of deposited TiO2 thin film. We have shown that optical fiber sensors utilizing SPR have the potential for real-time monitoring of the SPR technology of nanometer film thickness. The compact size of the SPR fiber sensor enables it to be positioned inside the deposition chamber, and it could thus measure the film thickness directly in real-time. This technology also has potential application for monitoring the deposition of other materials. Moreover, in-situ real-time SPR optical fiber sensor technology is in inexpensive, disposable technique that has anti-interference properties, and the potential to enable on-line monitoring and monitoring of organic coatings.
doi:10.3390/s130709513
PMCID: PMC3758660  PMID: 23881144
surface plasmon resonance; optical fiber sensor
16.  Advanced Nanoporous Materials for Micro-Gravimetric Sensing to Trace-Level Bio/Chemical Molecules 
Sensors (Basel, Switzerland)  2014;14(10):19023-19056.
Functionalized nanoporous materials have been developed recently as bio/chemical sensing materials. Due to the huge specific surface of the nano-materials for molecular adsorption, high hopes have been placed on gravimetric detection with micro/nano resonant cantilevers for ultra-sensitive sensing of low-concentration bio/chemical substances. In order to enhance selectivity of the gravimetric resonant sensors to the target molecules, it is crucial to modify specific groups onto the pore-surface of the nano-materials. By loading the nanoporous sensing material onto the desired region of the mass-type transducers like resonant cantilevers, the micro-gravimetric bio/chemical sensors can be formed. Recently, such micro-gravimetric bio/chemical sensors have been successfully applied for rapid or on-the-spot detection of various bio/chemical molecules at the trace-concentration level. The applicable nanoporous sensing materials include mesoporous silica, zeolite, nanoporous graphene oxide (GO) and so on. This review article focuses on the recent achievements in design, preparation, functionalization and characterization of advanced nanoporous sensing materials for micro-gravimetric bio/chemical sensing.
doi:10.3390/s141019023
PMCID: PMC4239959  PMID: 25313499
resonant micro-cantilever; gravimetric sensor; mesoporous silica; graphene; zeolites; functionalization; bio/chemical molecules
17.  Bio-nanocomposite Photoelectrode Composed of the Bacteria Photosynthetic Reaction Center Entrapped on a Nanocrystalline TiO2 Matrix 
Sensors (Basel, Switzerland)  2005;5(4):258-265.
A new kind of bio-nanocomposite photoelectrode was fabricated through direct immobilization of the bacterial photosynthetic reaction center (RC) proteins on a nanocrystalline TiO2 matrix prepared by anodic electrodeposition. The near-infrared (NIR)-visible absorption and fluorescence emission spectra displayed that structure and activity of the RC remained unaltered on the nano-TiO2 film surface. High efficient light-harvesting of the NIR light energy by RC contributed to the distinct enhancement of the photoelectric conversion on such nanoporous matrix, which would provide a new strategy to develop versatile biomimic energy convertors or photoelectric sensors.
PMCID: PMC3933899
Photosynthetic reaction center; nanocrystalline TiO2; photoelectric; light-harvesting
18.  Hierarchical Thin Film Architectures for Enhanced Sensor Performance: Liquid Crystal-Mediated Electrochemical Synthesis of Nanostructured Imprinted Polymer Films for the Selective Recognition of Bupivacaine 
Biosensors  2014;4(2):90-110.
Nanostructured bupivacaine-selective molecularly imprinted 3-aminophenylboronic acid-p-phenylenediamine co-polymer (MIP) films have been prepared on gold-coated quartz (Au/quartz) resonators by electrochemical synthesis under cyclic voltammetric conditions in a liquid crystalline (LC) medium (triton X-100/water). Films prepared in water and in the absence of template were used for control studies. Infrared spectroscopic studies demonstrated comparable chemical compositions for LC and control polymer films. SEM studies revealed that the topologies of the molecularly imprinted polymer films prepared in the LC medium (LC-MIP) exhibit discernible 40 nm thick nano-fiber structures, quite unlike the polymers prepared in the absence of the LC-phase. The sensitivity of the LC-MIP in a quartz crystal microbalance (QCM) sensor platform was 67.6 ± 4.9 Hz/mM under flow injection analysis (FIA) conditions, which was ≈250% higher than for the sensor prepared using the aqueous medium. Detection was possible at 100 nM (30 ng/mL), and discrimination of bupivacaine from closely related structural analogs was readily achieved as reflected in the corresponding stability constants of the MIP-analyte complexes. The facile fabrication and significant enhancement in sensor sensitivity together highlight the potential of this LC-based imprinting strategy for fabrication of polymeric materials with hierarchical architectures, in particular for use in surface-dependent application areas, e.g., biomaterials or sensing.
doi:10.3390/bios4020090
PMCID: PMC4264373  PMID: 25587412
bupivacaine; electropolymerization; liquid crystal; molecularly imprinted polymer; nanostructured polymer films; piezoelectric sensor; quartz crystal microbalance
19.  Fast-Response, Sensitivitive and Low-Powered Chemosensors by Fusing Nanostructured Porous Thin Film and IDEs-Microheater Chip 
Scientific Reports  2013;3:1669.
