Soft molecularly imprinted nanoparticles with simultaneous lossy mode and surface plasmon multi-resonances for femtomolar sensing of serum transferrin protein

: The simultaneous interrogation of both lossy mode (LMR) and surface plasmon (SPR) resonances was herein exploited for the first time to devise a sensor in combination with soft molecularly imprinting of nanoparticles (nanoMIPs), specifically entailed of the selectivity towards the protein biomarker human serum transferrin (HTR). Two distinct metal-oxide bilayers, i.e. TiO2-ZrO2 and ZrO2-TiO2, were used in the SPR-LMR sensing platforms. The responses to binding of the target protein HTR of both sensing configurations (TiO2-ZrO2-Au-nanoMIPs, ZrO2-TiO2-Au-nanoMIPs) showed femtomolar HTR detection, LODs of tens of fM and KDapp ~ 30 fM. Selectivity for HTR was demonstrated. The SPR interrogation was more efficient for the ZrO2-TiO2-Au-nanoMIPs configuration (sensitivity at low concentrations, S = 0.108 nm/fM) than for the TiO2-ZrO2-Au-nanoMIPs one (S = 0.061 nm/fM); while LMR was more efficient for TiO2-ZrO2-Au-nanoMIPs (S = 0.396 nm/fM) than for ZrO2-TiO2-Au-nanoMIPs (S = 0.177 nm/fM). The simultaneous resonance monitoring is advantageous for point of care determinations, both in terms of measurement's redundancy, that enables the cross-control of the measure and the optimization of the detection, by exploiting the individual characteristics of each resonance

Broadband Dielectric Spectroscopic Detection of Aliphatic Alcohol Vapors with Surface-Mounted HKUST-1 MOFs as Sensing Media †

We leveraged chemical-induced changes to microwave signal propagation characteristics (i.e., S-parameters) to characterize the detection of aliphatic alcohol (methanol, ethanol, and 2-propanol) vapors using TCNQ-doped HKUST-1 metal-organic-framework films as the sensing material, at temperatures under 100 ◦C. We show that the sensitivity of aliphatic alcohol detection depends on the oxidation potential of the analyte, and the impedance of the detection setup depends on the analyte-loading of the sensing medium. The microwaves-based detection technique can also afford new mechanistic insights into VOC detection, with surface-anchored metal-organic frameworks (SURMOFs), which is inaccessible with the traditional coulometric (i.e., resistance-based) measurements

Broadband Dielectric Spectroscopic Detection of Aliphatic Alcohol Vapors With Surface-Mounted HKUST-1 MOFs as Sensing Media

We leveraged chemical-induced changes to microwave signal propagation characteristics (i.e., S-parameters) to characterize the detection of aliphatic alcohol (methanol, ethanol, and 2-propanol) vapors using TCNQ-doped HKUST-1 metal-organic-framework films as the sensing material, at temperatures under 100 °C. We show that the sensitivity of aliphatic alcohol detection depends on the oxidation potential of the analyte, and the impedance of the detection setup depends on the analyte-loading of the sensing medium. The microwaves-based detection technique can also afford new mechanistic insights into VOC detection, with surface-anchored metal-organic frameworks (SURMOFs), which is inaccessible with the traditional coulometric (i.e., resistance-based) measurements

Synthesis and gas sensing properties of inorganic semiconducting, p-n heterojunction nanomaterials

