Signal‐Enhanced Amperometric Immunosensor Based on Ferrocene‐Branched Poly(allylamine)/Multiwalled Carbon Nanotubes Redox‐Active Composite

A signal‐enhanced immunosensor has been developed by self‐assembling Au NPs onto a ferrocene‐branched poly(allylamine)/multiwalled carbon nanotubes (PAA‐Fc/MWNTs) modified electrode for the sensitive determination of hepatitis B surface antigen (HBsAg) as a model protein. The formation of PAA‐Fc/MWNTs composite not only effectively avoided the leakage of Fc and retained its electrochemical activity, but also enhanced the conductivity and charge‐transport properties of the composite. Further adsorption of Au NPs into the PAA matrix provided both the interactive sites for the immobilization of hepatitis B surface antibody (HBsAb) and a favorable microenvironment to maintain its activity. Tests performed with this immunosensor showed a specific response to HBsAg in the range of 0.1–350.0 ng mL^?1 with a detection limit of 0.03 ng mL^?1.     

A Simple Layer‐by‐Layer Assembly Strategy for a Reagentless Biosensor Based on a Nanocomposite of Methylene Blue‐Multiwalled Carbon Nanotubes

A simple layer‐by‐layer (LBL) assembly strategy was established for constructing a novel reagentless biosensor based on a nanocomposite of methylene blue multiwalled carbon nanotubes (MB‐MWNTs). A nanocomposite of MB‐MWNTs was obtained by direct premixing and possessed good dispersion in barbital‐HCl buffer. Through electrostatic interactions, the nanocomposite of MB‐MWNTs could alternately be assembled with horseradish peroxidase (HRP) on the Au electrode modified with precursor films. UV/Vis spectra and scanning electron microscopy (SEM) were applied to reveal the formation of the nanocomposite of MB‐MWNTs. The LBL assembly process was also verified by electrochemical impedance spectroscopy (EIS). The MB is a well‐established mediator and efficiently facilitated the electron shuttle between the HRP and the electrode, as demonstrated by the cyclic voltammetry (CV) measurements. The as‐prepared reagentless biosensor exhibited a fast response for the determination of hydrogen peroxide (H₂O₂) and reached 95% of the steady‐state current within 3 s. It was found that the linear response range of the reagentless biosensor for H₂O₂ was from 4.0 μM to 3.78 mM with a detection limit of 1.0 μM and a sensitivity of 22.5 μA mM⁻¹. The biosensor exhibited a high reproducibility and stability.     

A Label‐Free Amperometric Immunosensor Based on Redox‐Active Ferrocene‐Branched Chitosan/Multiwalled Carbon Nanotubes Conductive Composite and Gold Nanoparticles

A novel immunosensor has been developed by self‐assembling Au NPs onto a ferrocene‐branched chitosan/multiwalled carbon nanotubes (CS‐Fc/MWCNTs) modified electrode for the sensitive determination of hepatitis B surface antigen (HBsAg). The formation of CS‐Fc effectively avoids the leakage of Fc and retains its electrochemical activity. Incorporation of MWCNTs and Au NPs into CS‐Fc further increases the electrochemical active Fc in the CS films and provides interactive sites for the immobilization of HBsAb. The morphologies and electrochemistry of the formed biofilm were investigated by using scanning electron microscopy and electrochemical techniques. The immunosensor exhibits a specific response to HBsAg in the range of 1.0–420 ng mL^?1. Excellent analytical performance, fabrication reproducibility and operational stability of the proposed immunosensor indicated its promising application in clinical diagnostics.     

