Nicola Menegazzo

Infrared hollow waveguide sensors for simultaneous gas phase detection of benzene, toluene, and xylenes in field environments.

Simultaneous and molecularly selective parts-per-billion detection of benzene, toluene, and xylenes (BTX) using a thermal desorption (TD)-FTIR hollow waveguide (HWG) trace gas sensor is demonstrated here for the first time combining laboratory calibration with real-world sample analysis in field. A calibration range of 100-1000 ppb analyte/N(2) was developed and applied for predicting the concentration of blinded environmental air samples within the same concentration range, and demonstrate close agreement with the validation method used here, GC-FID. The analyte concentration prediction capability of the TD-FTIR-HWG trace gas sensor also compares well with the industrial standard and other experimental techniques including GC-PID, ultrafast GC-FID, and GC-DMS, which were simultaneously operated in the field. With the advent of a quantum cascade laser with emission frequencies specifically tailored to efficiently overlap benzene absorption as the most relevant analyte, the overall sensor footprint could be considerably reduced to ultimately yield hand-held trace gas sensors facilitating direct and real-time detection of BTX in air down to low ppb levels.

Analytical and physical optimization of nanohole-array sensors prepared by modified nanosphere lithography

The analytical and physical properties are reported for nanohole arrays prepared with glancing angle deposition (GLAD) or plasma treatment of a nanosphere lithography (NSL) mask prior to the deposition of a thin Au film. The nanohole arrays obtained with a 450 nm nanospheres mask are characterized using atomic force microscopy (AFM) to determine the depth and the width of the nanoholes, and the periodicity of the nanohole arrays. The analytical properties are reported in terms of the surface plasmon (SP) excitation wavelength (500 nm to 1000 nm), sensitivity to refractive index (27 nm RIU(-1) to 487 nm RIU(-1)), sensitivity to monolayer formation (shift of the SP band by approx. 1 nm), and refractive index resolution (10(-4) RIU). These simple techniques produce well-ordered nanohole arrays with tunable analytical and physical properties for the development of biosensors.

Mid-Infrared Trace Gas Analysis with Single-Pass Fourier Transform Infrared Hollow Waveguide Gas Sensors:

A hollow core optical fiber gas sensor has been developed in combination with a Fourier transform infrared (FT-IR) spectrometer operating in the spectral range of 4000–500 cm−1, enabling continuous detection of small volume gas-phase analytes such as CH4, CO2, C2H5Cl, or their mixtures at trace levels. Ag/Ag-halide hollow core optical fibers simultaneously serve as an optical waveguide for broad-band mid-infrared radiation and as a miniaturized absorption gas cell. Specifically, carbon dioxide, methane, and ethyl chloride as well as binary mixtures in a carrier gas were analyzed during exponential dilution experiments. In the studies reported here, the integration of an optical gas sensor with FT-IR spectroscopy provides excellent detection limits for small gas volumes (∼1.5 mL) of individual analytes at a few tens of parts per billion (ppb, vol/vol) for carbon dioxide and a few hundreds of ppb (vol/vol) for methane. Furthermore, the broad-band nature of the radiation source and of the hollow core optical waveguide provides the capability of multi-constituent analysis in mixtures.

Discourse on the utilization of polyaniline coatings for surface plasmon resonance sensing of ammonia vapor.

Surface plasmon resonance spectroscopy is sensitive to near-surface (<300 nm) chemical and physical events that result in refractive index changes. The non-specific nature of the stimulus implies that chemical selectivity in SPR sensing configurations entirely relies upon the chemical recognition scheme employed. Biosensing applications commonly use surface layers composed of antibodies or enzymes for biomolecular recognition. Monitoring of volatile compounds with SPR spectroscopy, however, has not been widely discussed due to the difficulty in selectively responding to small molecules (<100 Da) in addition to the limited refractive index changes resulting from the interaction between the plasmon wave and volatile compounds. Different strategies explored thus far for sensing of small molecules have relied on optical and electrical changes of the recognition layer upon exposure to the analyte, yielding an indirect measurement. Examples of coatings used for gas-phase sensing with SPR include conducting metal oxides, polymers and organometallic dyes. Electrically conducting polymers, like polyaniline and polypyrrole, display dramatic conductivity changes in the presence of certain compounds. This property has resulted in their routine incorporation into different sensing schemes. However, application of electrically conducting polymers to SPR gas-phase sensing has been limited to a few examples, despite encouraging results. The emeraldine salt form of polyaniline (PAni) demonstrates a decreased electrical conductivity correlated to NH(3) concentration. In this contribution, PAni doped with camphorsulfonic acid (PAni-CSA) was applied to gas-phase sensing of NH(3) by way of SPR spectroscopy. Spectroscopic ellipsometry was used to determine the optical constants (n and k) for emeraldine salt and emeraldine base forms of PAni, confirming the wavelength-dependent response observed via SPR. The analytical performance of the coatings show that a limit of detection of 32 ppm NH(3) based on precision of the mass-flow controllers used and an estimated method limit of detection of ∼0.2 ppm based on three standard deviations of the blank. This is directly comparable to other, more established sensing architectures.

