High-Throughput Compatibility Screening of Materials for SF6-Alternative Insulation.

With the annual global electricity production exceeding 30,000 TWh, the safe transmission of electric power has been heavily relying on SF6, the most potent industrial greenhouse gas. While promising SF6 alternatives have been proposed, their compatibilities with materials used in gas-insulated equipment (GIE) must be thoroughly studied. This is particularly true as the emerging SF6 alternatives generally leverage their relatively higher reactivity to achieve lower global warming potentials (GWPs). Here, a high-throughput compatibility screening of common GIE materials was conducted with a representative SF6 alternative, namely, C4F7N (2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile)/CO2 gas mixtures. In this screening, the insulation performance of C4F7N/CO2 gas mixtures, as an indicator of the C4F7N/materials compatibility level, was periodically monitored during the thermal aging with tens of materials from SF6-insulated GIE, including desiccants/adsorbents, rubber, plastics, composites, ceramics, metals, etc. The identification of incompatible materials and the follow-up mechanism studies suggested that the acidity of materials represents the primary cause for C4F7N/materials incompatibility when C4F7N/CO2 gas mixtures are used as a drop-in replacement solution for existing SF6-insulated apparatuses. Mitigation strategies tackling the acidity of materials were then proposed and validated. Additionally, the amphoteric characteristics of C4F7N were briefly discussed. This work provides insight into the materials incompatibility of SF6 alternatives, along with validated mitigation strategies, for the selection and design of materials used in future eco-friendly GIE.

Multivariable Sensors for Ubiquitous Monitoring of Gases in the Era of Internet of Things and Industrial Internet.

Modern gas monitoring scenarios for medical diagnostics, environmental surveillance, industrial safety, and other applications demand new sensing capabilities. This Review provides analysis of development of new generation of gas sensors based on the multivariable response principles. Design criteria of these individual sensors involve a sensing material with multiresponse mechanisms to different gases and a multivariable transducer with independent outputs to recognize these different gas responses. These new sensors quantify individual components in mixtures, reject interferences, and offer more stable response over sensor arrays. Such performance is attractive when selectivity advantages of classic gas chromatography, ion mobility, and mass spectrometry instruments are canceled by requirements for no consumables, low power, low cost, and unobtrusive form factors for Internet of Things, Industrial Internet, and other applications. This Review is concluded with a perspective for future needs in fundamental and applied aspects of gas sensing and with the 2025 roadmap for ubiquitous gas monitoring.

Toward high value sensing: monolayer-protected metal nanoparticles in multivariable gas and vapor sensors.

For detection of gases and vapors in complex backgrounds, "classic" analytical instruments are an unavoidable alternative to existing sensors. Recently a new generation of sensors, known as multivariable sensors, emerged with a fundamentally different perspective for sensing to eliminate limitations of existing sensors. In multivariable sensors, a sensing material is designed to have diverse responses to different gases and vapors and is coupled to a multivariable transducer that provides independent outputs to recognize these diverse responses. Data analytics tools provide rejection of interferences and multi-analyte quantitation. This review critically analyses advances of multivariable sensors based on ligand-functionalized metal nanoparticles also known as monolayer-protected nanoparticles (MPNs). These MPN sensing materials distinctively stand out from other sensing materials for multivariable sensors due to their diversity of gas- and vapor-response mechanisms as provided by organic and biological ligands, applicability of these sensing materials for broad classes of gas-phase compounds such as condensable vapors and non-condensable gases, and for several principles of signal transduction in multivariable sensors that result in non-resonant and resonant electrical sensors as well as material- and structure-based photonic sensors. Such features should allow MPN multivariable sensors to be an attractive high value addition to existing analytical instrumentation.

Discovery of the surface polarity gradient on iridescent Morpho butterfly scales reveals a mechanism of their selective vapor response.

For almost a century, the iridescence of tropical Morpho butterfly scales has been known to originate from 3D vertical ridge structures of stacked periodic layers of cuticle separated by air gaps. Here we describe a biological pattern of surface functionality that we have found in these photonic structures. This pattern is a gradient of surface polarity of the ridge structures that runs from their polar tops to their less-polar bottoms. This finding shows a biological pattern design that could stimulate numerous technological applications ranging from photonic security tags to self-cleaning surfaces, gas separators, protective clothing, sensors, and many others. As an important first step, this biomaterial property and our knowledge of its basis has allowed us to unveil a general mechanism of selective vapor response observed in the photonic Morpho nanostructures. This mechanism of selective vapor response brings a multivariable perspective for sensing, where selectivity is achieved within a single chemically graded nanostructured sensing unit, rather than from an array of separate sensors.

