Understanding disorder in monolayer graphene devices with gate-defined superlattices.

Engineering superlattices (SLs)-which are spatially periodic potential landscapes for electrons-is an emerging approach for the realization of exotic properties, including superconductivity and correlated insulators, in two-dimensional materials. While moiré SL engineering has been a popular approach, nanopatterning is an attractive alternative offering control over the pattern and wavelength of the SL. However, the disorder arising in the system due to imperfect nanopatterning is seldom studied. Here, by creating a square lattice of nanoholes in the SiO2dielectric layer using nanolithography, we study the SL potential and the disorder formed in hBN-graphene-hBN heterostructures. Specifically, we observe that while electrical transport shows distinct SL satellite peaks, the disorder of the device is significantly higher than graphene devices without any SL. We use finite-element simulations combined with a resistor network model to calculate the effects of this disorder on the transport properties of graphene. We consider three types of disorder: nanohole size variations, adjacent nanohole mergers, and nanohole vacancies. Comparing our experimental results with the model, we find that the disorder primarily originates from nanohole size variations rather than nanohole mergers in square SLs. We further confirm the validity of our model by comparing the results with quantum transport simulations. Our findings highlight the applicability of our simple framework to predict and engineer disorder in patterned SLs, specifically correlating variations in the resultant SL patterns to the observed disorder. Our combined experimental and theoretical results could serve as a valuable guide for optimizing nanofabrication processes to engineer disorder in nanopatterned SLs.

Cellulose-Based Laser-Induced Graphene Devices for Electrochemical Monitoring of Bacterial Phenazine Production and Viability.

As an easily disposable substrate with a microporous texture, paper is a well-suited, generic substrate to build analytical devices for studying bacteria. Using a multi-pass lasing process, cellulose-based laser-induced graphene (cLIG) with a sheet resistance of 43.7 ± 2.3 Ωsq-1 is developed and utilized in the fabrication of low-cost and environmentally-friendly paper sensor arrays. Two case studies with Pseudomonas aeruginosa and Escherichia coli demonstrate the practicality of the cLIG sensors for the electrochemical analysis of bacteria. The first study measures the time-dependent profile of phenazines released from both planktonic (up to 60 h) and on-chip-grown (up to 22 h) Pseudomonas aeruginosa cultures. While similarities do exist, marked differences in phenazine production are seen with cells grown directly on cLIG compared to the planktonic culture. Moreover, in planktonic cultures, pyocyanin levels increase early on and plateau around 20 h, while optical density measurements increase monotonically over the duration of testing. The second study monitors the viability and metabolic activity of Escherichia coli using a resazurin-based electrochemical assay. These results demonstrate the utility of cLIG paper sensors as an inexpensive and versatile platform for monitoring bacteria and could enable new opportunities in high-throughput antibiotic susceptibility testing, ecological studies, and biofilm studies.

Experiences with telemedicine for HIV care in two federally qualified health centers in Los Angeles: a qualitative study.

BACKGROUND: The SARS-CoV-2 pandemic has resulted in an increase in telemedicine utilization for routine HIV care. However, there is limited information on perceptions of and experiences with telemedicine from United States (U.S.) federally qualified health centers (FQHCs) offering HIV care. We sought to understand telemedicine experiences of stakeholders with various roles: people living with HIV (PLHIV), clinical (clinicians and case managers), programmatic (clinic administrators), and policy (policymakers). METHODS: Qualitative interviews about benefits and challenges of telemedicine (telephone and video) for HIV care were conducted with 31 PLHIV and 23 other stakeholders (clinicians, case managers, clinic administrators, and policymakers). Interviews were transcribed, translated to English if conducted in Spanish, coded, and analyzed for major themes. RESULTS: Almost all PLHIV felt capable of engaging in telephone visits, with some expressing interest in learning how to use video visits as well. Nearly all PLHIV wanted to continue telemedicine as part of their routine HIV care, and this was also endorsed by clinical, programmatic and policy stakeholders. Interviewees agreed that telemedicine for HIV care has benefits for PLHIV, especially savings of time and transportation costs, which also reduced stress. Clinical, programmatic, and policy stakeholders expressed concerns around patients' technological literacy and resources, as well as their access to privacy, and some felt that PLHIV strongly preferred in-person visits. These stakeholders also commonly reported clinic-level implementation challenges, including integrating telephone and video telemedicine into workflows and difficulty with video visit platforms. CONCLUSIONS: Telemedicine for HIV care, largely delivered via telephone (audio-only), was highly acceptable and feasible for both PLHIV, clinicians, and other stakeholders. Addressing barriers for stakeholders in incorporating video visits will be important for the successful implementation of telemedicine with video as part of routine HIV care at FQHCs.