Glucose detection with surface plasmon resonance spectroscopy and molecularly imprinted hydrogel coatings.

Molecularly imprinted hydrogel membranes were developed and evaluated for detection of small analytes via surface plasmon resonance spectroscopy. Imprinting of glucose phosphate barium salt into a poly(allylamine hydrochloride) network covalently bound to gold surfaces yielded a selective sensor for glucose. Optimization of relative amounts of chemicals used for preparation of the hydrogel was performed to obtain highest sensitivity. Addition of gold nanoparticles into the hydrogel matrix significantly amplified its response and sensitivity due to the impact of gold nanoparticles on the refractive index of the sensing layer. Evaluation of its selectivity showed that the sensor displayed preferential recognition to glucose compared to structurally related sugars in addition to being unaffected by phosphate as well as compounds containing amine groups, like creatinine. The detection limit of glucose in deionized water was calculated to be 0.02 mg/mL. The developed sensor was finally exposed to human urine spiked with glucose illustrating the coatings ability to re-bind the analyte in complex matrices. While the working concentration range in water was determined to be suitable for glucose monitoring in diabetic individuals at physiological levels, the detection in urine was determined to be 0.12 mg/mL. The decreased performance in urine provided an initial perspective on the difficulties associated with measurements in complex media.

DC magnetron sputtered polyaniline-HCl thin films for chemical sensing applications.

Thin films of conducting polymers exhibit unique chemical and physical properties that render them integral parts in microelectronics, energy storage devices, and chemical sensors. Overall, polyaniline (PAni) doped in acidic media has shown metal-like electronic conductivity, though exact physical and chemical properties are dependent on the polymer structure and dopant type. Difficulties arising from poor processability render production of doped PAni thin films particularly challenging. In this contribution, DC magnetron sputtering, a physical vapor deposition technique, is applied to the preparation of conductive thin films of PAni doped with hydrochloric acid (PAni-HCl) in an effort to circumvent issues associated with conventional thin film preparation methods. Samples manufactured by the sputtering method are analyzed along with samples prepared by conventional drop-casting. Physical characterization (atomic force microscopy, AFM) confirm the presence of PAni-HCl and show that films exhibit a reduced roughness and potentially pinhole-free coverage of the substrate. Spectroscopic evidence (UV-vis, FT-IR, and X-ray photoelectron spectroscopy (XPS)) suggests that structural changes and loss of conductivity, not uncommon during PAni processing, does occur during the preparation process. Finally, the applicability of sputtered films to gas-phase sensing of NH(3) was investigated with surface plasmon resonance (SPR) spectroscopy and compared to previous contributions. In summary, sputtered PAni-HCl films exhibit quantifiable, reversible behavior upon exposure to NH(3) with a calculated LOD (by method) approaching 0.4 ppm NH(3) in dry air.

Characterization of a Variable Angle Reflection Fourier Transform Infrared Accessory Modified for Surface Plasmon Resonance Spectroscopy

The Harrick AutoSeagull variable angle reflection accessory for Fourier transform infrared (FT-IR) spectrometers provides access to various spectroscopic techniques in a highly flexible platform. In particular, its ability to perform total internal reflection measurements is of interest because it also forms the basis for surface plasmon resonance (SPR) spectroscopy in prism-based configurations. The work presented here discusses the modification of the AutoSeagull to perform SPR spectroscopy, allowing for easy incorporation of the technique into most common FT-IR spectrometers. The wavelength dependency of the dielectric constant of the plasmon-supporting metal (in our case, gold) is largely responsible for the sensitivity attributed to changes in the samples refractive index (RI) monitored by SPR spectroscopy. Furthermore, the optical properties of gold are such that when near-infrared (NIR) and/or mid-infrared (mid-IR) wavelengths are used to excite surface plasmons, higher sensitivities to RI changes are experienced compared to surface plasmons excited with visible wavelengths. The result is that in addition to instrumental simplicity, SPR analysis on FT-IR spectrometers, as permitted by the modified AutoSeagull, also benefits from the wavelength ranges accessible. Adaptation of the AutoSeagull to SPR spectroscopy involved the incorporation of slit apertures to minimize the angular spread reaching the detector, resulting in sharper SPR “dips” but at the cost of noisier spectra. In addition, discussion of the systems analytical performance includes comparison of dip quality as a function of slit size, tailoring of the dip minima location with respect to incident angle, and sensitivity to bulk RI changes.

