MXene Supported Surface Plasmon Polaritons for Optical Microfiber Ammonia Sensing.

The properties of surface plasmons are notoriously dependent on the supporting materials system. However, new capabilities cannot be obtained until the technique of surface plasmon enabled by advanced two-dimensional materials is well understood. Herein, we present the experimental demonstration of surface plasmon polaritons (SPPs) supported by single-layered MXene flakes (Ti3C2Tx) coating on an optical microfiber and its application as an ammonia gas sensor. Enabled by its high controllability of chemical composition, unique atomistically thin layered structure, and metallic-level conductivity, MXene is capable of supporting not only plasmon resonances across a wide range of wavelengths but also a selective sensing mechanism through frequency modulation. Theoretical modeling and optics experiments reveal that, upon adsorbing ammonia molecules, the free electron motion at the interface between the SiO2 microfiber and the MXene coating is modulated (i.e., the modulation of the SPPs under applied light), thus inducing a variation in the evanescent field. Consequently, a wavelength shift is produced, effectively realizing a selective and highly sensitive ammonia sensor with a 100 ppm detection limit. The MXene supported SPPs open a promising path for the application of advanced optical techniques toward gas and chemical analysis.

Molecular Structure Engineering of Isomeric Additives for Long Lifetime Zn Anodes.

Modulating the solvation structure of hydrated zinc ions using organic additives stands as a pragmatic approach to suppress dendrite formation and corrosion on zinc metal anodes (ZMAs), thereby enhancing the rechargeability of aqueous Zn-ion batteries. However, fundamental screening principles for organic additives with diverse molecular structures remain elusive, especially for isomers with the same molecular formula. This study delves into the impact of three isomeric hexagonal alcohols (mannitol, sorbitol, and galactitol) as additives in adjusting Zn2+ solvation structural behaviors within ZnSO4 baseline electrolytes. Electrical measurements and molecular simulations reveal the specific molecular structure of mannitol, which features interweaving electron clouds between adjacent hydroxyl groups, achieving a high local electron cloud density. This phenomenon significantly enhances desolvation abilities, thus establishing a more stable anode/electrolyte interface chemistry. Even at 5 mA cm-2 for 2.5 mAh cm-2 capacity, Zn||Zn symmetric cells with mannitol-regulated electrolyte display an impressive 1170 h lifespan, far exceeding those with other isomer additives and is nearly tenfold longer than that with a pure ZnSO4 electrolyte (120 h). Rather than strictly adhering to focusing on chemical composition, this study with emphasis on optimizing molecular structure offers a promising untapped dimension to screen more efficient additives to enhance the reversibility of ZMAs.

Shock waves generated by toroidal bubble collapse are imperative for kidney stone dusting during Holmium:YAG laser lithotripsy.

Holmium:yttrium-aluminum-garnet (Ho:YAG) laser lithotripsy (LL) has been the treatment of choice for kidney stone disease for more than two decades, yet the mechanisms of action are not completely clear. Besides photothermal ablation, recent evidence suggests that cavitation bubble collapse is pivotal in kidney stone dusting when the Ho:YAG laser operates at low pulse energy (Ep) and high frequency (F). In this work, we perform a comprehensive series of experiments and model-based simulations to dissect the complex physical processes in LL. Under clinically relevant dusting settings (Ep = 0.2 J, F = 20 Hz), our results suggest that majority of the irradiated laser energy (>90 %) is dissipated by heat generation in the fluid surrounding the fiber tip and the irradiated stone surface, while only about 1 % may be consumed for photothermal ablation, and less than 0.7 % is converted into the potential energy at the maximum bubble expansion. We reveal that photothermal ablation is confined locally to the laser irradiation spot, whereas cavitation erosion is most pronounced at a fiber tip-stone surface distance about 0.5 mm where multi foci ring-like damage outside the thermal ablation zone is observed. The cavitation erosion is caused by the progressively intensified collapse of jet-induced toroidal bubble near the stone surface (<100 µm), as a result of Raleigh-Taylor and Richtmyer-Meshkov instabilities. The ensuing shock wave-stone interaction and resultant leaky Rayleigh waves on the stone surface may lead to dynamic fatigue and superficial material removal under repeated bombardments of toroidal bubble collapses during dusting procedures in LL.

d-Band Center Optimization of Ti3C2Tx MXene Nanosheets for Ultrahigh NO2 Gas Sensitivity at Room Temperature.

