Escherichia coli O157:H7 detection limit of millimeter-sized PZT cantilever sensors is 700 cells/mL.

A composite self-excited millimeter-sized lead zirconate titanate (PZT) glass cantilever (2 mm x 1.8 mm; sensing area of 6 mm2) was fabricated for the detection of Escherichia coli (E. coli) O157:H7. The fundamental and second mode resonance in air was 10.95 +/- 0.05 kHz and 43.45 +/- 0.05 kHz, respectively. Affinity purified monoclonal antibody (anti-E. coli O157:H7) specific to the pathogen E. coli O157:H7 was immobilized at the cantilever glass tip, and then immersed in liquid containing the pathogen (70 to 7 x 10(7) cells/mL). The resonant frequency showed a reduction and reached a steady state shift of 0 +/- 5, 46 +/- 5, 260 +/- 5, and 1010 +/- 5 Hz corresponding to 0, 700, 7000, and 7 x 10(7) cells/mL. From the experiments conducted, the detection limit of the sensor was 700 cells/mL.     

Effects of Pt diffusion barrier layer on the interface reaction and electric properties of PZT film/Si (111) sample

The effects of the Pt diffusion barrier layer on the interface diffusion and reaction, crystallization, dielectric and ferroelectric properties of the PZT/Si(111) sample have been studied using XPS, AES and XRD techniques. Hie results indicate that the Pt diffusion barrier layer between the PZT layer and the Si substrate prohibits the formation of TiCx TiSix and SiO2 species in the PZT layer. The Pt barrier layer also completely interrupts the diffusion of Si from the Si substrate into the PZT layer and impedes the diffusion of oxygen from air to the Si substrate greatly. Although the Pt layer can not prevent completely the diffusion and reaction between oxygen and silicon, it can prevent the formation of a stable SiO2 interface layer on the interface of PZT/Si. The Pt layer reacts with silicon to form PtSix species on the interface of Pt/Si, which can intensify the chemical binding strength between the Pt layer and the Si substrate. To play a good role as a diffusion barrier layer, the Pt barrier layer     

Analysis of DNA hybridization regarding the conformation of molecular layer with piezoelectric microcantilevers

Lead Zirconate Titanate (PZT)-embedded microcantilevers were fabricated with dimensions of 30 × 90 × 3 μm(3) (width × length × thickness). A thicker PZT layer improved the actuation and enabled long-term data acquisition in common aqueous buffers with a frequency resolution of 20 Hz. A quantitative assay was conducted in the range of 1-20 μM and the resonant frequency was found to increase with the concentration of target DNAs and the probe DNAs were almost saturated at 20 μM. Back-filling with ethyleneglycol-modified alkanethiol was shown to facilitate the hybridization efficiency and stabilize the surface reaction, resulting in a signal enhancement of 40%. We report for the first time how secondary structures in oligonucleotide monolayer change the surface property of a dynamic mode microcantilever and subsequently affect its oscillating behavior. Using fabricated microcantilevers, the real time changes in resonant frequency upon hybridization were measured by utilizing different probe and target sets. The results revealed that the microcantilevers experienced a resonant frequency upshift during the hybridization with complementary DNAs if a dimer structure was present between DNA probes. A resonant frequency downshift was observed for DNA probes that did not contain any complex secondary structures. In addition, the results demonstrate the potential of using these microcantilevers to extract structural information of oligonucleotides.     

High-resolution cantilever biosensor resonating at air-liquid in a microchannel

We have developed a highly mass-sensitive cantilever resonating at the interface of air and liquid. The cantilever is applicable as a biosensor by measuring its resonance frequency shift associated with the selective trapping of target molecules. One surface of the cantilever facing to the liquid is functionalized for label-free detection, while the opposite side is exposed to air to improve the resonance characteristics, such as the quality factor. The quality factor at resonance is 15, which is 50% higher than the same cantilever in liquid. The beam was excited through the photothermal effect of a power modulated laser and detected by laser Doppler velocimetry. Due to the proposed configuration, the signal-to-noise-ratio is 5.7 times larger than the completely submerged case. A micro-slit around the cantilever separates the air and liquid phases at a meniscus. We analyzed the cantilever motion including the meniscus membrane, and examined the effect of surface tension by applying various solutions. A slit width of 6 μm was found to give the best performance within the few prototypes. We measured the covalent immobilization of antibody molecules on a cantilever surface for three different concentrations: 20, 40, and 80 μg ml(-1). The kinetics measured by both resonance frequency shift of the cantilever and fluorescent intensity showed good agreement.     