Development and investigation of a dual-pad in-channel referencing surface plasmon resonance sensor.

Herein, we describe the construction of a novel dual-pad referencing surface plasmon resonance (SPR) sensor utilizing electrolytic grafting of diazonium salts to individually functionalize two gold pads positioned in a single fluidic channel. Using a dove prism, a simple single axis optical train may be employed without compromising the analytical performance. Once functionalized, one pad is used as the analytical sensing pad for detection of molecular interactions while the other serves as the reference pad, compensating for background refractive index fluctuations. The reference pad effectively compensates bulk refractive index changes and temperature variations as well as other nonspecific effects. The sensor was applied to calibration of a pH-responsive polymer layer in the presence of bulk refractive index and temperature variations. Monitoring selective attachment of a protein is also demonstrated. To our knowledge, this is the first implementation of in-channel referencing SPR sensor utilizing diazonium salt-based surface chemistry.

Characterization of electrografted 4-aminophenylalanine layers for low non-specific binding of proteins

Novel diazonium salts based on the 4-amino derivative of phenylalanine were electrografted onto gold surfaces with the ultimate goal of formation of surfaces resistant to nonspecific adsorption of proteins. A pulsed potential deposition profile was used instead of the more conventional approaches in order to circumvent mass-transport limitations. The influence of the deposition parameters, including pulse potentials, pulse width and number of pulses, with respect to electrode coverage was evaluated as a function of the blocking effect towards the diffusion of Fe(CN)64−/3− to electrode surfaces. By appropriately choosing the deposition parameters, peak potential differences (ΔEp) of ∼750 mV (for ν = 100 mV s−1), contrasting the ∼440 mV obtained for layers deposited via conventional electrochemical methods. FT-IR spectra confirm that the general structure of the electografted layers displays the same chemical functionality as the precursor molecule. Furthermore, the presence of the carboxylic acid group, characterized by the absorption feature at 1724 cm−1, indicates that the layers retain the ability to undergo post-deposition functionalization with bioreceptors. Ellipsometric analysis demonstrates the versatility of this method by depositing layers ranging from ∼1 to ∼24 nm thick. Finally, surface plasmon resonance spectroscopy was used to monitor the modified surfaces upon exposure to highly fouling media (76 mg mL−1 bovine serum albumin in phosphate buffered saline solution). A protein surface coverage equivalent to 62 ng cm−2 was measured, representing a significant improvement compared with more established antifouling layers based on polyethylene glycol (100 ng cm−2) and alkanethiol self-assembled monolayers (268 ng cm−2). The resistance towards nonspecific adsorption may be associated with the hydration layer tightly bound by the ionic charges present in the organic layer at physiological pH.

Adsorbate-metal bond effect on empirical determination of surface plasmon penetration depth.

The penetration depth of surface plasmons is commonly determined empirically from the observed response for adsorbate loading on gold surface plasmon resonance (SPR) substrates. However, changes in the SPR spectrum may originate from both changes in the effective refractive index near the metal surface and changes in the metal permittivity following covalent binding of the adsorbate layer. Herein, the significance of incorporating an additional adsorbate-metal bonding effect in the calculation is demonstrated in theory and in practice. The bonding effect is determined from the nonzero intercept of a SPR shift versus adsorbate thickness calibration and incorporated into the calculation of penetration depth at various excitation wavelengths. Determinations of plasmon penetration depth with and without the bonding response for alkanethiolate-gold are compared and are shown to be significantly different for a thiol monolayer adsorbate system. Additionally, plasmon penetration depth evaluated with bonding effect compensation shows greater consistency over different adsorbate thicknesses and better agreement with theory derived from Maxwells equation, particularly for adsorbate thicknesses that are much smaller (<5%) than the plasmon penetration depth. The method is also extended to a more practically applicable polyelectrolyte multilayer adsorbate system.