MXene exhibits numerous advantageous properties such as high electronic conductivity, high surface area, and ease of surface modification via tailoring of functional groups. However, the mechanism by which MXene functionalization enhances gas sensing performance has not yet been well understood, let alone the development of a rational sensor design optimization strategy. This work presents a functionalization methodology for MXene based on d-band center modulation, which can be implemented by introducing Fe onto the surface of Ti3C2Tx nanosheets, for significantly improved gas sensing response and selectivity. The strategy is demonstrated in the design of gas sensors. The optimized gas sensor shows a response of 50% toward 10 ppm of NO2 at room temperature, which is over 6-fold improvement from its pristine counterpart, an unprecedented performance level among all reported MXene gas sensors. XPS characterizations, valence band analyses, and density functional theory (DFT) calculations all indicate that the underlying enhancement mechanism can be attributed to the tuning of the d-band center energy toward the Fermi level. This work provides a new design strategy based on the optimization of the d-band center energy and adds a much needed systematic and quantitative method to the design of two-dimensional materials based semiconducting gas sensors.

An engineered Sox17 induces somatic to neural stem cell fate transitions independently from pluripotency reprogramming.

Advanced strategies to interconvert cell types provide promising avenues to model cellular pathologies and to develop therapies for neurological disorders. Yet, methods to directly transdifferentiate somatic cells into multipotent induced neural stem cells (iNSCs) are slow and inefficient, and it is unclear whether cells pass through a pluripotent state with full epigenetic reset. We report iNSC reprogramming from embryonic and aged mouse fibroblasts as well as from human blood using an engineered Sox17 (eSox17FNV). eSox17FNV efficiently drives iNSC reprogramming while Sox2 or Sox17 fail. eSox17FNV acquires the capacity to bind different protein partners on regulatory DNA to scan the genome more efficiently and has a more potent transactivation domain than Sox2. Lineage tracing and time-resolved transcriptomics show that emerging iNSCs do not transit through a pluripotent state. Our work distinguishes lineage from pluripotency reprogramming with the potential to generate more authentic cell models for aging-associated neurodegenerative diseases.

Evaluation of the determinants for improved pluripotency induction and maintenance by engineered SOX17.

An engineered SOX17 variant with point mutations within its DNA binding domain termed SOX17FNV is a more potent pluripotency inducer than SOX2, yet the underlying mechanism remains unclear. Although wild-type SOX17 was incapable of inducing pluripotency, SOX17FNV outperformed SOX2 in mouse and human pluripotency reprogramming. In embryonic stem cells, SOX17FNV could replace SOX2 to maintain pluripotency despite considerable sequence differences and upregulated genes expressed in cleavage-stage embryos. Mechanistically, SOX17FNV co-bound OCT4 more cooperatively than SOX2 in the context of the canonical SoxOct DNA element. SOX2, SOX17, and SOX17FNV were all able to bind nucleosome core particles in vitro, which is a prerequisite for pioneer transcription factors. Experiments using purified proteins and in cellular contexts showed that SOX17 variants phase-separated more efficiently than SOX2, suggesting an enhanced ability to self-organise. Systematic deletion analyses showed that the N-terminus of SOX17FNV was dispensable for its reprogramming activity. However, the C-terminus encodes essential domains indicating multivalent interactions that drive transactivation and reprogramming. We defined a minimal SOX17FNV (miniSOX) that can support reprogramming with high activity, reducing the payload of reprogramming cassettes. This study uncovers the mechanisms behind SOX17FNV-induced pluripotency and establishes engineered SOX factors as powerful cell engineering tools.