Ferroelectric and Pyroelectric Properties of Highly (111)-oriented Nanocrystalline Pb(Zr0:95Ti0:05)O3 Thin Films

"Lead zirconate titanate Pb(Zr0:95Ti0:05)O3 (PZT95/5) antiferroelectric thin films with 300 nm thickness were grown on Pt/Ti/SiO2/Si substrates by a sol-gel method with rapid thermal annealing processing. The X-ray diffraction results showed that the highly (111)-oriented pervoskite PZT95/5 thin films were grown on Pt/Ti/SiO2/Si substrates when annealed at 600-700 oC. Electrical measurements were conducted on PZT95/5 films in metal-ferroelectric-metal capacitor configuration. The PZT95/5 thin films annealed at 600-700 oC showed well-saturated hysteresis loops at an applied voltage of 20 V. At 1 kHz, the dielectric constant and dielectric loss of the films were 519 and 0.028, 677 and 0.029, 987 and 0.025, respectively for the thin films annealed at 600, 650, and 700 oC. The average remanent polarization (Pr) and the coercive electric field (Ec) obtained from the P-E hysteresis loops, were 19.1 1C/cm2 and 135.6 kV/cm, 29.31C/cm2 and 88.57 kV/cm, 45.3 1C/cm2 and 102.1 kV/cm, respectively for PZT95/5 thin films annealed at 600, 650 and 700 oC for 10 min in the oxygen atmosphere. This showed a good ferroelectricity of the prepared PZT95/5 films on Pt/Ti/SiO2/Si substrates by the simple sol-gel processing. The pyroelectric coeocient (p) of antiferroelectric PZT95/5 films was measured by a dynamic technique. At room temperature, the p values of the antiferroelectric PZT95/5 films at 1 kHz were 274, 238, and 212 1C/m2K."     

Dielectric and Pyroelectric Properties of Compositionally Graded Pb(Zr1-xTix)O3 Thin Films Prepared by Sol-gel Process

"Compositionally graded ferroelectric lead zirconate titanate Pb(Zr1-xTix)O3 (PZT) thin films were grown on Pt/Ti/SiO2/Si substrates by using a sol-gel process. The final structure consists of six layers, up-graded graded films starting from PbZrO3 on the Pt electrode to the top PZT(50) layer, it consists of no Ti, 10%Ti, 20%Ti, 30%Ti, 40%Ti, and 50%Ti respectively. Whereas films with opposite gradient are called down-graded graded films. Structure and dielectric properties of the graded films was investigated by X-ray diffraction, Auger electron spectroscopy and by impedance analysis. The up-graded and down-graded PZT films annealed at 600 o, exhibited the remanent polarization values of 18.0 and 24.2 1C/cm2, respectively. The typical small signal dielectric constants and loss tanffi at a frequency of 100 Hz were 523 and 0.018, 544, and 0.020, respectively, for up-graded and down-graded PZT thin films. The temperature dependence of pyroelectric coeoients of the graded PZT films was measured by a dynamic technique. From 20 o to 82 o, the pyroelectric coeoients of the up-graded and down-graded PZT films up to 374 and 407 1C/m2K, respectively."     