The chemiresistive thin film gas sensors with fast response, high sensitivity, low power consumption and mass-produced potency, have been expected for practical application. It requires both sensitive materials, especially exquisite nanomaterials, and efficient substrate chip for heating and electrical addressing. However, it is challenging to achieve repeatable microstructures across the films and low power consumption of substrate chip. Here we presented a new sensor structure via the fusion of metal-oxide nanoporous films and micro-electro-mechanical systems (MEMS)-based sensing chip. An interdigital-electrodes (IDEs) and microheater integrated MEMS structure is designed and employed as substrate chip to in-situ fabricate colloidal monolayer template-induced metal-oxide (egg. SnO2) nanoporous sensing films. This fused sensor demonstrates mW-level low power, ultrafast response (~1 s), and parts-per-billion lever detection for ethanol gas. Due to the controllable template strategy and mass-production potential, such micro/nano fused high-performance gas sensors will be next-generation key miniaturized/integrated devices for advanced practical applications.
doi:10.1038/srep01669
PMCID: PMC3628220  PMID: 23591580
20.  A non-labeled DNA biosensor based on light addressable potentiometric sensor modified with TiO2 thin film*  
Titanium dioxide (TiO2) thin film was deposited on the surface of the light addressable potentiometric sensor (LAPS) to modify the sensor surface for the non-labeled detection of DNA molecules. To evaluate the effect of ultraviolet (UV) treatment on the silanization level of TiO2 thin film by 3-aminopropyltriethoxysilane (APTS), fluorescein isothiocyanate (FITC) was used to label the amine group on the end of APTS immobilized onto the TiO2 thin film. We found that, with UV irradiation, the silanization level of the irradiated area of the TiO2 film was improved compared with the non-irradiated area under well-controlled conditions. This result indicates that TiO2 can act as a coating material on the biosensor surface to improve the effect and efficiency of the covalent immobilization of biomolecules on the sensor surface. The artificially synthesized probe DNA molecules were covalently linked onto the surface of TiO2 film. The hybridization of probe DNA and target DNA was monitored by the recording of I-V curves that shift along the voltage axis during the process of reaction. A significant LAPS signal can be detected at 10 μmol/L of target DNA sample.
doi:10.1631/jzus.B0920090
PMCID: PMC2772892  PMID: 19882762
DNA biosensor; Titanium dioxide (TiO2) thin film; Light addressable potentiometric sensor (LAPS); Silanization; Fluorescein label; Gene chip
21.  Sensing and Tactile Artificial Muscles from Reactive Materials 
Sensors (Basel, Switzerland)  2010;10(4):2638-2674.
Films of conducting polymers can be oxidized and reduced in a reversible way. Any intermediate oxidation state determines an electrochemical equilibrium. Chemical or physical variables acting on the film may modify the equilibrium potential, so that the film acts as a sensor of the variable. The working potential of polypyrrole/DBSA (Dodecylbenzenesulfonic acid) films, oxidized or reduced under constant currents, changes as a function of the working conditions: electrolyte concentration, temperature or mechanical stress. During oxidation, the reactive material is a sensor of the ambient, the consumed electrical energy being the sensing magnitude. Devices based on any of the electrochemical properties of conducting polymers must act simultaneously as sensors of the working conditions. Artificial muscles, as electrochemical actuators constituted by reactive materials, respond to the ambient conditions during actuation. In this way, they can be used as actuators, sensing the surrounding conditions during actuation. Actuating and sensing signals are simultaneously included by the same two connecting wires.
doi:10.3390/s100402638
PMCID: PMC3274195  PMID: 22319265
conducting polymers; reactive materials; sensors; actuators; artificial muscles; tactile muscles; sensing actuators
22.  Selective Iron(III) ion uptake using CuO-TiO2 nanostructure by inductively coupled plasma-optical emission spectrometry 
Background
CuO-TiO2 nanosheets (NSs), a kind of nanomaterials is one of the most attracting class of transition doped semiconductor materials due to its interesting and important optical, electrical, and structural properties and has many technical applications, such as in metal ions detection, photocatalysis, Chemi-sensors, bio-sensors, solar cells and so on. In this paper the synthesis of CuO-TiO2 nanosheets by the wet-chemically technique is reported.
Methods
CuO-TiO2 NSs were prepared by a wet-chemical process using reducing agents in alkaline medium and characterized by UV/vis., FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM) etc.
Results
The structural and optical evaluation of synthesized NSs were measured by XRD pattern, Fourier transform infrared (FT-IR) and UV–vis spectroscopy, respectively which confirmed that the obtained NSs are well-crystalline CuO-TiO2 and possessing good optical properties. The morphological analysis of CuO-TiO2 NSs was executed by FE-SEM, which confirmed that the doped products were sheet-shaped and growth in large quantity. Here, the analytical efficiency of the NSs was applied for a selective adsorption of iron(III) ion prior to detection by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NSs towards various metal ions, including Au(III), Cd(II), Co(II), Cr(III), Fe(III), Pd(II), and Zn(II) was analyzed.