Unwelcoming: The Church Experiences of HIV-Infected Adolescents and Emerging Adults.

Acceptance among family, friends, and within the community is a critical developmental milestone during adolescence. Having a diagnosis of HIV may hinder or impede one's ability to develop socially. The purpose of our original study was to describe the role spirituality may play in HIV-infected adolescents and emerging adults. We interviewed 21 Christian-identified males using constructivist grounded theory methodology. The theory of the church not embracing HIV-infected youth was generated. The theme "unwelcoming" describes young people's attempts to connect with the church. Embracing adolescents and emerging adults in church may offer support and enhance their ability to cope with HIV.

Reconnecting to Spirituality: Christian-Identified Adolescents and Emerging Adult Young Men's Journey from Diagnosis of HIV to Coping.

Spirituality is important to holistic health, yet little is known about its impact on young people with HIV. To address this knowledge deficit, a grounded theory study used semi-structured interviews of 20 Christian-identified adolescent and emerging adult gay males and one perinatally infected male. This study revealed that, to cope with HIV health issues, participants used a process of reconnecting with their spirituality. In order to successfully reconnect with their spirituality, study participants reported a need to re-embrace and re-engage in spiritual practices, hold onto hope, believe they are normal, and commit to beliefs and practices despite rejection from the church.

Heart-on-a-chip systems: disease modeling and drug screening applications.

Cardiovascular disease (CVD) is the leading cause of death worldwide, casting a substantial economic footprint and burdening the global healthcare system. Historically, pre-clinical CVD modeling and therapeutic screening have been performed using animal models. Unfortunately, animal models oftentimes fail to adequately mimic human physiology, leading to a poor translation of therapeutics from pre-clinical trials to consumers. Even those that make it to market can be removed due to unforeseen side effects. As such, there exists a clinical, technological, and economical need for systems that faithfully capture human (patho)physiology for modeling CVD, assessing cardiotoxicity, and evaluating drug efficacy. Heart-on-a-chip (HoC) systems are a part of the broader organ-on-a-chip paradigm that leverages microfluidics, tissue engineering, microfabrication, electronics, and gene editing to create human-relevant models for studying disease, drug-induced side effects, and therapeutic efficacy. These compact systems can be capable of real-time measurements and on-demand characterization of tissue behavior and could revolutionize the drug development process. In this review, we highlight the key components that comprise a HoC system followed by a review of contemporary reports of their use in disease modeling, drug toxicity and efficacy assessment, and as part of multi-organ-on-a-chip platforms. We also discuss future perspectives and challenges facing the field, including a discussion on the role that standardization is expected to play in accelerating the widespread adoption of these platforms.

Agar-Integrated Three-Dimensional Microelectrodes for On-Chip Impedimetric Monitoring of Bacterial Viability.