Order-disorder engineering of RuO2 nanosheets towards pH-universal oxygen evolution.

Ru-based electrocatalysts are considered promising anode catalysts towards water electrolysis due to their impressive activity under acidic conditions. Yet, caused by the collapse of the local crystalline domains and concurrent leaching of Ru species during the OER process, durability against structural degradation remains poor. Herein, we present an order-disorder structure optimization strategy, based on RuO2 nanosheets with well-defined amorphous-crystalline boundaries supported on carbon cloth (a/c-RuO2/CC), to effectively catalyze water oxidation, especially in the case of an acidic medium. Specifically, the as-prepared a/c-RuO2/CC sample has achieved a lower overpotential of 150 mV at 10 mA cm-2, a smaller Tafel slope of 47 mV dec-1, and a significantly higher durability with suppressed dissolution of Ru, with regard to its crystalline (c-RuO2/CC) and amorphous (a-RuO2/CC) counterparts. Computational simulations combined with experimental characterizations uncover that the construction of the structurally ordered-disordered boundary enables a weakened Ru-O covalency with regard to the ordered counterpart, which suppresses the leaching of active Ru species from the crystalline phase, thus enhances stability. An upshift of the d-band center in a/c-RuO2/CC relative to a-RuO2/CC reduces the energy barrier of the potential-determining step (*O → *OOH), thereby dramatically boosting activity.

Atomic Plasma Grafting: Precise Control of Functional Groups on Ti3C2Tx MXene for Room Temperature Gas Sensors.

Gas sensing properties of two-dimensional (2D) materials are derived from charge transfer between the analyte and surface functional groups. However, for sensing films consisting of 2D Ti3C2Tx MXene nanosheets, the precise control of surface functional groups for achieving optimal gas sensing performance and the associate mechanism are still far from well understood. Herein, we present a functional group engineering strategy based on plasma exposure for optimizing the gas sensing performance of Ti3C2Tx MXene. For performance assessment and sensing mechanism elucidation, we synthesize few-layered Ti3C2Tx MXene through liquid exfoliation and then graft functional groups via in situ plasma treatment. Functionalized Ti3C2Tx MXene with large amounts of -O functional groups shows NO2 sensing properties that are unprecedented among MXene-based gas sensors. Density functional theory (DFT) calculations reveal that -O functional groups are associated with increased NO2 adsorption energy, thereby enhancing charge transport. The -O functionalized Ti3C2Tx sensor shows a record-breaking response of 13.8% toward 10 ppm NO2, good selectivity, and long-term stability at room temperature. The proposed technique is also capable of improving selectivity, a well-known challenge in chemoresistive gas sensing. This work paves the way to the possibility of using plasma grafting for precise functionalization of MXene surfaces toward practical realization of electronic devices.

Bilateral Cystoid Macular Edema and Corneal Endothelial Graft Rejection following Influenza and Varicella-Zoster Vaccinations.

PURPOSE: Multiple cases of corneal graft rejection after various vaccinations have been reported over the past decades. Here we described a case of bilateral cystoid macular edema (CME) and endothelial rejection in a DSAEK patient following influenza and varicella vaccines. CASE REPORT: A 72-year-old woman with bilateral Fuch's endothelial dystrophy received bilateral DSAEK surgeries. She received an influenza vaccination and her left visual acuity (VA) decreased due to CME. Half a year later, the patient received a varicella-zoster virus vaccine. 11 days later, she was found to have signs of endothelial graft rejection in both eyes. Unfortunately, her vision further deteriorated despite intensive topical steroid treatment. CONCLUSIONS: In view of the current worldwide efforts on mass vaccination against the COVID-19 pandemic, we suggest an increased use of topical corticosteroids both before and after vaccination may be helpful in reducing this risk.