En aquesta tesis utilitzant principalment Aerosol Assited Chemical Vapor Deposition, AACVD, com a metodologia de síntesis d'òxid de tungstè nanoestructurat s'han fabricat diferents sensors de gasos. Per tal d'estudiar la millora en la selectivitat i la sensibilitat dels sensors de gasos basats en òxid de tungstè aquest s'han decorat, via AACVD, amb nanopartícules d'altres òxids metàl·lics per a crear heterojuncions per tal d'obtenir un increment en la sensibilitat electrònica, les propietats químiques del material o bé ambdues. En particular, s'han treballat en diferents sensors de nanofils d'òxid de tungstè decorats amb nanopartícules d'òxid de níquel, òxid de cobalt i òxid d'iridi resultant en sensors amb un gran increment de resposta i selectivitat cap al sulfur d'hidrogen, per a l'amoníac i per a l'òxid de nitrogen respectivament a concentracions traça. A més a més, s'han estudiat els mecanismes de reacció que tenen lloc entre les espècies d'oxigen adsorbides a la superfície del sensor quan interactua amb un gas. I també s'ha treballat en intentar controlar el potencial de superfície de les capes nanoestructurades per tal de controlar la deriva en la senyal al llarg del temps, quan el sensor està operant, a través d'un control de temperatura.En esta tesis utilizando principalmente Aerosol Assited Chemical Vapor Deposition, AACVD, como metodología de síntesis de óxido de tungsteno nanoestructurado se han fabricado diferentes sensores de gases. Para estudiar la mejora en la selectividad y la sensibilidad de los sensores de gases basados en óxido de tungsteno estos se han decorado, vía AACVD, con nanopartículas de otros óxidos metálicos para crear heterouniones para obtener un incremento en la sensibilidad electrónica, las propiedades químicas del material o bien ambas. En particular, se han trabajado en diferentes sensores de nanohilos de óxido de tungsteno decorados con nanopartículas de óxido de níquel, óxido de cobalto y óxido de iridio resultante en sensores con un gran incremento de respuesta y selectividad hacia el sulfuro de hidrógeno, para el amoníaco y para el óxido de nitrógeno respectivamente a concentraciones traza. Además, se han estudiado los mecanismos de reacción que tienen lugar entre las especies de oxígeno adsorbidas en la superficie del sensor cuando interactúa con un gas. Y también se ha trabajado en intentar controlar el potencial de superficie de las capas nanoestructuradas para controlar la deriva en la señal a lo largo del tiempo, cuando el sensor está trabajando, a través de un control de temperatura.In this thesis, using mainly Aerosol Assited Chemical Vapor Deposition, AACVD, as a synthesis methodology for nanostructured tungsten oxide, different gas sensors have been manufactured. To study the improvement in the selectivity and sensitivity of gas sensors based on tungsten oxide, they have been decorated, via AACVD, with nanoparticles of other metal oxides to create heterojunctions to obtain an increase in electronic sensitivity, in the chemical properties of the material or at the same time in both. Particularly, we have worked on different tungsten oxide nanowire sensors decorated with nanoparticles of nickel oxide, cobalt oxide and iridium oxide resulting in sensors with a large increase in response and selectivity towards hydrogen sulfide, for ammonia. and for nitrogen oxide respectively at trace concentrations. In addition, the reaction mechanisms that take place between oxygen species adsorbed on the sensor surface when it interacts with a gas have been also studied. Furthermore, efforts have been put on trying to control the surface potential of the nanostructured layers to control the drift in the signal over time, when operating the sensors, through temperature control

Molecular Imprinted Polymers Coupled to Photonic Structures in Biosensors: The State of Art

Optical sensing, taking advantage of the variety of available optical structures, is a rapidly expanding area. Over recent years, whispering gallery mode resonators, photonic crystals, optical waveguides, optical fibers and surface plasmon resonance have been exploited to devise different optical sensing configurations. In the present review, we report on the state of the art of optical sensing devices based on the aforementioned optical structures and on synthetic receptors prepared by means of the molecular imprinting technology. Molecularly imprinted polymers (MIPs) are polymeric receptors, cheap and robust, with high affinity and selectivity, prepared by a template assisted synthesis. The state of the art of the MIP functionalized optical structures is critically discussed, highlighting the key progresses that enabled the achievement of improved sensing performances, the merits and the limits both in MIP synthetic strategies and in MIP coupling

Monolithic Integration Piezoelectric Resonators on CMOS for Radio-Frequency and Sensing Applications

Software cognitive radios and Internet of Things (IoT) are recent interest areas that need low loss and low power consumption hardware. More specifically, the area of software cognitive radios requires that hardware be frequency agile and highly selective. Meanwhile, IoT relies on multiple low power sensor networks. By combining Complementary Metal Oxide Semiconductors (CMOS) technology with piezoelectric Micro-Electro-Mechanical Systems (MEMS), we can fabricate Systems-on-Chip (SoC) that can be used as filters or references (oscillators) and highly selective sensors. In this work we developed a die-level compatible process for the monolithic integration of Bulk Acoustic Resonators (BAWs) on CMOS for low power, reduced area and high-quality passives for radio frequency applications. Using CMOS as a fabrication substrate some stringent requirements were added to maintain the dies and the technology’s integrity. A few of these limitations were the need for a low thermal budget fabrication process, die handling and electro-static discharge (ESD) protection. The devices were first fabricated on glass for modeling extraction that was later used for the design of the integrated circuits (IC). Three integrated circuits were designed as substrates for the integration using IBM’s 180nm and TSMC’s 65nm technology. A monolithic BAW oscillator with a resonance frequency of 1.8GHz was demonstrated with an FOM ~186dBc/Hz, comparable to other academia work. Using the developed process, a membrane BAW structure (FBAR) was integrated as well. Using a susceptor coating and zinc oxide’s (ZnO) high temperature coefficient of frequency (TCF) the device was studied as an alternative uncooled infrared sensor. Finally, a reprogrammable IC and an RF PCB were designed for volatile organic compound (VOC) testing using self-assembled monolayers (SAMs) as the absorber layer

High frequency thin-film bulk acoustic wave resonators for gas- and bio-analytical applications