Monitoring bacterial viability is critical in food safety, clinical microbiology, therapeutics, and microbial fuel cell applications. Traditional techniques for detecting and counting viable cells are slow, require expensive and bulky analytical tools and labeling agents, or are destructive to cells. Development of low-cost, portable diagnostics to enable label-free detection and in situ probing of bacterial viability can significantly advance the biomedical field (both applied and basic research). We developed a highly sensitive method for the detection of bacterial viability based on their metabolic activity using non-Faradaic impedimetric sensors comprised of three-dimensional (3D) interdigitated microelectrodes (3D-IDME). Specifically, the 3D-IDME is modified with electrolessly deposited gold (Au) nanoparticles which amplify the sensitivity by increasing the sensing area. A nutrient-rich agarose gel as the seeding layer is integrated with the sensor to enable direct culturing of bacteria and probing of their metabolic activity in situ. The proposed platform enables monitoring of bacterial viability, even in lag-phase, as they metabolize and release ionic species into the surrounding environment (nutrient agar layer). The sensor can detect down to 104 CFU/mL (~2.5 CFU/mm2) of Escherichia coli K12 (a model strain) in under 1 h without the need for any labeling. By integrating these sensors with agar layers containing different types/concentrations of antibacterial agents, this work can be expanded to enable rapid, high-throughput antibacterial susceptibility testing which can in turn assist caregivers in early prescription of the right treatment to patients with clinical conditions.

Rapid and sensitive detection of viral particles by coupling redox cycling and electrophoretic enrichment.

The COVID-19 pandemic has highlighted the need for rapid, low-cost, and sensitive virus detection platforms to monitor and mitigate widespread outbreaks. Electrochemical sensors are a viable choice to fill this role but still require improvements to the signal magnitude, especially for early detection and low viral loads. Herein, finite element analysis of a novel biosensor concept for single virion counting using a generator-collector microelectrode design is presented. The proposed design combines a redox-cycling amplified electrochemical current with electrophoresis-driven electrode-particle collision for rapid virus detection. The effects of experimental (e.g. scan rate, collector bias) and geometric factors are studied to optimize the sensor design. Two generator-collector configurations are explored: a ring-disk configuration to analyze sessile droplets and an interdigitated electrode (IDE) design housed in a microchannel. For the ring-disk configuration, we calculate an amplification factor of ∼5 and collector efficiency of ∼0.8 for a generator-collector spacing of 600 nm. For the IDE, the collector efficiency is even larger, approaching unity. The dual-electrode mode is critical for increasing the current and electric field strength. As a result, the current steps upon virus capture are more than an order of magnitude larger compared to single-mode. Additionally, single virus capture times are reduced from over 700 s down to ∼20 s. Overall, the frequency of virus capture and magnitude of the electrochemical current steps depend on the virus properties and electrode configuration, with the IDE capable of single virus detection within seconds owing to better particle confinement in the microchannel.

A machine learning-based multimodal electrochemical analytical device based on eMoSx-LIG for multiplexed detection of tyrosine and uric acid in sweat and saliva.

Multiplexed detection of biomolecules is of great value in various fields, from disease diagnosis to food safety and environmental monitoring. However, accurate and multiplexed analyte detection is challenging to achieve in mixtures using a single device/material. In this paper, we demonstrate a machine learning (ML)-powered multimodal analytical device based on a single sensing material made of electrodeposited molybdenum polysulfide (eMoSx) on laser induced graphene (LIG) for multiplexed detection of tyrosine (TYR) and uric acid (UA) in sweat and saliva. Electrodeposition of MoSx shows an increased electrochemically active surface area (ECSA) and heterogeneous electron transfer rate constant, k0. Features are extracted from the electrochemical data in order to train ML models to predict the analyte concentration in the sample (both singly spiked and mixed samples). Different ML architectures are explored to optimize the sensing performance. The optimized ML-based multimodal analytical system offers a limit of detection (LOD) that is two orders of magnitude better than conventional approaches which rely on single peak analysis. A flexible and wearable sensor patch is also fabricated and validated on-body, achieving detection of UA and TYR in sweat over a wide concentration range. While the performance of the developed approach is demonstrated for detecting TYR and UA using eMoSx-LIG sensors, it is a general analytical methodology and can be extended to a variety of electrochemical sensors to enable accurate, reliable, and multiplexed sensing.

Electrochemical Sensors Based on MoSx -Functionalized Laser-Induced Graphene for Real-Time Monitoring of Phenazines Produced by Pseudomonas aeruginosa.