Biaxial Stretching Array Based on High-Energy-Efficient MXene-Based Al-Ion Micro-supercapacitor Island and Editable Stretchable Bridge.

Employment of multivalent charge carriers with higher charge density to replace frequently used univalent ones can effectively increase the areal capacitance of micro-supercapacitors utilizing few-layered MXene self-assembled electrodes. However, their larger charge density and ionic size usually lead to a sluggish extraction/insertion dynamic between MXene interlayers with limited free space, greatly offsetting the benefits. Herein, we show how to facilitate de-/intercalation of high-valence charge carriers (Al3+) by using polypyrrole-coated bacterial cellulose (BC@PPy) nanospacers to expand MXene interlayer space. Together with the longitudinal electron transport path between interlayers synchronously constructed by the conductive PPy shell, a significant 496% areal capacitance enhancement (232.79 mF cm-2) is realized in the fabricated symmetric Al3+-ion micro-supercapacitors (AMSCs) with the obtained MXene/BC@PPy hybrid film electrodes employing polyacrylamide/1 M AlCl3·6H2O hydrogel electrolyte relative to the cell with pure MXene film electrodes (39.02 mF cm-2). Further benefiting from a high output voltage of 1.2 V, the AMSCs acquire an areal energy density up to 45.3 µW h cm-2. As a device demonstration, we further fabricate a biaxially stretchable AMSC array, simulate its spatial strain distribution during biaxial stretching, and characterize its electrochemical and mechanical properties up to an extreme areal strain of 300%. The proposed rational fabrication paradigm achieves a new level of combined energy density, stretch performance, and architectural simplicity, which presents a route toward a commercially viable stretchable micro energy-storage system with high energy efficiencies.

Evaluation of psychological impact of COVID-19 on anesthesiology residents in the United States.

The aim of our study was to evaluate the impact of COVID-19 on the mental health of in-training anesthesiology residents in the United States. A link containing validated survey tools including the Depression-Anxiety-Stress-Scale (DASS-21), the Abbreviated Maslach Burnout Inventory (aMBI), and the Brief Resilient Coping Scale (BRCS) along with questions related to work environment, and additional personal factors were emailed to 159 Anesthesiology residency programs across the US. 143 responses were received of which 111 were complete. The prevalence of depression, anxiety, stress and burnout was 42%, 24%, 31% and 71% respectively. Emotional exhaustion, depersonalization, and reduced feelings of personal accomplishment were experienced by 80%, 53%, and 65% of respondents, respectively. The BRCS scale showed 33% of respondents with low, 44% with moderate and 22% with high coping scales. Logistic regression analyses indicated those with a prior mental health diagnosis were 3 times more likely to have a non-normal DASS depression score, 4 times more likely to have a non-normal DASS anxiety score, and 11.74 times more prone to emotional exhaustion. Increased work hours and higher training levels were associated with increased levels of stress. In our survey, prior mental health illness, gender and increased work hours were the main drivers of increased risk.

The Retrograde Basilic Approach for Balloon-Assisted Maturation of Brachiocephalic Arteriovenous Fistulas.

PURPOSE: To assess the feasibility and outcomes of an approach utilizing transbasilic access for balloon-assisted maturation (BAM) of brachiocephalic arteriovenous fistulas (BCAVFs). MATERIALS AND METHODS: This retrospective analysis comprised 28 patients (mean age, 63 years ± 10.8) who underwent endovascular treatment of their immature BCAVFs via a basilic approach from December 2016 to December 2018. The mean age of the BCAVFs was 3.3 months ± 1.4 at the time of BAM. Other demographic data, vascular access characteristics, procedural data, technical and clinical success rates, and adverse events were also evaluated. RESULTS: All patients had inflow juxta-anastomotic stenoses, with 4 patients (14%) having concomitant outflow tract stenoses and 1 patient (4%) having a short-segment occlusion at the stenotic juxta-anastomotic segment. Technical success was achieved in 27 patients (96%). The mean diameter of the largest balloon used was 5.7 mm ± 0.6. Clinical success was achieved in 22 patients (79%), with 6 patients (21%) requiring a subsequent additional intervention before successful cannulation. No perioperative adverse events were observed. CONCLUSIONS: The retrograde basilic approach is feasible, safe, and effective for BAM of BCAVFs.