Fabrication of a Sensitive Electrochemical Biosensor for Detection of DNA Hybridization Based on Gold Nanoparticles/CuO Nanospindles Modified Glassy Carbon Electrode

In this work, a sensitive electrochemical DNA biosensor for the detection of sequence‐specific target DNA was reported. Firstly, CuO nanospindles (CuO NS) were immobilized on the surface of a glassy carbon electrode (GCE). Subsequently, gold nanoparticles (Au NPs) were introduced to the surface of CuO NS by the electrochemical deposition mode. Probe DNA with SH (HS‐DNA) at the 5′‐phosphate end was covalently immobilized on the surface of the Au NPs through Au? S bond. Scanning electron microscopy (SEM) was used to elucidate the morphology of the assembled film, and electrochemical impedance spectroscopy technique (EIS) was used to investigate the DNA sensor assembly process. Hybridization detection of DNA was performed with differential pulse voltammetry (DPV) and the methylene blue (MB) was hybridization indicator. Under the optimal conditions, the decline of reduction peak current of MB (ΔI) was linear with the logarithm of the concentration of complementary DNA from 1.0×10^?13 to 1.0×10^?6 mol·L^?1 with a detection limit of 3.5×10^?14 mol·L^?1 (S/N=3). In addition, this DNA biosensor has good selectivity, and even can distinguish single‐mismatched target DNA.     

Multiple plasmonic effect on photocurrent generation of metal‐loaded titanium dioxide composite/dye films on gold grating surface

We demonstrate the multiple plasmonic effect on the photocurrent properties of photoanodes containing Ag or Au nanoparticles (NPs) loaded onto titanium dioxide film (Ag–TiO₂ or Au–TiO₂) on Au grating surfaces. Ag–TiO₂ or Au–TiO₂ nanocomposite particles are prepared by a flame spray pyrolysis route. The structures and morphologies of the prepared products are characterized by high‐resolution transmission electron microscopy. The Ag–TiO₂ or Au–TiO₂ composite NPs are deposited by spin coating onto the Au grating surfaces. The photoanode electrode is a layered structure of blu‐ray disc‐recordable grating substrate/Au/Ag (or Au)–TiO₂/dye/electrolyte/indium‐tin oxide. The plasmonic effect is induced when Ag or Au NPs are located within the propagating surface plasmon (SP) field on the Au grating surface. The short‐circuit photocurrent is increased by exciting the grating‐coupled propagating SP on the Au gratings and is further enhanced by positioning the Ag or Au NPs within the grating‐coupled SP field. Copyright © 2014 John Wiley & Sons, Ltd.     

Self‐Assembled Redox System for Bioelectrocatalytic Assay of L‐Ascorbylphosphate and Alkaline Phosphatase Activity

Ferrocene‐terminated self‐assembled monolayer (Fc‐SAM) on gold was used as an electron‐transfer mediator in the electrochemical assay of L ‐ascorbic acid 2‐phosphate (AAP). The assay is based on the enzymatic action of alkaline phosphatase (ALP), which triggers the release of vitamin C (L ‐ascorbic acid, AA) from AAP. The latter is easily oxidized on the Fc‐SAM under the diffusion limiting conditions that favors quantitative measurement of the AA concentration on a rotating disk electrode. We demonstrate the utility of the electrochemically active Fc‐SAM to probe the mechanism and to determine the kinetic parameters of an enzymatic reaction. The electrochemical technique was compared to a conventional spectrophotometric method of ALP activity detection using p‐nitrophenylphosphate (p‐NPP) as a substrate. We demonstrate that our new technique is also suitable for the analytical determination of ALP activity. The detection limits for both AAP and ALP were found to be 13 μM and 2 pM, respectively.     

Electrochemistry and Electrocatalysis of Hemoglobin on 1‐Pyrenebutanoic Acid Succinimidyl Ester/Multiwalled Carbon Nanotube and Au Nanoparticle Modified Electrode

A biocompatible nanocomposite film was fabricated for hemoglobin (Hb) molecules immobilization. This film consists of multiwalled carbon nanotubes (MWNTs), 1‐pyrenebutanoic acid, succinimidyl ester (PASE), hemoglobin (Hb) and Au nanoparticles (AuNPs). Herein, PASE molecules physically adsorbed onto MWNTs, and its groups then covalently bond with Hb. AuNPs were then linked with Hb/PASE/MWNTs via electrostatic adsorption force. UV‐visible adsorption spectra, Fourier transform infrared spectra, scanning electron microscope and electrochemical impedance spectroscopy have characterized the film. Cyclic voltammetry (CV) scans showed that in the film Hb has well‐defined redox reaction, with the formal potential (E°) at about ?0.27 V (vs. Ag/AgCl). Herein, differential pulse voltammetry (DPV) was employed to electrochemically detect the Hb in the film with a detection limit of 9.3×10^?8 M. The proposed method was also succeeded for Hb detection in clinical blood samples. Furthermore, the Hb in the film showed good electrocatalytic activities to the reduction of H₂O₂, TCA, NaNO₂ and O₂.     