Thin Film Bulk Acoustic Wave Resonators (FBAR) are mechanical micro scale devices that operate in the UHF/Microwave frequency range. This high frequency of operation potentially offers increased sensitivity to the addition of surface mass loading as implied by the famous Sauerbrey equation. FBAR was shown to be responsive to physical and chemical changes in the environment and was further adapted to act as bio-sensor. Thus indicating a universal platform from which to launch an enhanced sensing technology. This thesis follows the research and development of a prototype chemical and biological sensor based on FBAR FBAR devices were fabricated in a clean room and on die RF measurements were made to identify the units with performance characteristics of high enough quality to be useful as sensors. The FBAR design was then adapted so that it could be environmentally isolated, and microwave circuitry was devised to allow the FBAR to remain in electrical contact with the outside world during its isolation. This allowed for controllable environments in which to test FBAR responses to chemical and biological agents free from interfering signals. A software suite was written to specifically address the requirements for accurate and sensitive data processing of FBAR responses to measured analytes in real time. The isolation assembly and software was tested thoroughly, and the ultimate limits of resolution and sensitivity for the instrumentation were found using temperature change as the variable input parameter. A gas delivery apparatus was constructed and the FBAR was coated with hygroscopic polymer layers to sensitise the device to water vapour. Changes in the concentration of water vapour in a gas stream were tracked and the range of detection was established along with stability and resolution of the chemically sensitised FBAR. FBAR device gold surfaces were coated with biological antibodies, these made the devices ultra specific to measurand. Direct experimental comparisons between the FBAR and the relative performance of well established but lower frequency acoustic wave immunosensor technology systems were made and the relative increase in sensitivity was established for the FBAR based immunosensor. Optical methods were used to compliment the acoustic ones in determining the thickness and density of the protein layers adsorbed to equivalent gold surfaces. The thesis concludes with a section of speculative ideas for future work, with the experimental results for a potential rheological probe device shown. A brief demonstration of the FBAR performance when submerged in semi-infinite liquid environments is shown. Arrays of FBAR devices are software modelled in a novel way and demonstration of their possible applications are presented

The UV Effect on the Chemiresistive Response of ZnO Nanostructures to Isopropanol and Benzene at PPM Concentrations in Mixture with Dry and Wet Air

Towards the development of low-power miniature gas detectors, there is a high interest in the research of light-activated metal oxide gas sensors capable to operate at room temperature (RT). Herein, we study ZnO nanostructures grown by the electrochemical deposition method over Si/SiO$_{2}$ substrates equipped by multiple Pt electrodes to serve as on-chip gas monitors and thoroughly estimate its chemiresistive performance upon exposing to two model VOCs, isopropanol and benzene, in a wide operating temperature range, from RT to 350 °C, and LED-powered UV illumination, 380 nm wavelength; the dry air and humid-enriched, 50 rel. %, air are employed as a background. We show that the UV activation allows one to get a distinctive chemiresistive signal of the ZnO sensor to isopropanol at RT regardless of the interfering presence of H$_{2}$O vapors. On the contrary, the benzene vapors do not react with UV-illuminated ZnO at RT under dry air while the humidity’s appearance gives an opportunity to detect this gas. Still, both VOCs are well detected by the ZnO sensor under heating at a 200–350 °C range independently on additional UV exciting. We employ quantum chemical calculations to explain the differences between these two VOCs’ interactions with ZnO surface by a remarkable distinction of the binding energies characterizing single molecules, which is −0.44 eV in the case of isopropanol and −3.67 eV in the case of benzene. The full covering of a ZnO supercell by H$_{2}$O molecules taken for the effect’s estimation shifts the binding energies to −0.50 eV and −0.72 eV, respectively. This theory insight supports the experimental observation that benzene could not react with ZnO surface at RT under employed LED UV without humidity’s presence, indifference to isopropanol

Spectral Signature Modification By Application Of Infrared Frequency-selective Surfaces

It is desirable to modify the spectral signature of a surface, particularly in the infrared (IR) region of the electromagnetic spectrum. To alter the surface signature in the IR, two methods are investigated: thin film application and antenna array application. The former approach is a common and straightforward incorporation of optically-thin film coatings on the surface designated for signature modification. The latter technique requires the complex design of a periodic array of passive microantenna elements to cover the surface in order to modify its signature. This technology is known as frequency selective surface (FSS) technology and is established in the millimeter-wave spectral regime, but is a challenging technology to scale for IR application. Incorporation of thin films and FSS antenna elements on a surface permits the signature of a surface to be changed in a deterministic manner. In the seminal application of this work, both technologies are integrated to comprise a circuit-analog absorbing IR FSS. The design and modeling of surface treatments are accomplished using commercially-available electromagnetic simulation software. Fabrication of microstructured antenna arrays is accomplished via microlithographic technology, particularly using an industrial direct-write electron-beam lithography system. Comprehensive measurement methods are utilized to study the patterned surfaces, including infrared spectral radiometry and Fourier-transform infrared spectrometry. These systems allow for direct and complementary spectral signature measurements--the radiometer measures the absorption or emission of the surface, and the spectrometer measures its transmission and reflection. For the circuit-analog absorbing square-loop IR FSS, the spectral modulation in emission is measured to be greater than 85% at resonance. Other desirable modifications of surface signature are also explored; these include the ability to filter radiation based on its polarization orientation and the ability to dynamically tune the surface signature. An array of spiral FSS elements allows for circular polarization conditioning. Three techniques for tuning the IR FSS signature via voltage application are explored, including the incorporation of a pn junction substrate, a piezoelectric substrate and a liquid crystal superstrate. These studies will ignite future explorations of IR FSS technology, enabling various unique applications