Dual Defocused Laser Pyrolysis: A Lasing-Centric Strategy for Defect and Morphological Optimization in Microsupercapacitor Electrodes.

Laser-induced graphene (LIG) has shown great potential for controllable and scalable realization of microsupercapacitors (MSCs). However, as is well-known, LIG electrodes suffer from low charge storage capacity and conductance. In this paper, a lasing-centric method is presented for defect control and morphological enhancement in LIG electrodes through unique dual laser pyrolysis. This method encompasses dual lasing pyrolysis, one for the synthesis of defocused LIG, and another for the decoration of Ru nanoparticles to enhance electrochemical performance. Fundamentally, the investigation simultaneously optimizes for defocused lasing distance and lasing speed, which to the best of the author's knowledge, has not been previously reported. The defocused LIG electrode exhibits a remarkably improved electrochemical capacitance of over 25 times (114 mF cm-2 ) compared to the one based on focused laser-induced graphene (FLIG). As a device demonstration, a flexible and self-healable MSC has been fabricated based on DFLIG/Ru-PEDOT/Au electrodes, exhibiting a high areal specific capacitance (25.7 mF cm-2 ), excellent electrochemical stability (91% retention of specific capacitance after 8000 cycles), and good self-healing performance (85.6% retention of specific capacitance after two cut-heal cycles). By enhancing material properties via dual defocused laser pyrolysis, this work presents a strategy for highly controllable and scalable realization of electrodes in micro-energy storage devices.

Dissipation-enabled hydrodynamic conductivity in a tunable bandgap semiconductor.

Electronic transport in the regime where carrier-carrier collisions are the dominant scattering mechanism has taken on new relevance with the advent of ultraclean two-dimensional materials. Here, we present a combined theoretical and experimental study of ambipolar hydrodynamic transport in bilayer graphene demonstrating that the conductivity is given by the sum of two Drude-like terms that describe relative motion between electrons and holes, and the collective motion of the electron-hole plasma. As predicted, the measured conductivity of gapless, charge-neutral bilayer graphene is sample- and temperature-independent over a wide range. Away from neutrality, the electron-hole conductivity collapses to a single curve, and a set of just four fitting parameters provides quantitative agreement between theory and experiment at all densities, temperatures, and gaps measured. This work validates recent theories for dissipation-enabled hydrodynamic conductivity and creates a link between semiconductor physics and the emerging field of viscous electronics.

Comparison of Different Pulse Modulation Modes for Holmium:Yttrium-Aluminum-Garnet Laser Lithotripsy Ablation in a Benchtop Model.

Introduction: Manipulation of Holmium:Yttrium-Aluminum-Garnet laser parameters such as pulse energy (PE), frequency, and duration can impact laser lithotripsy ablation efficiency. In 2017, Lumenis introduced Moses™ Technology, which uses pulse modulation to enhance the delivery of energy from fiber to stone as well as to minimize stone retropulsion. Since the introduction of Moses Technology, other companies have brought additional pulse modulation concepts to market. The purpose of this in vitro study is to compare the pulse characteristics and stone ablation efficiency of Lumenis Moses Technology with Quanta's Vapor Tunnel™. Materials and Methods: Submerged BegoStone phantoms were systematically ablated using either the Lumenis Moses Pulse 120H or the Quanta Litho 100 clinical laser system. Two PEs (0.4 and 1 J), three fiber-stone standoff distances (SDs) (0.5, 1, 2 mm), and all available pulse duration and modulation modes for each laser were tested in combination. Fiber speed was adjusted to scan across the stone surface at either 1 or 10 pulses/mm to form single pulse craters or an ablation trough, respectively. Volumes of single craters and 1 mm trough segments were imaged and quantified using optical coherence tomography. Results: Ablation volumes decreased with decreasing PE and increasing SD. Statistically significant variability was seen between pulse types (PT) at every tested parameter set. Among pulse modulation modes, Moses Distance (MD) was superior at 0.5 mm in all testing and at 2 mm in trough testing. Vapor Tunnel (VT) was superior in 2 mm single crater testing. All modulated pulses performed similarly at 1 mm. Conclusions: In this benchtop model of laser lithotripsy, stone ablation was significantly impacted by PT. MD demonstrated superior or noninferior stone ablation at most tested parameters. VT maintained its efficacy the best as SD increased. Future work should focus on the mechanistic differences of these modes relative to other traditional laser pulse modes.