One‐Dimensional Carbon Nanotube/SnO2/Noble Metal Nanoparticle Hybrid Nanostructure: Synthesis,Characterization, and Electrochemical Sensing

Herein we report a facile and efficient method for self‐assembling noble‐metal nanoparticles (NPs) to the surface of SnO₂‐coated carbon nanotubes (CNT@SnO₂) to construct CNT@SnO₂/noble metal NP hybrids. By using SnCl₄ as the precursor of the SnO₂ shell on the surface of CNTs, the hydrolysis speed of SnCl₄ was slowed down in ethanol containing a trace amount of urea and water. The coaxial nanostructure of CNT@SnO₂ was confirmed by using X‐ray powder diffraction (XRD) and transmission electron microscopy (TEM). It was found that the coating layer of SnO₂ was homogeneous with the mean thickness of 8 nm. The CNT@SnO₂/noble‐metal NP hybrids were obtained by mixing noble‐metal NPs with as‐prepared CNT@SnO₂ coaxial nanocables by means of a self‐assembly strategy. With the amino group terminated, the CNT@SnO₂ coaxial nanocable can readily adsorb the as‐prepared noble‐metal NPs (Au, Ag, Au? Pt, and Au? Pd NPs). The presence of an amino group at the surface of SnO₂ was proved by use of X‐ray photoelectron spectroscopy (XPS). In addition, H₂O₂ sensing by amperometric methods could serve as detection models for investigating the electrocatalytic ability of as‐prepared hybrid materials. It was found that wide linear ranges and low detection limits were obtained by using the enzyme‐free CNT@SnO₂@Au? Pt modified electrode, which indicated the potential utilizations of the hybrid based on CNT@SnO₂ for electrochemical sensing.     

On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au–alkanedithiol–NP–molecule hybrid entity. The NP appears to relay long‐range electron transfer (ET) so that the rate of the redox reaction may be as efficient as directly on a bare Au electrode, even though the ET distance is increased by several nanometers. In this study, we have employed a fast redox reaction of surface‐confined 6‐(ferrocenyl) hexanethiol molecules and NPs of Au, Pt and Pd to address the dependence of the rate of ET through the hybrid on the particular NP metal. Cyclic voltammograms show an increasing difference in the peak‐to‐peak separation for NPs in the order Au<Pt<Pd, especially when the length of the alkanedithiol increases from octanedithiol to decanedithiol. The corresponding apparent rate constants, k_app, for decanedithiol are 1170, 360 and 14 s^?1 for NPs of Au, Pt and Pd, respectively, indicating that the efficiency of NP mediation of the ET clearly depends on the nature of the NP. Based on a preliminary analysis rooted in interfacial electrochemical ET theory, combined with a simplified two‐step view of the NP coupling to the electrode and the molecule, this observation is referred to the density of electronic states of the NPs, reflected in a broadening of the molecular electron/NP bridge group levels and energy‐gap differences between the Fermi levels of the different metals.     

Ternary Ag/Polyaniline/Au nanocomposites: Preparation,characterization and electrochemical properties

Ternary Ag/Polyaniline/Au nanocomposites were synthesized successfully by immobilizing of Au nanoparticles (NPs) on the surface of Ag/Polyaniline (PANI) nanocomposites. Ag/PANI nanocomposites were prepared via in situ chemical polymerization of aniline in the presence of 4-aminothiophenol (4-ATP) capped silver colloidal NPs. Then, uniform gold (Au) NPs were assembled on the surface of resulted Ag/PANI nanocomposites through electrostatic interaction to get Ag/Polyaniline/Au nanocomposites. The nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), ultraviolet visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). Moreover, Ag/PANI/Au nanocomposites were immobilized on the surface of a glassy carbon electrode and showed enhanced electrocatalytic activity for the reduction of H₂O₂ compared with Ag/PANI.     

