Low cost 3D printable flow reactors for electrochemistry.

Transition to carbon neutrality requires the development of more sustainable pathways to synthesize the next generation of chemical building blocks. Electrochemistry is a promising pathway to achieve this goal, as it allows for the use of renewable energy to drive chemical transformations. While the electroreduction of carbon dioxide (CO2) and hydrogen evolution are attracting significant research interest, fundamental challenges exist in moving the research focus toward performing these reactions on scales relevant to industrial applications. To bridge this gap, we aim to facilitate researchers' access to flow reactors, which allow the characterization of electrochemical transformations under conditions closer to those deployed in the industry. Here, we provide a 3D-printable flow cell design (manufacturing cost < $5), which consists of several plates, offering a customizable alternative to commercially available flow reactors (cost > $6,000). The proposed design and detailed build instructions allow the performance of a wide variety of chemical reactions in flow, including gas and liquid phase electroreduction, electro(less)plating, and photoelectrochemical reactions, providing researchers with more flexibility and control over their experiments. By offering an accessible, low-cost reactor alternative, we reduce the barriers to performing research on sustainable electrochemistry, supporting the global efforts necessary to realize the paradigm shift in chemical manufacturing.

High Signal-to-Noise Ratio Event-Driven MEMS Motion Sensing.

Two solutions for improving MEMS triboelectric vibration sensors performance in contact-separation mode are reported experimentally and analytically. Triboelectric sensors have mostly been studied in the mesoscale. The gap variation between the electrodes induces a potential difference that represents the external vibration. Miniaturizing the device limits the sensor output because of the limited gap. This work offers a warped MEMS diaphragm constrained on its edges. The dome-shaped structure provides one order of magnitude larger displacement after contact-separation than standard designs resulting in one order of magnitude greater voltage and signal-to-noise-ratio. Second, micro triboelectric sensors do not operate unless the external vibration is sufficiently forceful to initiate contact between layers. The proposed constraints on the edge of the diaphragm provide friction during periodic motion and generate charges. The combination of the warped diaphragm and boundary constraints instead of serpentine springs increases the charge density and voltage generation. The mechanical properties and electrical output are thoroughly investigated including nonlinearity, sensitivity, and signal-to-noise ratio. A sensitivity of 250 mV g-1 and signal-to-noise-ratio of 32 dB is provided by the presented device at resonance, which is very promising for event-driven motion sensors because it does not require signal conditioning and therefore simplifies the sensing circuitry.

Quantum Oscillations in Graphene Using Surface Acoustic Wave Resonators.

Surface acoustic waves (SAWs) provide a contactless method for measuring wave-vector-dependent conductivity. This technique has been used to discover emergent length scales in the fractional quantum Hall regime of traditional, semiconductor-based heterostructures. SAWs would appear to be an ideal match for van der Waals heterostructures, but the right combination of substrate and experimental geometry to allow access to the quantum transport regime has not yet been found. We demonstrate that SAW resonant cavities fabricated on LiNbO_{3} substrates can be used to access the quantum Hall regime of high-mobility, hexagonal boron nitride encapsulated, graphene heterostructures. Our work establishes SAW resonant cavities as a viable platform for performing contactless conductivity measurements in the quantum transport regime of van der Waals materials.

Polymer interdigitated pillar electrostatic (PIPE) actuators.

This work reports a three-dimensional polymer interdigitated pillar electrostatic actuator that can produce force densities 5-10× higher than those of biological muscles. The theory of operation, scaling, and stability is investigated using analytical and FEM models. The actuator consists of two high-density arrays of interdigitated pillars that work against a restoring force generated by an integrated flexure spring. The actuator architecture enables linear actuation with higher displacements and pull-in free actuation to prevent the in-use stiction associated with other electrostatic actuators. The pillars and springs are 3D printed together in the same structure. The pillars are coated with a gold-palladium alloy layer to form conductive electrodes. The space between the pillars is filled with liquid dielectrics for higher breakdown voltages and larger electrostatic forces due to the increase in the dielectric constant. We demonstrated a prototype actuator that produced a maximum work density of 54.6 µJ/cc and an electrical-to-mechanical energy coupling factor of 32% when actuated at 4000 V. The device was operated for more than 100,000 cycles with no degradation in displacements. The flexible polymer body was robust, allowing the actuator to operate even after high mechanical force impact, which was demonstrated by operation after drop tests. As it is scaled further, the reported actuator will enable soft and flexible muscle-like actuators that can be stacked in series and parallel to scale the resulting forces. This work paves the way for high-energy density actuators for microrobotic applications.

Non-contact ultrasound oocyte denudation.