Conclusions
Based on the selectivity study, it was confirmed that the selectivity of doped NSs phase was the most towards Fe(III) ion. The static adsorption capacity for Fe(III) was calculated to be 110.06 mgg−1. Results from adsorption isotherm also verified that the adsorption process was mainly monolayer-adsorption onto a surface containing a finite number of CuO-TiO2 NSs adsorption sites.
doi:10.1186/1752-153X-6-158
PMCID: PMC3570428  PMID: 23244218
CuO-TiO2 nanosheets; Wet-chemical process; Optical property; Structural property; Adsorption isotherm; Iron(III) ion detection
23.  Recent Advances in Polymeric Materials Used as Electron Mediators and Immobilizing Matrices in Developing Enzyme Electrodes 
Sensors (Basel, Switzerland)  2012;12(1):923-953.
Different classes of polymeric materials such as nanomaterials, sol-gel materials, conducting polymers, functional polymers and biomaterials have been used in the design of sensors and biosensors. Various methods have been used, for example from direct adsorption, covalent bonding, crossing-linking with glutaraldehyde on composites to mixing the enzymes or use of functionalized beads for the design of sensors and biosensors using these polymeric materials in recent years. It is widely acknowledged that analytical sensing at electrodes modified with polymeric materials results in low detection limits, high sensitivities, lower applied potential, good stability, efficient electron transfer and easier immobilization of enzymes on electrodes such that sensing and biosensing of environmental pollutants is made easier. However, there are a number of challenges to be addressed in order to fulfill the applications of polymeric based polymers such as cost and shortening the long laboratory synthetic pathways involved in sensor preparation. Furthermore, the toxicological effects on flora and fauna of some of these polymeric materials have not been well studied. Given these disadvantages, efforts are now geared towards introducing low cost biomaterials that can serve as alternatives for the development of novel electrochemical sensors and biosensors. This review highlights recent contributions in the development of the electrochemical sensors and biosensors based on different polymeric material. The synergistic action of some of these polymeric materials and nanocomposites imposed when combined on electrode during sensing is discussed.
doi:10.3390/s120100923
PMCID: PMC3279247  PMID: 22368503
polymeric material; mediator; electrochemical sensor; biosensor; enzyme electrode
24.  Development of a Novel Biosensor Using Cationic Antimicrobial Peptide and Nickel Phthalocyanine Ultrathin Films for Electrochemical Detection of Dopamine 
The antimicrobial peptide dermaseptin 01 (DS 01), from the skin secretion of Phyllomedusa hypochondrialis frogs, was immobilized in nanostructured layered films in conjunction with nickel tetrasulfonated phthalocyanines (NiTsPc), widely used in electronic devices, using layer-by-layer technique. The films were used as a biosensor to detect the presence of dopamine (DA), a neurotransmitter associated with diseases such as Alzheimer's and Parkinson's, with detection limits in the order of 10−6 mol L−1. The use of DS 01 in LbL film generated selectivity in the detection of DA despite the presence of ascorbic acid found in biological fluids. This work is the first to report that the antimicrobial peptide and NiTsPc LbL film exhibits electroanalytical activity to DA oxidation. The selectivity in the detection of DA is a fundamental aspect for the development of electrochemical sensors with potential applications in the biomedical and pharmaceutical industries.
doi:10.1155/2012/850969
PMCID: PMC3263607  PMID: 22287966
25.  Cellobiose dehydrogenase modified electrodes: advances by materials science and biochemical engineering 
Analytical and Bioanalytical Chemistry  2013;405(11):3637-3658.
The flavocytochrome cellobiose dehydrogenase (CDH) is a versatile biorecognition element capable of detecting carbohydrates as well as quinones and catecholamines. In addition, it can be used as an anode biocatalyst for enzymatic biofuel cells to power miniaturised sensor–transmitter systems. Various electrode materials and designs have been tested in the past decade to utilize and enhance the direct electron transfer (DET) from the enzyme to the electrode. Additionally, mediated electron transfer (MET) approaches via soluble redox mediators and redox polymers have been pursued. Biosensors for cellobiose, lactose and glucose determination are based on CDH from different fungal producers, which show differences with respect to substrate specificity, pH optima, DET efficiency and surface binding affinity. Biosensors for the detection of quinones and catecholamines can use carbohydrates for analyte regeneration and signal amplification. This review discusses different approaches to enhance the sensitivity and selectivity of CDH-based biosensors, which focus on (1) more efficient DET on chemically modified or nanostructured electrodes, (2) the synthesis of custom-made redox polymers for higher MET currents and (3) the engineering of enzymes and reaction pathways. Combination of these strategies will enable the design of sensitive and selective CDH-based biosensors with reduced electrode size for the detection of analytes in continuous on-site and point-of-care applications.
doi:10.1007/s00216-012-6627-x
PMCID: PMC3608873  PMID: 23329127
Biosensors; Carbohydrates; Catecholamines; Cellobiose dehydrogenase; Electron transfer; Nanomaterials

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