Nonenzymatic Hydrogen Peroxide Electrochemical Sensor Based on Au‐HS/SO3H‐PMO (Et) Nanocomposite

A newly nonenzymatic sensor for hydrogen peroxide (H₂O₂) based on the (Au‐HS/SO₃H‐PMO (Et)) nanocomposite is demonstrated. The electrochemical properties of the as‐prepared nanocomposite were studied. It displayed an excellent performance towards H₂O₂ sensing in the linear response range from 0.20 µM to 4.30 mM (R=0.9999) with a sensitivity of 6.35×10² µA µM^?1 cm^?2 and a low detection limit of 0.0499 µM. Furthermore, it was not affected by electroactive interference species. These features proved that the modified electrode was suitable for determination of H₂O₂.     

Label‐free Electrochemical Bisphenol A Aptasensor Based on Designing and Fabrication of a Magnetic Gold Nanocomposite

The present study focuses on designing and fabricating an electrochemical aptasensor for the label free detection of bisphenol A (BPA) using gold nanoparticles (Au NPs) immobilized on functional cupper magnetic nanoparticles (CuFe₂O₄‐SH) and multiwall carbon nanotubes (MWCNTs) modified with aptamer and 6‐mercapto‐1‐hexanol (MCH). A number of analysis techniques were used to characterize the nanocomposite, including Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometer, elemental mapping analysis and energy dispersive x‐ray diffraction. The results of the analyses revealed that the fabricated aptasensor had an acceptable linearity index (0.05‐9 nM) with an ultralow detection limit (25.2 pM) when used to determine BPA. Electrochemical experiments were conducted using a [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ redox system. The results of the electrochemical tests indicated that the existence of Au NPs along with magnetic nanoparticles and MWCNTs in nanocomposite led to a synergistic augmentation on the surface of the modified electrode, thus facilitating the efficient sensing of BPA. This method is highly selective, sensitive and environmentally friendly. Moreover, proposed aptasensor has valuable potential applications in medical diagnostics and food industries where a fast and reliable detection of BPA is of paramount importance for the health of the public.     

A quadruplet electrochemical platform for ultrasensitive and simultaneous detection of ascorbic acid,dopamine, uric acid and acetaminophen based on a ferrocene derivative functional Au NPs/carbon dots nanocomposite and graphene

In this work, a new nanomaterial of thiol functional ferrocene derivative (Fc-SH) stabilized Au NPs/carbon dots nanocomposite (Au/C NC) coupling with graphene modified glassy carbon electrode (Fc-S-Au/C NC/graphene/GCE) was fabricated to serve as a quadruplet detection platform for ultrasensitive and simultaneous determination of ascorbic acid (AA), dopamine (DA), uric acid (UA) and acetaminophen (AC). The Au/C NC was synthesized by adding HAuCl₄ into carbon nanodots solution without using any additional reductant and stabilizing agent. Then the Fc-SH was utilized as the protective and capping agent to modify the Au/C NC. Transmission electron microscopy (TEM), UV–Vis, Fourier-transform infrared (FT-IR), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) were adopted to characterize the morphology and electrochemical properties of the materials and the electrodes. The Fc-S-Au/C NC/graphene/GCE exhibits a synergistic catalytic and amplification effects towards oxidation of AA, DA, UA and AC owing to the existence of the nanomaterial and electron mediator. When simultaneous detection of AA, DA, UA and AC, the oxidation peak potentials of the four compounds on the electrode can be well separated and the peak currents were linearly dependent on their concentrations. The quadruplet detection platform shows excellent linear range and ultrasensitive response to the four components, the detection limits were estimated to be as low as 1.00, 0.05, 0.12 and 0.10 μM (S/N = 3), and the modified electrode exhibits excellent stability and reproducibility. The proposed electrode has been successfully applied to detect of these four analytes in real samples with satisfactory results.     