Pseudomonas aeruginosa (P. aeruginosa) is an opportunistic pathogen causing infections in blood and implanted devices. Traditional identification methods take more than 24 h to produce results. Molecular biology methods expedite detection, but require an advanced skill set. To address these challenges, this work demonstrates functionalization of laser-induced graphene (LIG) for developing flexible electrochemical sensors for P. aeruginosa based on phenazines. Electrodeposition as a facile approach is used to functionalize LIG with molybdenum polysulfide (MoSx ). The sensor's limit of detection (LOD), sensitivity, and specificity are determined in broth, agar, and wound simulating medium (WSM). Control experiments with Escherichia coli, which does not produce phenazines, demonstrate specificity of sensors for P. aeruginosa. The LOD for pyocyanin (PYO) and phenazine-1-carboxylic acid (PCA) is 0.19 × 10-6  and 1.2 × 10-6  m, respectively. Furthermore, the highly stable sensors enable real-time monitoring of P. aeruginosa biofilms over several days. Comparing square wave voltammetry data over time shows time-dependent generation of phenazines. In particular, two configurations-"Normal" and "Flipped"-are studied, showing that the phenazines time dynamics vary depending on how cells interact with sensors. The reported results demonstrate the potential of the developed sensors for integration with wound dressings for early diagnosis of P. aeruginosa infection.

Non-Enzymatic Detection of Glucose in Neutral Solution Using PBS-Treated Electrodeposited Copper-Nickel Electrodes.

Transition metals have been explored extensively for non-enzymatic electrochemical detection of glucose. However, to enable glucose oxidation, the majority of reports require highly alkaline electrolytes which can be damaging to the sensors and hazardous to handle. In this work, we developed a non-enzymatic sensor for detection of glucose in near-neutral solution based on copper-nickel electrodes which are electrochemically modified in phosphate-buffered saline (PBS). Nickel and copper were deposited using chronopotentiometry, followed by a two-step annealing process in air (Step 1: at room temperature and Step 2: at 150 °C) and electrochemical stabilization in PBS. Morphology and chemical composition of the electrodes were characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Cyclic voltammetry was used to measure oxidation reaction of glucose in sodium sulfate (100 mM, pH 6.4). The PBS-Cu-Ni working electrodes enabled detection of glucose with a limit of detection (LOD) of 4.2 nM, a dynamic response from 5 nM to 20 mM, and sensitivity of 5.47 ± 0.45 µA cm-2/log10(mole.L-1) at an applied potential of 0.2 V. In addition to the ultralow LOD, the sensors are selective toward glucose in the presence of physiologically relevant concentrations of ascorbic acid and uric acid spiked in artificial saliva. The optimized PBS-Cu-Ni electrodes demonstrate better stability after seven days storage in ambient compared to the Cu-Ni electrodes without PBS treatment.

Facile Post-deposition Annealing of Graphene Ink Enables Ultrasensitive Electrochemical Detection of Dopamine.

A growing body of research focuses on engineering materials for electrochemical detection of dopamine (DA), a critical neurotransmitter involved in motor function, reward processes, and blood pressure regulation. Among various sensing materials, graphene is highly attractive due to its excellent electrical conductivity and, in particular, the π-π interaction between the aromatic rings of DA and graphene. However, the lowest detection limits reported solely using graphene are nominally 1 nM. To improve the sensor sensitivity, various strategies are being explored, including chemical functionalization, heterostructure/composite formation, elemental doping, and modification with biomolecules (aptamers, enzymes, etc.). In this work, we demonstrate that commercially available graphene ink can exhibit selective and highly sensitive detection of DA by tuning the surface chemistry utilizing a simple, one-step annealing process. The annealing condition directly impacts the sensor response to DA, with the optimal conditions (30 min at 300 °C under 3% H2 + Ar) yielding a distinguishable and selective response to DA down to 5 pM. X-ray photoelectron spectroscopy (XPS) confirms that the improved selectivity is due to the increased fraction of oxygen functionalities (in particular, C-OH), while Raman spectroscopy shows a higher degree of defectiveness for this condition compared to others. Evaluation of the interaction of three molecular components of DA (i.e., aromatic ring, hydroxyl groups, and amine group) with graphene confirms that the π-π interaction and -OH groups play a prominent role in the improved adsorption of DA on the graphene surface. Furthermore, we demonstrate a proof-of-concept, all-solution processable sensor on polyimide substrates using graphene ink. Tuning the sensor response by varying the annealing condition offers a simple avenue for developing sensitive, selective, and low-cost point-of-care biosensors, while low-temperature annealing ensures compatibility with flexible substrates, such as polyimide.