High sensitivity of diamond resonant microcantilevers for direct detection in liquids as probed by molecular electrostatic surface interactions

Resonant microcantilevers have demonstrated that they can play an important role in the detection of chemical and biological agents. Molecular interactions with target species on the mechanical microtransducers surface generally induce a change of the beam's bending stiffness, resulting in a shift of the resonance frequency. In most biochemical sensor applications, cantilevers must operate in liquid, even though damping deteriorates the vibrational performances of the transducers. Here we focus on diamond-based microcantilevers since their transducing properties surpass those of other materials. In fact, among a wide range of remarkable features, diamond possesses exceptional mechanical properties enabling the fabrication of cantilever beams with higher resonant frequencies and Q-factors than when made from other conventional materials. Therefore, they appear as one of the top-ranked materials for designing cantilevers operating in liquid media. In this study, we evaluate the resonator sensitivity performances of our diamond microcantilevers using grafted carboxylated alkyl chains as a tool to investigate the subtle changes of surface stiffness as induced by electrostatic interactions. Here, caproic acid was immobilized on the hydrogen-terminated surface of resonant polycrystalline diamond cantilevers using a novel one-step grafting technique that could be also adapted to several other functionalizations. By varying the pH of the solution one could tune the -COO(-)/-COOH ratio of carboxylic acid moieties immobilized on the surface, thus enabling fine variations of the surface stress. We were able to probe the cantilevers resonance frequency evolution and correlate it with the ratio of -COO(-)/-COOH terminations on the functionalized diamond surface and consequently the evolution of the electrostatic potential over the cantilever surface. The approach successfully enabled one to probe variations in cantilevers bending stiffness from several tens to hundreds of millinewtons/meter, thus opening the way for diamond microcantilevers to direct sensing applications in liquids. The evolution of the diamond surface chemistry was also investigated using X-ray photoelectron spectroscopy.     

MoO_x促进的Pt基催化剂用于低温水汽变换反应(英文)

通过浸渍还原法制备了不同比例的Pt-Mo/SiO_2催化剂,采用X射线衍射、透射电镜、X射线近边吸收谱和X射线光电子能谱表征了Pt-Mo/SiO_2催化剂的组成、结构及价态.研究结果表明,少量MoO_x修饰Pt-Mo/SiO_2催化剂在低温水汽变换反应中表现出比Pt/SiO_2催化剂更高的催化活性,过量MoO_x包覆的Pt-Mo/SiO_2催化剂活性较低.低温水汽变换反应活性来自于Pt与表面MoO_x的界面协同作用,限域在Pt纳米颗粒表面的MoO_x表现出较低价态,高分散MoO_x纳米岛修饰的Pt纳米颗粒是低温水汽变换反应的活性结构.     

Interface diffusion and chemical reaction of PZT layer/Si (111) sample during the annealing treatment in air

The interface diffusion and chemical reaction between a PZT (PbZrxTi1-xO3) layer and a Si(111) substrate during the annealing treatment in air have been studied by using XPS (X-Ray Photoelectron Spectroscopy) and AES (Auger Electron Spectroscopy). The results indicate that the Ti element in the PZT precursor reacted with residual carbon and silicon, diffused from the Si substrate, to form TiCx, TiSix species in the PZT layer during the thermal treatment. A great interface diffusion and chemical reaction took place on the interface of PZT Si also. The silicon atoms diffused from silicon substrate onto the surface of PZT layer. The oxygen atoms, which came from air, diffused into silicon substrate also and reacted with Si atoms to form a SiO2 interlayer between the PZT layer and the Si (111) substrate. The thickness of SiO2 interlayer was proportional to the square root of treatment time. The formation of the SiO2 interlayer was governed by the diffusion of oxygen in the PZT layer at low annealing tempera     

Chemical solution-deposited PbZr 0.53 Ti 0.47 O3 on La 0.5 Sr 0.5 Co O3. SIMS investigation of the effect of different precursor additives on the layer structure

Chemical solution-deposited thin films of PbZr(0.53)Ti(0.47)O(3)/La(0.5)Sr(0.5)CoO(3) on Pt/TiO(2)/SiO(2)/Si substrates have been investigated by dynamic SIMS. The PbZr(0.53)Ti(0.47)O(3) (PZT) is intended to serve as a ferroelectric layer for microelectronic or microelectromechanical applications; conducting La(0.5)Sr(0.5)CoO(3) (LSCO) is a buffer layer intended to eliminate fatigue effects which usually occur at the Pt/PZT interface. Depth profiles of the main components were obtained and revealed that significant diffusion occurred during the deposition and crystallisation processes. Two types of sample, with different thickness of PZT and different types of poly(vinyl alcohol) (PVA) added to the LSCO precursor, were investigated.     