Au‐TiO2/Graphene Nanocomposite Film for Electrochemical Sensing of Hydrogen Peroxide and NADH

We describe a simple method for preparing Au‐TiO₂/graphene (GR) nanocomposite by deposition of Au nanoparticles (NPs) on TiO₂/GR substrates. The as‐prepared Au‐TiO₂/GR was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The presence of Au NPs on TiO₂/GR surface remarkably improves the electrocatalytic activity towards the oxidation of hydrogen peroxide (H₂O₂) and β‐nicotinamide adenine dinucleotide (NADH). The Au‐TiO₂/GR modified glassy carbon (GC) electrode exhibits good amperometric response to H₂O₂ and NADH, with linear range from 10 to 200 µM and 10 to 240 µM, and detection limit of 0.7 and 0.2 µM, respectively.     

A Novel Hydrogen Peroxide Biosensor Based on the Synergistic Effect of Gold‐Platinum Alloy Nanoparticles/Polyaniline Nanotube/Chitosan Nanocomposite Membrane

Based on the immobilization of horseradish peroxidase (HRP) in chitosan(CS) on a glassy carbon electrode (GCE) modified with the Au‐Pt alloy nanoparticles (NPs) / polyaniline nanotube (nanoPAN) nanocomposite film, a novel hydrogen peroxide biosensor was constructed. The modified processes of GCE were monitored by cyclic voltammetry and electrochemical impedance spectroscopy. Au‐PtNPs/nanoPAN/CS had a better synergistic electrochemical effect than did AuNPs/nanoPAN/CS or PtNPs/nanoPAN/CS. The amperometric response of the biosensor towards H₂O₂ was investigated by successively adding aliquots of H₂O₂ to a continuous stirring phosphate buffer solution under the optimized conditions. Because Au‐PtNPs have unique catalytic properties and good biocompatibility, and especially Au‐PtNPs and nanoPAN have synergistic augmentation for facilitating electron‐transfer, the biosensor displayed a fast response time (<2 s) and broad linear response to H₂O₂ in the range from 1.0 to 2200 μmol L^?1 with a relatively low detection limit of 0.5 μmol L^?1 at 3 times the background noise. Moreover, the biosensor can be applied in practical analysis and exhibited high sensitivity, good reproducibility, and long‐term stability.     

Polyethylenimine‐assisted Synthesis of Au Nanoparticles for Efficient Syngas Production

The ability to capture, store, and use CO₂ is important for remediating greenhouse‐gas emissions and combatting global warming. Herein, Au nanoparticles (Au‐NPs) are synthesized for effective electrochemical CO₂ reduction and syngas production, using polyethylenimine (PEI) as a ligand molecule. The PEI‐assisted synthesis provides uniformly sized 3‐nm Au NPs, whereas larger irregularly shaped NPs are formed in the absence of PEI in the synthesis solution. The Au‐NPs synthesized with PEI (PEI?Au/C, average PEI Mw=2000) exhibit improved CO₂ reduction activities compared to Au‐NPs formed in the absence of PEI (bare Au NPs/C). PEI?Au/C displays a 34 % higher activity toward CO₂ reduction than bare Au NPs/C; for example, PEI?Au/C exhibits a CO partial current density (j_CO) of 28.6 mA cm^?2 at ?1.13 V_RHE, while the value for bare Au NPs/C is 21.7 mA cm^?2; the enhanced j_CO is mainly due to the larger surface area of PEI?Au/C. Furthermore, the PEI?Au/C electrode exhibits stable performance over 64 h, with an hourly current degradation rate of 0.25 %. The developed PEI?Au/C is employed in a CO₂‐reduction device coupled with an IrO₂ water‐oxidation catalyst and a proton‐conducting perfluorinated membrane to form a PEI?Au/C|Nafion|IrO₂ membrane‐electrode assembly. The device using PEI?Au/C as the CO₂‐reduction catalyst exhibits a j_CO of 4.47 mA/cm² at 2.0 V_cell. Importantly, the resulted PEI?Au/C is appropriate for efficient syngas production with a CO ratio of around 30–50 %.     