Organic redox-active crystalline layers for reagent-free electrochemical antibiotic susceptibility testing (ORACLE-AST).

Rapid antibiotic susceptibility testing (AST) is critical in determining bacterial resistance or susceptibility to a particular antibiotic. Simple-to-use phenotype-based AST platforms can assist care-givers in timely prescription of the right antibiotic. Monitoring the change of bacterial viability by measuring electrochemical Faradaic current is a promising approach for rapid AST. However, the existing works require mixing redox-active reagents in the solution which can interfere with the antibiotics. In this paper, we developed a facile electrodeposition process for creating a redox-active crystalline layer (denoted as RZx) on pyrolytic graphite sheets (PGS), which was then utilized as the sensing layer for reagent-free electrochemical AST. To demonstrate the proof-of-principle, we tested the sensors with Escherichia coli (E. coli) K-12 treated with two antibiotics, ampicillin and kanamycin. While the sensors enable detection of bacterial metabolism mainly due to pH-sensitivity of RZx (∼ 53 mV/pH), secreted redox-active metabolites/compounds from whole cells are likely contributing to the signal as well. By monitoring the differential voltammetric signals, the sensors enable accurate prediction of the minimum inhibitory concentration (MIC) in 60 min (p < 0.03). The sensors are stable after 60 days storage in ambient conditions and enable analysis of microbial viability in complex solutions, as demonstrated in spiked milk and human whole blood.

Single-atom doping of MoS2 with manganese enables ultrasensitive detection of dopamine: Experimental and computational approach.

Two-dimensional transition metal dichalcogenides (TMDs) emerged as a promising platform to construct sensitive biosensors. We report an ultrasensitive electrochemical dopamine sensor based on manganese-doped MoS2 synthesized via a scalable two-step approach (with Mn ~2.15 atomic %). Selective dopamine detection is achieved with a detection limit of 50 pM in buffer solution, 5 nM in 10% serum, and 50 nM in artificial sweat. Density functional theory calculations and scanning transmission electron microscopy show that two types of Mn defects are dominant: Mn on top of a Mo atom (MntopMo) and Mn substituting a Mo atom (MnMo). At low dopamine concentrations, physisorption on MnMo dominates. At higher concentrations, dopamine chemisorbs on MntopMo, which is consistent with calculations of the dopamine binding energy (2.91 eV for MntopMo versus 0.65 eV for MnMo). Our results demonstrate that metal-doped layered materials, such as TMDs, constitute an emergent platform to construct ultrasensitive and tunable biosensors.

Detection of bacterial metabolism in lag-phase using impedance spectroscopy of agar-integrated 3D microelectrodes.

Traditional methods for detection of metabolically-active bacterial cells, while effective, require several days to complete. Development of sensitive electrical biosensors is highly desirable for rapid detection and counting of pathogens in food, water, or clinical samples. Herein, we develop a highly-sensitive non-Faradaic impedance sensor which detects metabolic activity of E. coli cells in a mere 1 µl of sample volume and without any sample filtration/purification. The three dimensional (3D) interdigitated electrodes (IDEs) along with self-assembled gold-nickel (Au-Ni) nanostructures significantly amplify the sensitivity by increasing the sensing area almost three-fold. The developed microsystem is integrated with an agar-based growth medium and monitors the metabolism of bacterial cells, enabling bacterial detection in approximately one hour after inoculation, i.e. in the lag-phase. Incorporation of a secondary agar layer as a biocompatible passivation layer protects the IDEs from potential Faradaic reactions and enhances sensitivity to modulation of the non-Faradaic impedance due to cellular metabolism. The resultant label-free sensor is capable of selective identification of metabolizing cells (vs. dead cells) across a wide linear range (10-1000 cells/µl). These results help pave the way for rapid antibacterial susceptibility testing at the point-of-need, which is currently a major challenge in healthcare.