Design and Application of Variable Temperature Setup for Scanning Electron Microscopy in Gases and Liquids at Ambient Conditions.

Scanning electron microscopy (SEM) of nanoscale objects in dry and fully hydrated conditions at different temperatures is of critical importance in revealing details of their interactions with an ambient environment. Currently available WETSEM capsules are equipped with thin electron-transparent membranes and allow imaging of samples at atmospheric pressure, but do not provide temperature control over the sample. Here, we developed and tested a thermoelectric cooling/heating setup for WETSEM capsules to allow ambient pressure in situ SEM studies with a temperature range between -15 and 100°C in gaseous, liquid, and frozen conditions. The design of the setup also allows for correlation of the SEM with optical microscopy and spectroscopy. As a demonstration of the possibilities of the developed approach, we performed real-time in situ microscopy studies of water condensation on a surface of Morpho sulkowskyi butterfly wing scales. We observed that initial water nucleation takes place on top of the scale ridges. These results confirmed earlier discovery of a preexisting polarity gradient of the ridges of Morpho butterflies. Our developed thermoelectric cooling/heating setup for environmental capsules meets the diverse needs for in situ nanocharacterization in material science, catalysis, microelectronics, chemistry, and biology.

Towards maintenance-free biosensors for hundreds of bind/release cycles.

A single aptamer bioreceptor layer was formed using a common streptavidin-biotin immobilization strategy and employed for 100-365 bind/release cycles. Chemically induced aptamer unfolding and release of its bound target was accomplished using alkaline solutions with high salt concentrations or deionized (DI) water. The use of DI water scavenged from the ambient atmosphere represents a first step towards maintenance-free biosensors that do not require the storage of liquid reagents. The aptamer binding affinity was determined by surface plasmon resonance and found to be almost constant over 100-365 bind/release cycles with a variation of less than 5% relative standard deviation. This reversible operation of biosensors based on immobilized aptamers without storage of liquid reagents introduces a conceptually new perspective in biosensing. Such new biosensing capability will be important for distributed sensor networks, sensors in resource-limited settings, and wearable sensor applications.

Selective sensing of vapors of similar dielectric constants using peptide-capped gold nanoparticles on individual multivariable transducers.

Peptide-capped AYSSGAPPMPPF gold nanoparticles were demonstrated for highly selective chemical vapor sensing using individual multivariable inductor-capacitor-resistor (LCR) resonators. Their multivariable response was achieved by measuring their resonance impedance spectra followed by multivariate spectral analysis. Detection of model toxic vapors and chemical agent simulants, such as acetonitrile, dichloromethane and methyl salicylate, was performed. Dichloromethane (dielectric constant εr = 9.1) and methyl salicylate (εr = 9.0) were discriminated using a single sensor. These sensing materials coupled to multivariable transducers can provide numerous opportunities for tailoring the vapor response selectivity based on the diversity of the amino acid composition of the peptides, and by the modulation of the nature of peptide-nanoparticle interactions through designed combinations of hydrophobic and hydrophilic amino acids.

A Passive Radio-Frequency Identification (RFID) Gas Sensor With Self-Correction Against Fluctuations of Ambient Temperature.

Uncontrolled fluctuations of ambient temperature in the field typically greatly reduce accuracy of gas sensors. In this study, we developed an approach for the self-correction against fluctuations of ambient temperature of individual gas and vapor sensors. The main innovation of our work is in the temperature correction which is accomplished without the need for a separate uncoated reference sensor or a separate temperature sensor. Our sensors are resonant inductor-capacitor-resistor (LCR) transducers coated with sensing materials and operated as multivariable passive (battery-free) radio-frequency identification (RFID) sensors. Using our developed approach, we performed quantitation of an exemplary vapor over the temperature range from 25 to 40 °C. This technical solution will be attractive in numerous applications where temperature stabilization of a gas sensor or addition of auxiliary temperature or uncoated reference sensors is prohibitive.

Selective gas sensing with a single pristine graphene transistor.

We show that vapors of different chemicals produce distinguishably different effects on the low-frequency noise spectra of graphene. It was found in a systematic study that some gases change the electrical resistance of graphene devices without changing their low-frequency noise spectra while other gases modify the noise spectra by inducing Lorentzian components with distinctive features. The characteristic frequency f(c) of the Lorentzian noise bulges in graphene devices is different for different chemicals and varies from f(c) = 10-20 Hz to f(c) = 1300-1600 Hz for tetrahydrofuran and chloroform vapors, respectively. The obtained results indicate that the low-frequency noise in combination with other sensing parameters can allow one to achieve the selective gas sensing with a single pristine graphene transistor. Our method of gas sensing with graphene does not require graphene surface functionalization or fabrication of an array of the devices with each tuned to a certain chemical.