Self‐Assembly of Platinum Nanoparticle/Multiwalled Carbon Nanotube Multilayer Film on Au Substrate Electrode

A novel approach to assemble multilayer films of Pt nanoparticle/multiwalled carbon nanotube (MWNTs) composites on Au substrate has been developed for the purpose of improving the methanol oxidation efficiency by providing high catalytic surface area. MWNTs were firstly functionalized with 4‐mercaptobenzene and then assembled on an Au substrate electrode. Pt nanoparticles were fabricated and attached to the surface of the functionalized MWNTs subsequently. Thus a layer of Pt/MWNT composites were assembled on the Au substrate electrode. Repeating above process can assemble different layers of film of Pt/MWNTs composites on the Au electrode. Cyclic voltammetry shows that the Au electrode modified with two layers of film of Pt/MWNT composites exhibits high catalytic ability and long‐term stability for methanol oxidation. The layer‐by‐layer self‐assembly technique provides an efficient strategy to construct complex nanostructure for improving the methanol oxidation efficiency by providing high catalytic surface area.     

Molecular Dynamics Simulation of the Binding Interaction between Hormone Glucagon Protein and Self-Assembled Monolayer Molecules

Restrained molecular dynamics simulations were performed to study the binding affinity of the peptide with alkanethiols of different tail-groups, S（CH2）7CH3, S（CH2）7OH and S（CH2）7COOH, which self-assembled on Au（111） surface in the presence of water molecules. The curves of binding affinity were calculated by fixing the center of mass of the peptide at various distances from the assembling surface. Simulation results show that the binding affin- ity is in the order as COOH-SAMs〉OH-SAMs〉CH3-SAMs, while 100% COOH-SAMs〉5% COOH-SAMS in concentration. The effects on binding affinity by different tail-groups were also studied. Results show that the binding affinity between COOH-SAMs and the peptide is bigger than those of the others and increasing the acidity of COOH-SAMs will result in stronger attractive power.     

In Situ Synthesis of a Novel Quinone Imine Self‐Assembled Monolayer and Consideration of Its Reactivity with L‐Arginine

In situ functionalization of a 4‐aminothiophenol (4ATP) self‐assembled monolayer (SAM) on a Au electrode (4ATP/Au SAM) by the Michael addition reaction is considered. Under optimized conditions, the nucleophilic attack of the amino group of 4ATP/Au SAM to give an electrogenerated ortho‐quinone produced a novel electroactive SAM (ESAM). The ESAM could be oxidized to quinone‐imine SAM (QI SAM) for the covalent immobilization of L ‐arginine monolayers. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Fourier transform infrared (FTIR) spectroscopy are employed to characterize these systems.. The apparent heterogeneous rate constant (k_s^app) for ESAM/Au and the rate constant (k′) of the pseudo‐first order Michael addition reaction of L ‐arginine and ESAM/Au are calculated.     

Noncovalent Assembly of Picket‐Fence Porphyrins on Nitrogen‐Doped Carbon Nanotubes for Highly Efficient Catalysis and Biosensing

A water‐insoluble picket‐fence porphyrin was first assembled on nitrogen‐doped multiwalled carbon nanotubes (CN_x MWNTs) through Fe? N coordination for highly efficient catalysis and biosensing. Scanning electron micrographs, Raman spectra, X‐ray photoelectron spectra, UV/Vis absorption spectra, and electrochemical impedance spectra were employed to characterize this novel nanocomposite. By using electrochemical methods on the porphyrin at low potential in neutral aqueous solution, the presence of CN_x MWNTs led to the direct formation of a high‐valent iron(IV)–porphyrin unit, which produced excellent catalytic activity toward the oxidation of sulfite ions. By using sulfite ions, a widely used versatile additive and preservative in the food and beverage industries, as a model, a highly sensitive amperometric biosensor was proposed. The biosensor showed a linear range of four orders of magnitude from 8.0×10^?7 to 4.9×10^?3 mol L^?1 and a detection limit of 3.5×10^?7 mol L^?1 due to the highly efficient catalysis of the nanocomposite. The designed platform and method had good analytical performance and could be successfully applied in the determination of sulfite ions in beverages. The direct noncovalent assembly of porphyrin on CN_x MWNTs provided a facile way to design novel biofunctional materials for biosensing and photovoltaic devices.