Two-Dimensional Materials in Biosensing and Healthcare: From In Vitro Diagnostics to Optogenetics and Beyond.

Since the isolation of graphene in 2004, there has been an exponentially growing number of reports on layered two-dimensional (2D) materials for applications ranging from protective coatings to biochemical sensing. Due to the exceptional, and often tunable, electrical, optical, electrochemical, and physical properties of these materials, they can serve as the active sensing element or a supporting substrate for diverse healthcare applications. In this review, we provide a survey of the recent reports on the applications of 2D materials in biosensing and other emerging healthcare areas, ranging from wearable technologies to optogenetics to neural interfacing. Specifically, this review provides (i) a holistic evaluation of relevant material properties across a wide range of 2D systems, (ii) a comparison of 2D material-based biosensors to the state-of-the-art, (iii) relevant material synthesis approaches specifically reported for healthcare applications, and (iv) the technological considerations to facilitate mass production and commercialization.

Air-Stable CuInSe2 Nanocrystal Transistors and Circuits via Post-Deposition Cation Exchange.

Colloidal semiconductor nanocrystals (NCs) are a promising materials class for solution-processable, next-generation electronic devices. However, most high-performance devices and circuits have been achieved using NCs containing toxic elements, which may limit their further device development. We fabricate high mobility CuInSe2 NC field-effect transistors (FETs) using a solution-based, post-deposition, sequential cation exchange process that starts with electronically coupled, thiocyanate (SCN)-capped CdSe NC thin films. First Cu+ is substituted for Cd2+ transforming CdSe NCs to Cu-rich Cu2Se NC films. Next, Cu2Se NC films are dipped into a Na2Se solution to Se-enrich the NCs, thus compensating the Cu-rich surface, promoting fusion of the Cu2Se NCs, and providing sites for subsequent In-dopants. The liquid-coordination-complex trioctylphosphine-indium chloride (TOP-InCl3) is used as a source of In3+ to partially exchange and n-dope CuInSe2 NC films. We demonstrate Al2O3-encapsulated, air-stable CuInSe2 NC FETs with linear (saturation) electron mobilities of 8.2 ± 1.8 cm2/(V s) (10.5 ± 2.4 cm2/(V s)) and with current modulation of 105, comparable to that for high-performance Cd-, Pb-, and As-based NC FETs. The CuInSe2 NC FETs are used as building blocks of integrated inverters to demonstrate their promise for low-cost, low-toxicity NC circuits.

"I Am Normal": Claiming Normalcy in Christian-Identified HIV-Infected Adolescent and Emerging Adult Males.

Acquiring HIV in adolescence and young adulthood, when development of self-identity, personal values, and life purpose are central, is challenging. The purpose of our study was to explore the spiritual needs of young people with HIV, learning strategies they used to cope with the disease. A constructivist grounded theory study was conducted. A purposive sample of 21 Christian-identified HIV-infected males was interviewed. The iterative coding phases of grounded theory, including open, axial, selective, and theoretical, were used to analyze data, and a theory of claiming normalcy with HIV was generated. We present the salient theme "I am normal," describing young people's attempts to function the same as peers despite requiring daily treatment. Conditions associated with feelings of normalcy included disclosure status, stigma experiences, support, and health status. Participants sought meaning in the disease, ongoing social engagement, and self-belief. Reinforcing feelings of normalcy may help young people cope with HIV.

High-pressure adsorption of CO2 on NaY zeolite and model prediction of adsorption isotherms.

Supercritical carbon dioxide is an efficient solvent for adsorptive separations because it can potentially be used as both the carrier solvent for adsorption and the desorbent for regeneration. Recent results have demonstrated an anomalous peak or "hump" in the adsorption isotherm near the bulk critical point when the adsorption isotherm is plotted as a function of bulk density. This work presents new data for the adsorption and desorption of carbon dioxide in the near-critical region on a crystalline, well-structured adsorbent (NaY zeolite). The results indicate a strong affinity for CO(2) as well as a significant hump near the critical point. The lattice model previously developed by Aranovich and Donohue is applied to analyze the adsorption.