First-Order Individual Gas Sensors as Next Generation Reliable Analytical Instruments.

It is conventionally expected that the performance of existing gas sensors may degrade in the field compared to laboratory conditions because (i) a sensor may lose its accuracy in the presence of chemical interferences and (ii) variations of ambient conditions over time may induce sensor-response fluctuations (i.e., drift). Breaking this status quo in poor sensor performance requires understanding the origins of design principles of existing sensors and bringing new principles to sensor designs. Existing gas sensors are single-output (e.g., resistance, electrical current, light intensity, etc.) sensors, also known as zero-order sensors (Karl Booksh and Bruce R. Kowalski, Analytical Chemistry, DOI: 10.1021/ac00087a718). Any zero-order sensor is undesirably affected by variable chemical background and sensor drift that cannot be distinguished from the response to an analyte. To address these limitations, we are developing multivariable gas sensors with independent responses, which are first-order analytical instruments. Here, we demonstrate self-correction against drift in two types of first-order gas sensors that operate in different portions of the electromagnetic spectrum. Our radiofrequency sensors utilize dielectric excitation of semiconducting metal oxide materials on the shoulder of their dielectric relaxation peak and achieve self-correction of the baseline drift by operation at several frequencies. Our photonic sensors utilize nanostructured sensing materials inspired by Morpho butterflies and achieve self-correction of the baseline drift by operation at several wavelengths. These principles of self-correction for drift effects in first-order sensors open opportunities for diverse emerging monitoring applications that cannot afford frequent periodic maintenance that is typical of traditional analytical instruments.

Wireless sensors and sensor networks for homeland security applications.

New sensor technologies for homeland security applications must meet the key requirements of sensitivity to detect agents below risk levels, selectivity to provide minimal false-alarm rates, and response speed to operate in high throughput environments, such as airports, sea ports, and other public places. Chemical detection using existing sensor systems is facing a major challenge of selectivity. In this review, we provide a brief summary of chemical threats of homeland security importance; focus in detail on modern concepts in chemical sensing; examine the origins of the most significant unmet needs in existing chemical sensors; and, analyze opportunities, specific requirements, and challenges for wireless chemical sensors and wireless sensor networks (WSNs). We further review a new approach for selective chemical sensing that involves the combination of a sensing material that has different response mechanisms to different species of interest, with a transducer that has a multi-variable signal-transduction ability. This new selective chemical-sensing approach was realized using an attractive ubiquitous platform of battery-free passive radio-frequency identification (RFID) tags adapted for chemical sensing. We illustrate the performance of RFID sensors developed in measurements of toxic industrial materials, humidity-independent detection of toxic vapors, and detection of chemical-agent simulants, explosives, and strong oxidizers.

Multivariable passive RFID vapor sensors: roll-to-roll fabrication on a flexible substrate.

We demonstrate roll-to-roll (R2R) fabrication of highly selective, battery-free radio frequency identification (RFID) sensors on a flexible polyethylene terephthalate (PET) polymeric substrate. Selectivity of our developed RFID sensors is provided by measurements of their resonance impedance spectra, followed by the multivariate analysis of spectral features, and correlation of these spectral features to the concentrations of vapors of interest. The multivariate analysis of spectral features also provides the ability for the rejection of ambient interferences. As a demonstration of our R2R fabrication process, we employed polyetherurethane (PEUT) as a "classic" sensing material, extruded this sensing material as 25, 75, and 125-µm thick films, and thermally laminated the films onto RFID inlays, rapidly producing approximately 5000 vapor sensors. We further tested these RFID vapor sensors for their response selectivity toward several model vapors such as toluene, acetone, and ethanol as well as water vapor as an abundant interferent. Our RFID sensing concept features 16-bit resolution provided by the sensor reader, granting a highly desired independence from costly proprietary RFID memory chips with a low-resolution analog input. Future steps are being planned for field-testing of these sensors in numerous conditions.

Theoretical limit of localized surface plasmon resonance sensitivity to local refractive index change and its comparison to conventional surface plasmon resonance sensor.