Cumulus removal (CR) is a central prerequisite step for many protocols involved in the assisted reproductive technology (ART) such as intracytoplasmic sperm injection (ICSI) and preimplantation genetic testing (PGT). The most prevalent CR technique is based upon laborious manual pipetting, which suffers from inter-operator variability and therefore a lack of standardization. Automating CR procedures would alleviate many of these challenges, improving the odds of a successful ART or PGT outcome. In this study, a chip-scale ultrasonic device consisting of four interdigitated transducers (IDT) on a lithium niobate substrate has been engineered to deliver megahertz (MHz) range ultrasound to perform denudation. The acoustic streaming and acoustic radiation force agitate COCs inside a microwell placed on top of the LiNbO3 substrate to remove the cumulus cells from the oocytes. This paper demonstrates the capability and safety of the denudation procedure utilizing surface acoustic wave (SAW), achieving automation of this delicate manual procedure and paving the steps toward improved and standardized oocyte manipulation.

Gradient-Based Microfluidic Platform for One Single Rapid Antimicrobial Susceptibility Testing.

Antimicrobial resistance is a growing problem, necessitating rapid antimicrobial susceptibility testing (AST) to enable effective in-clinic diagnostic testing and treatment. Conventional AST using broth microdilution or the Kirby-Bauer disk diffusion are time-consuming (e.g., 24-72 h), labor-intensive, and costly and consume reagents. Here, we propose a novel gradient-based microchamber microfluidic (GM2) platform to perform AST assay for a wide range of antibiotic concentrations plus zero (positive control) and maximum (negative control) concentrations all in a single test. Antibiotic lateral diffusion within enriched to depleted (Cmax and zero, respectively) cocurrent flowing fluids, moving alongside a micron-sized main channel, is led to form an antibiotic concentration profile in microchambers, connected to the depleted side of the main channel. We examined the tunability of the GM2 platform, in terms of producing a wide range of antibiotic concentrations in a gradient mode between two consecutive microchambers with changing either the loading fluids' flow rates or their initial concentrations. We also tested the GM2 platform for profiling bacteria associated with human Crohn's disease and bovine mastitis. Time to result for performing a complete AST assay was ∼ 3-4 h in the GM2 platform. Lastly, the GM2 platform tracked the bacterial growth independent of an antibiotic mechanism of action or bacterial species in a robust and easy-to-implement fashion.

Biological small-molecule assays using gradient-based microfluidics.

Studying the potency of small-molecules on eukaryotic and prokaryotic cells using conventional biological settings requires time-consuming procedures and large volumes of expensive small-molecules. Microfluidics could significantly expedite these assays by enabling operation in high-throughput and (semi)automated modes. Here, we introduce a microfluidics platform based on multi-volume microchamber arrays that can produce a wide range of small-molecule concentrations with a desired gradient-based profile for rapid and precise biological testing within a single device with minimal hands-on time. The concept behind this device is based on introducing the same amount of a small-molecule into microchambers of different volumes to spontaneously generate a gradient concentration profile via diffusion. This design enables to obtain an unprecedented concentration range (e.g., three orders of magnitude) that can be easily adjusted, allowing us to pinpoint the precise effect of small-molecules on pre-loaded prokaryotic and eukaryotic cells. We also propose a comprehensive relationship for determining the loading time (the only required parameter for implementing this platform) in order to study the effects of any small-molecule on a biological species in a desired test. We demonstrate the versatility of this microfluidics platform by conducting two small-molecule assays-antimicrobial resistance and sugar-phosphate toxicity for both eukaryotic and prokaryotic biological systems.

Microscale direct measurement of localized photothermal heating in tissue-mimetic hydrogels.

Photothermal hyperthermia is proven to be an effective diagnostic tool for cancer therapy. The efficacy of this method directly relies on understanding the localization of the photothermal effect in the targeted region. Realizing the safe and effective concentration of nano-particles and the irradiation intensity and time requires spatiotemporal temperature monitoring during and after laser irradiation. Due to uniformities of the nanoparticle distribution and the complexities of the microenvironment, a direct temperature measurement in micro-scale is crucial for achieving precise thermal dose control. In this study, a 50 nm thin film nickel resistive temperature sensor was fabricated on a 300 nm SiN membrane to directly measure the local temperature variations of a hydrogel-GNR mixture under laser exposure with 2 mK temperature resolution. The chip-scale approach developed here is an effective tool to investigate localization of photothermal heating for hyperthermia applications for in-vitro and ex-vivo models. Considering the connection between thermal properties, porosity and the matrix stiffness in hydrogels, we present our results using the interplay between matrix stiffness of the hydrogel and its thermal properties: the stiffer the hydrogel, the higher the thermal conductivity resulting in lower photothermal heating. We measured 8.1, 7.4, and 5.6 °C temperature changes (from the room temperature, 20 °C) in hydrogel models with stiffness levels corresponding to adipose (4 kPa), muscle (13 kPa) and osteoid (30 kPa) tissues respectively by exposing them to 2 W/cm2 laser (808 nm) intensity for 150 seconds.