Low-temperature water gas shift reaction on Cu/SiO2 prepared by an atomic layer epitaxy technique

An atomic layer epitaxy technique was used to produce nanoscale 2.9-3.4 nm copper particles supported on silica, and the nanoscale Cu/SiO2 catalysts can show surprisingly high activity for the water gas shift reaction, in comparison with the 5.6 wt% Pt/SiO2 and 10.3 wt% Cu/SiO2 prepared by the impregnation method.     

H2S gas sensor based on integrated resonant dual-microcantilevers with high sensitivity and identification capability

Detection of trace-level hydrogen sulfide (H₂S) gas is of great importance whether in industrial production or disease diagnosis. This research presents a novel H₂S gas sensor based on integrated resonant dual-microcantilevers which can identify and detect trace-level H₂S in real-time. The sensor consists of two integrated resonant microcantilever sensors with different functions. One cantilever sensor can identify H₂S by outputting positive frequency shift signals, while the other cantilever sensor will detect H₂S as a normally used cantilever sensor with negative frequency shifts. Combined the two cantilever sensors, the proposed gas sensor can distinguish H₂S from a variety of common gases, and the detection limit to H₂S of the sensor is as sensitive as below 1 ppb.     

A new method for non-labeling attomolar detection of diseases based on an individual gold nanorod immunosensor

Herein, we present the use of a single gold nanorod sensor for detection of diseases on an antibody-functionalized surface, based on antibody-antigen interaction and the localized surface plasmon resonance (LSPR) λ(max) shifts of the resonant Rayleigh light scattering spectra. By replacing the cetyltrimethylammonium bromide (CTAB), a tightly packed self-assembled monolayer of HS(CH(2))(11)(OCH(2)CH(2))(6)OCH(2)COOH(OEG(6)) has been successfully formed on the gold nanorod surface prior to the LSPR sensing, leading to the successful fabrication of individual gold nanorod immunosensors. Using prostate specific antigen (PSA) as a protein biomarker, the lowest concentration experimentally detected was as low as 111 aM, corresponding to a 2.79 nm LSPR λ(max) shift. These results indicate that the detection platform is very sensitive and outperforms detection limits of commercial tests for PSA so far. Correlatively, its detection limit can be equally compared to the assays based on DNA biobarcodes. This study shows that a gold nanorod has been used as a single nanobiosensor to detect antigens for the first time; and the detection method based on the resonant Rayleigh scattering spectrum of individual gold nanorods enables a simple, label-free detection with ultrahigh sensitivity.     

Surface plasmon resonance-enhanced photoelectrochemical immunoassay of prostate-specific antigen based on BiOCl-Au heterojunction

Taking advantage of the high-efficiency photocurrent response of bismuth oxychloride sensitized with gold nanoparticles (BiOCl−Au) in combination with the antigen-antibody biological recognition reaction, a convenient photoelectrochemical (PEC) immunoassay (model target: prostate-specific antigen; PSA) has been fabricated. In particular, the enhanced photocurrent response could be attributed to the enhanced optical absorption of visible light from surface plasmon resonance (SPR) effect of gold nanoparticles in the hierarchical structure of BiOCl layered. To realize the biological detection process, an immunoreaction was implemented between target PSA and alkaline phosphatase (ALP)-labeled anti-PSA antibodies. With the formation of ternary sandwich immunocomplex, the carried and loaded ALP catalysed the substrate ascorbic acid 2-phosphate (AAP) to generate ascorbic acid for increasing the photocurrent intensity of BiOCl−Au/FTO. Under optimum reaction time, the photocurrent peak intensity of BiOCl−Au/FTO increased with the increasing of target PSA concentration in the range of 0.01 ng/mL to 50 ng/mL with a limit of detection (LOD) down to 2.3 pg/mL. In the photocurrent control experiment, the photocurrent of BiOCl−Au/FTO was not only higher than that of BiOCl/FTO, but also showed greater changes in photocurrent under the same target PSA concentration. Impressively, the proposed split-type PEC immunoassay was applied to detect PSA concentration in human serum samples, giving acceptable and satisfactory accuracy compared with the gold standard PSA ELISA method.     