Cavitation Plays a Vital Role in Stone Dusting During Short Pulse Holmium:YAG Laser Lithotripsy.

Objective: To investigate the mechanism of stone dusting in Holmium (Ho): YAG laser lithotripsy (LL). Materials and Methods: Cylindrical BegoStone samples (6 × 6 mm, H × D) were treated in water using a clinical Ho:YAG laser lithotripter in dusting mode (0.2-0.4 J with 70-78 µs in pulse duration, 20 Hz) at various fiber tip to stone standoff distances (SD = 0, 0.5, and 1 mm). Stone damage craters were quantified by optical coherence tomography and bubble dynamics were captured by high-speed video imaging. To differentiate the contribution of cavitation vs thermal ablation to stone damage, three additional experiments were performed. First, presoaked wet stones were treated in air to assess stone damage without cavitation. Second, the laser fiber was advanced at various offset distances (OSD = 0.25, 1, 2, 3, and 10 mm) from the tip of a flexible ureteroscope to alter the dynamics of bubble collapse. Third, stones were treated with parallel fiber to minimize photothermal damage while isolating the contribution of cavitation to stone damage. Results: Treatment in water resulted in 2.5- to 90-fold increase in stone damage compared with those produced in air where thermal ablation dominates. With the fiber tip placed at OSD = 0.25 mm, the collapse of the bubble was distracted away from the stone surface by the ureteroscope tip, leading to significantly reduced stone damage compared with treatment without the scope or with scope at large OSD of 3-10 mm. The average crater volume produced by parallel fiber orientation at 0.2 J after 100 pulses, where cavitation is the dominant mechanism of stone damage, was comparable with those produced by using perpendicular fiber orientation within SD = 0.25-1 mm. Conclusion: Cavitation plays a dominant role over photothermal ablation in stone dusting during short pulse Ho:YAG LL when 10 or more pulses are delivered to the same location.

Ischemic lumbosacral plexopathy after embolization of type 2 endoleak: Progress and functional outcome.

An endoleak is a complication that can occur after an endovascular aneurysm repair. We report a rare case of ischemic lumbosacral plexopathy post embolization of type 2 endoleak, including its presentation, neurological progress, rehabilitation strategy and functional outcome.

Carrier transport theory for twisted bilayer graphene in the metallic regime.

Understanding the normal-metal state transport in twisted bilayer graphene near magic angle is of fundamental importance as it provides insights into the mechanisms responsible for the observed strongly correlated insulating and superconducting phases. Here we provide a rigorous theory for phonon-dominated transport in twisted bilayer graphene describing its unusual signatures in the resistivity (including the variation with electron density, temperature, and twist angle) showing good quantitative agreement with recent experiments. We contrast this with the alternative Planckian dissipation mechanism that we show is incompatible with available experimental data. An accurate treatment of the electron-phonon scattering requires us to go well beyond the usual treatment, including both intraband and interband processes, considering the finite-temperature dynamical screening of the electron-phonon matrix element, and going beyond the linear Dirac dispersion. In addition to explaining the observations in currently available experimental data, we make concrete predictions that can be tested in ongoing experiments.