On-chip detection of gel transition temperature using a novel micro-thermomechanical method.

We present a new thermomechanical method and a platform to measure the phase transition temperature at microscale. A thin film metal sensor on a membrane simultaneously measures both temperature and mechanical strain of the sample during heating and cooling cycles. This thermomechanical principle of operation is described in detail. Physical hydrogel samples are prepared as a disc-shaped gels (200 µm thick and 1 mm diameter) and placed between an on-chip heater and sensor devices. The sol-gel transition temperature of gelatin solution at various concentrations, used as a model physical hydrogel, shows less than 3% deviation from in-depth rheological results. The developed thermomechanical methodology is promising for precise characterization of phase transition temperature of thermogels at microscale.

A patterned single layer graphene resistance temperature sensor.

Micro-fabricated single-layer graphenes (SLGs) on a silicon dioxide (SiO2)/Si substrate, a silicon nitride (SiN) membrane, and a suspended architecture are presented for their use as temperature sensors. These graphene temperature sensors act as resistance temperature detectors, showing a quadratic dependence of resistance on the temperature in a range between 283 K and 303 K. The observed resistance change of the graphene temperature sensors are explained by the temperature dependent electron mobility relationship (~T-4) and electron-phonon scattering. By analyzing the transient response of the SLG temperature sensors on different substrates, it is found that the graphene sensor on the SiN membrane shows the highest sensitivity due to low thermal mass, while the sensor on SiO2/Si reveals the lowest one. Also, the graphene on the SiN membrane reveals not only the fastest response, but also better mechanical stability compared to the suspended graphene sensor. Therefore, the presented results show that the temperature sensors based on SLG with an extremely low thermal mass can be used in various applications requiring high sensitivity and fast operation.

Thermal Measurement Techniques in Analytical Microfluidic Devices.

Thermal measurement techniques have been used for many applications such as thermal characterization of materials and chemical reaction detection. Micromachining techniques allow reduction of the thermal mass of fabricated structures and introduce the possibility to perform high sensitivity thermal measurements in the micro-scale and nano-scale devices. Combining thermal measurement techniques with microfluidic devices allows performing different analytical measurements with low sample consumption and reduced measurement time by integrating the miniaturized system on a single chip. The procedures of thermal measurement techniques for particle detection, material characterization, and chemical detection are introduced in this paper.

A novel on-chip three-dimensional micromachined calorimeter with fully enclosed and suspended thin-film chamber for thermal characterization of liquid samples.

A microfabricated calorimeter (µ-calorimeter) with an enclosed reaction chamber is presented. The 3D micromachined reaction chamber is capable of analyzing liquid samples with volume of 200 nl. The thin film low-stress silicon nitride membrane is used to reduce thermal mass of the calorimeter and increase the sensitivity of system. The µ-calorimeter has been designed to perform DC and AC calorimetry, thermal wave analysis, and differential scanning calorimetry. The µ-calorimeter fabricated with an integrated heater and a temperature sensor on opposite sides of the reaction chamber allows to perform thermal diffusivity and specific heat measurements on liquid samples with same device. Measurement results for diffusivity and heat capacitance using time delay method and thermal wave analysis are presented.

A paper-based calorimetric microfluidics platform for bio-chemical sensing.

In this report, a paper-based micro-calorimetric biochemical detection method is presented. Calorimetric detection of biochemical reactions is demonstrated as an extension of current colorimetric and electrochemical detection mechanisms of paper-based biochemical analytical systems. Reaction and/or binding temperature of glucose/glucose oxidase, DNA/hydrogen peroxide, and biotin/streptavidin, are measured by the paper-based micro-calorimeter. Commercially available glucose calibration samples of 0.05, 0.15 and 0.3% wt/vol concentration are used for comparing the device performance with a commercially available glucose meter (electrochemical detection). The calorimetric glucose detection demonstrates a measurement error less than 2%. The calorimetric detection results of DNA concentrations from 0.9 to 7.3 mg/mL and temperature changes in biotin and streptavidin reaction are presented to demonstrate the feasibility of integrating the calorimetric detection method with paper based microfluidic devices.