Monitoring of the self-assembled monolayer of 1-hexadecanethiol on a gold surface at nanomolar concentration using a piezo-excited millimeter-sized cantilever sensor

In this paper, we describe a new method of measuring alkanethiol monolayer formation on a gold surface. A gold-coated millimeter-sized rectangular-shaped lead zirconate titanate (PZT) cantilever of dimensions 3.5 x 2 x 0.05 mm, previously shown to detect a picogram level of mass change, was used to measure the adsorption kinetics of 1-hexadecanethiol in ethanol over six orders of concentration range (1 nM to 10 mM) in real time. The flexural mode of cantilever vibration, 45.5 +/- 0.01 kHz, was monitored during the self-assembly. The total resonant frequency change obtained for the 1 nM, 10 nM, 100 nM, 1 microM, 4 mM, 8 mM, and 10 mM thiol concentrations were 116 +/- 2 (n = 2), 225 (n = 1), 270 +/- 10 (n = 2), 440 +/- 10 (n = 2), 900 +/- 10 (n = 2), 900 +/- 10 (n = 2), and 900 +/- 10 (n = 2) Hz, respectively. These results compare favorably to literature results in that the rate of the monolayer formation is concentration-dependent and the exponential change during adsorption follows the reversible first-order Langmuir kinetic model. The rate constants of adsorption and desorption were 0.061 M(-1) s(-1) and 3.61 x 10(-4) s(-1), respectively. The significance of the results is that millimeter-sized PZT cantilevers can be used in real-time for characterizing self-assembly of monolayer formation at nanomolar concentration levels. In addition, at 1 nM, the adsorption was found not to be diffusion limited.     

Application of a new microcantilever biosensor resonating at the air-liquid interface for direct insulin detection and continuous monitoring of enzymatic reactions

Here we describe the application of a recently developed high-resolution microcantilever biosensor resonating at the air-liquid interface for the continuous detection of antigen-antibody and enzyme-substrate interactions. The cantilever at the air-liquid interface demonstrated 50% higher quality factor and a 5.7-fold increase in signal-to-noise-ratio (SNR) compared with one immersed in the purified water. First, a label-free detection of a low molecular weight protein (insulin, 5.8 kDa) in physiological concentration was demonstrated. The liquid facing side of the cantilever was functionalized by coating its surface with insulin antibodies, while the opposite side was exposed to air. The meniscus membrane at the micro-slit around the cantilever sustained the liquid in the microchannel. After optimizing the process of surface functionalization, the resonance frequency shift was successfully measured for insulin solutions of 0.4, 2.0, and 6.3 ng ml(-1). To demonstrate additional application of the device for monitoring enzymatic protein degradation, the liquid facing microcantilever surface was coated with human recombinant SOD1 (superoxide dismutase 1) and exposed to various concentrations of proteinase K solution, and the kinetics of the SOD1 digestion was continuously monitored. The results showed that it is a suitable tool for sensitive protein detection and analysis.     

基于CdSe-CdTe量子点能量转移荧光猝灭法测定前列腺抗原

研究了CdSe-CdTe量子点间发生的荧光共振能量转移,并用于荧光猝灭法测定超痕量前列腺抗原(PSA)。在pH 8.0的Tris-HCl缓冲溶液中,CdSe-CdTe间发生有效能量转移,使CdTe荧光大大增强。PSA抗原与CdTe标记的PSA抗体发生特异性反应,使能量转移体系的CdTe上的荧光强度降低,即发生猝灭。建立了CdSe-CdTe能量转移荧光猝灭法测定PSA抗原的方法。在优化的实验条件下,PSA抗原的线性范围为0.28～10μg/L,相关系数r=0.9992,检出限达1.5×10-2μg/L(n=11)。     

Microstructure and ferroelectric properties of r.f. magnetron sputtering derived PZT thin films deposited on interlayer (PbO/TiO2)