In this paper, the theoretical sensitivity limit of the localized surface plasmon resonance (LSPR) to the surrounding dielectric environment is discussed. The presented theoretical analysis of the LSPR phenomenon is based on perturbation theory. Derived results can be further simplified assuming quasistatic limit. The developed theory shows that LSPR has a detection capability limit independent of the particle shape or arrangement. For a given structure, sensitivity is directly proportional to the resonance wavelength and depends on the fraction of the electromagnetic energy confined within the sensing volume. This fraction is always less than unity; therefore, one should not expect to find an optimized nanofeature geometry with a dramatic increase in sensitivity at a given wavelength. All theoretical results are supported by finite-difference time-domain calculations for gold nanoparticles of different geometries (rings, split rings, paired rings, and ring sandwiches). Numerical sensitivity calculations based on the shift of the extinction peak are in good agreement with values estimated by perturbation theory. Numerical analysis shows that, for thin (≤10 nm) analyte layers, sensitivity of the LSPR is comparable with a traditional surface plasmon resonance sensor and LSPR has the potential to be significantly less sensitive to temperature fluctuations.

Direct laser writing of vapour-responsive photonic arrays.

Using direct laser writing, arrays of optically responsive ionogel structures were fabricated. To demonstrate their responsive nature, visible colour changes in the presence of different solvent vapours were investigated. This represents a new departure for photonic structural colouration, in which the fabricating structure shows a programmable, controllable, and dynamic stimuli response.

Digital electrical impedance analysis for single bacterium sensing and antimicrobial susceptibility testing.

Single-molecule and single-cell analysis techniques have opened new opportunities for characterizing and analyzing heterogeneity within biological samples. These detection methods are often referred to as digital assays because the biological sample is partitioned into many small compartments and each compartment contains a discrete number of targets (e.g. cells). Using digital assays, researchers can precisely detect and quantify individual targets, and this capability has made digital techniques the basis for many modern bioanalytical tools (including digital PCR, single cell RNA sequencing, and digital ELISA). However, digital assays are dominated by optical analysis systems that typically utilize microscopy to analyze partitioned samples. The utility of digital assays may be dramatically enhanced by implementing cost-efficient and portable electrical detection capabilities. Herein, we describe a digital electrical impedance sensing platform that enables direct multiplexed measurement of single cell bacterial cells. We outline our solutions to the challenge of multiplexing impedance sensing across many culture compartments and demonstrate the potential for rapidly differentiating antimicrobial resistant versus susceptible strains of bacteria.

Combinatorial screening of polymeric sensing materials using RFID sensors: combined effects of plasticizers and temperature.

Recently, we have developed battery-free, passive RFID chemical and biological sensors that are attractive in diverse applications where sensor performance is needed at a low cost and when battery-free operation is critical. In this study, we apply this attractive low-cost sensing platform for the combinatorial screening of formulated sensing materials. As a model system, a 6 x 8 array of polymer-coated RFID sensors was constructed to study the combined effects of polymeric plasticizers and annealing temperature. A solid polymer electrolyte Nafion was formulated with five different phthalate plasticizers: dimethyl phthalate, butyl benzyl phthalate, di-(2-ethylhexyl) phthalate, dicapryl phthalate, and diisotridecyl phthalate. These sensing film formulations and control sensing films without a phthalate plasticizer were deposited onto 9-mm diameter RFID sensors, exposed to eight temperatures ranging from 40 to 140 degrees C using a gradient temperature heater, and evaluated for their response stability and gas-selectivity response patterns. This study demonstrated that our RFID-based sensing approach permits rapid cost-effective combinatorial screening of dielectric properties of sensing materials.

Label-free independent quantitation of viable and non-viable cells using a multivariable multi-resonant sensor.

Biological cells are utilized for diverse biotechnological and bioengineering purposes ranging from the production of biopharmaceuticals, to cell therapy, "human-on-a-chip" drug and toxicology assays, and drug-resistance tests. In these and other applications, it is critical to quantify the levels of not only viable but also non-viable cells. While traditional off-line cell-staining methods are available for counting of non-viable cells, many applications cannot periodically remove cells for their off-line analysis because of the risk of contamination or workflow logistics. Here we show in-situ label-free quantitation of viable and non-viable cells with multivariable multi-resonant sensors. We used Chinese hamster ovary (CHO) cells in suspension culture in single-use bioreactors as a representative example. The resonant sensor design strategy permitted enhanced sensor sensitivity versus conventional non-resonant measurements and probed the spectral dispersion of viable and non-viable cells with multiple resonances. These capabilities of label-free in-situ analysis of cell viability can be attractive in diverse cell applications such as cell suspensions, adhered cells, and their 3D assemblages.