Lead zirconate titanate (PZT) thin films were deposited on Pt/Ti/SiO₂/Si and interlayer/Pt/Ti/SiO₂/Si substrate by radio frequency (r.f.) magnetron sputtering with a Pb_1.1Zr_0.53Ti_0.47O₃ target. The crystallization of the PZT thin films was formed only by substrate temperature. When interlayer (PbO/TiO₂) was inserted between the PZT thin film and the Pt electrode, the grain growth and processing temperature of the PZT thin films were considerably improved. Compared to PZT/Pt structure, the dielectric constant and polarization properties of the PZT/interlayer/Pt structure were fairly improved. In particular, PZT/interlayer/Pt at the substrate temperature of 400 °C showed prevalent ferroelectric properties (_r=475.97, tanδ=0.0591, P_r=23 μC/cm²). As a result of an X-ray photoelectron spectroscopy (XPS) depth-profile analysis, it was found that PZT/interlayer/Pt deposited only by substrate temperature without the post-annealing process via r.f. magnetron sputtering method remained independent of each other regardless of substrate temperatures.     

Furfuraldehyde hydrogenation on titanium oxide-supported platinum nanoparticles studied by sum frequency generation vibrational spectroscopy: Acid-base catalysis explains the molecular origin of strong metal-support interactions

This work describes a molecular-level investigation of strong metal-support interactions (SMSI) in Pt/TiO(2) catalysts using sum frequency generation (SFG) vibrational spectroscopy. This is the first time that SFG has been used to probe the highly selective oxide-metal interface during catalytic reaction, and the results demonstrate that charge transfer from TiO(2) on a Pt/TiO(2) catalyst controls the product distribution of furfuraldehyde hydrogenation by an acid-base mechanism. Pt nanoparticles supported on TiO(2) and SiO(2) are used as catalysts for furfuraldehyde hydrogenation. As synthesized, the Pt nanoparticles are encapsulated in a layer of poly(vinylpyrrolidone) (PVP). The presence of PVP prevents interaction of the Pt nanoparticles with their support, so identical turnover rates and reaction selectivity is observed regardless of the supporting oxide. However, removal of the PVP with UV light results in a 50-fold enhancement in the formation of furfuryl alcohol by Pt supported on TiO(2), while no change is observed for the kinetics of Pt supported on SiO(2). SFG vibrational spectroscopy reveals that a furfuryl-oxy intermediate forms on TiO(2) as a result of a charge transfer interaction. This furfuryl-oxy intermediate is a highly active and selective precursor to furfuryl alcohol, and spectral analysis shows that the Pt/TiO(2) interface is required primarily for H spillover. Density functional calculations predict that O-vacancies on the TiO(2) surface activate the formation of the furfuryl-oxy intermediate via an electron transfer to furfuraldehyde, drawing a strong analogy between SMSI and acid-base catalysis.     

Development of a peptide inhibitor-based cantilever sensor assay for cyclic adenosine monophosphate-dependent protein kinase

A highly sensitive nanomechanical cantilever sensor assay based on an electrical measurement has been developed for detecting activated cyclic adenosine monophosphate (cyclic AMP)-dependent protein kinase (PKA). Employing a peptide derived from the heat-stable protein kinase inhibitor (PKI), a magnetic bead system was first selected as a vehicle to immobilize the PKI-(5-24) peptide for capturing PKA catalytic subunit and the activity assay was applied for indirectly assessing the binding. Synergistic interactions of adenosine triphosphate (ATP) and the peptide inhibitor with the kinase were then investigated by a solution phase capillary electrophoretic assay, and by surface plasmon resonance technology which involved immobilization of the peptide inhibitor. After systemically evaluated by a homogeneous direct binding assay, the ATP-dependent recognition of the catalytic subunit of PKA by PKI-(5-24) was successfully transferred on to the nanomechanical cantilevers at protein concentrations of 6.6 pM-66 nM, exhibiting much higher sensitivity and wider dynamic range than the conventional activity assay. Thus, direct assessment of activated kinases using the cantilever sensor system functionalized with specific peptide inhibitors holds great promise in analytical applications and clinical medicine.