High-speed mapping of surface charge dynamics using sparse scanning Kelvin probe force microscopy.

Unraveling local dynamic charge processes is vital for progress in diverse fields, from microelectronics to energy storage. This relies on the ability to map charge carrier motion across multiple length- and timescales and understanding how these processes interact with the inherent material heterogeneities. Towards addressing this challenge, we introduce high-speed sparse scanning Kelvin probe force microscopy, which combines sparse scanning and image reconstruction. This approach is shown to enable sub-second imaging (>3 frames per second) of nanoscale charge dynamics, representing several orders of magnitude improvement over traditional Kelvin probe force microscopy imaging rates. Bridging this improved spatiotemporal resolution with macroscale device measurements, we successfully visualize electrochemically mediated diffusion of mobile surface ions on a LaAlO3/SrTiO3 planar device. Such processes are known to impact band-alignment and charge-transfer dynamics at these heterointerfaces. Furthermore, we monitor the diffusion of oxygen vacancies at the single grain level in polycrystalline TiO2. Through temperature-dependent measurements, we identify a charge diffusion activation energy of 0.18 eV, in good agreement with previously reported values and confirmed by DFT calculations. Together, these findings highlight the effectiveness and versatility of our method in understanding ionic charge carrier motion in microelectronics or nanoscale material systems.

Occurrence and clinical relevance of postoperative hypernatremia in dogs undergoing cholecystectomy.

BACKGROUND: Patients undergoing cholecystectomy have not been reported previously to develop clinically relevant postoperative hypernatremia. OBJECTIVES: Describe the frequency of postoperative hypernatremia in dogs undergoing cholecystectomy and its clinical relevance (duration of hospitalization and survival). ANIMALS: Thirty-seven dogs undergoing cholecystectomy at 2 private referral hospitals. METHODS: Retrospective study of dogs undergoing cholecystectomy with available preoperative and postoperative serum sodium concentrations. RESULTS: Postoperative hypernatremia (>150 mEq/L) was common (56%; 95% confidence interval [CI], 40%-70%) and was associated with significantly higher mortality compared to nonhypernatremic patients (52%; 95% CI, 30%-70% vs 12.5%; 95% CI, 2%-40%; P = .02). Nonsurvivors had higher mean postoperative peak serum sodium concentrations (155 mEq/L; range, 146-172) than survivors (150 mEq/L; range, 142-156; P = .01). Dogs developing hypernatremia within 6 hours after surgery had 7.7 higher odds of nonsurvival (odds ratio [OR], 7.7; 95% CI, 5.9-9.4). A delta value (serum sodium concentration on admission [T0] - serum sodium concentration 6 hours postoperatively [T2]) of ≥10 mEq/L carried 3.3 higher odds of mortality (OR, 3.3; 95% CI, 1.6-5.1). All dogs with a postoperative peak sodium concentration >160 mEq/L did not survive. Admission acute patient physiologic laboratory evaluation fast (APPLEfast ) scores were not different between survivors and nonsurvivors or between postoperative hypernatremic and normonatremic patients. Hospitalization time was no different between hypernatremic and normonatremic patients (6 days vs 4.5 days; P = .15). Dogs with gallbladder mucocele were more likely to develop postoperative hypernatremia and have poorer outcomes. CONCLUSIONS: Hypernatremia was a common and clinically relevant postoperative complication in dogs after cholecystectomy. Detection of hypernatremia within 6 hours after surgery may be associated with poorer outcomes.

Tunable Molecular Electrodes for Bistable Polarization Screening.

The polar discontinuity at any ferroelectric surface creates a depolarizing field that must be screened for the polarization to be stable. In capacitors, screening is done by the electrodes, while in bare ferroelectric surfaces it is typically accomplished by atmospheric adsorbates. Although chemisorbed species can have even better screening efficiency than conventional electrodes, they are subject to unpredictable environmental fluctuations and, moreover, dominant charged species favor one polarity over the opposite. This paper proposes a new screening concept, namely surface functionalization with resonance-hybrid molecules, which combines the predictability and bipolarity of conventional electrodes with the screening efficiency of adsorbates. Thin films of barium titanate (BaTiO3 ) coated with resonant para-aminobenzoic acid (pABA) display increased coercivity for both signs of ferroelectric polarization irrespective of the molecular layer thickness, thanks to the ability of these molecules to swap between different electronic configurations and adapt their surface charge density to the screening needs of the ferroelectric underneath. Because electron delocalization is only in the vertical direction, unlike conventional metals, chemical electrodes allow writing localized domains of different polarity underneath the same electrode. In addition, hybrid capacitors composed of graphene/pABA/ferroelectric have been made with enhanced coercivity compared to pure graphene-electode capacitors.

Emergency treatment with intravenous infusion of methylene blue followed by oral administration in a cat presented with severe recurrent methemoglobinemia.

OBJECTIVE: To describe the use of IV infusion followed by oral administration of methylene blue (MB) to successfully treat recurrent methemoglobinemia (MetHb) in a young cat. CASE SUMMARY: A 6-month-old male Ragdoll cat presented with recurrent episodes of severe MetHb and was successfully managed with IV infusion of MB followed by a course of oral MB. Although the definitive cause of the patient's MetHb remains unknown, the cat made a full recovery following treatment without developing any significant side effects secondary to therapy and at the time of writing not had any further recurrences. Follow-up at 6 months found the patient in good health and without any long-term consequences. NEW INFORMATION PROVIDED: To the authors' knowledge, this is the first report of a cat presented with severe MetHb quantitatively assessed via co-oximetry and successfully treated with both IV and oral administration of MB.

Deconvolution of Phonon Scattering by Ferroelectric Domain Walls and Point Defects in a PbTiO3 Thin Film Deposited in a Composition-Spread Geometry.

We present a detailed analysis of the temperature dependence of the thermal conductivity of a ferroelectric PbTiO3 thin film deposited in a composition-spread geometry enabling a continuous range of compositions from ∼25% titanium deficient to ∼20% titanium rich to be studied. By fitting the experimental results to the Debye model we deconvolute and quantify the two main phonon-scattering sources in the system: ferroelectric domain walls (DWs) and point defects. Our results prove that ferroelectric DWs are the main agent limiting the thermal conductivity in this system, not only in the stoichiometric region of the thin film ([Pb]/[Ti] ≈ 1) but also when the concentration of the cation point defects is significant (up to ∼15%). Hence, DWs in ferroelectric materials are a source of phonon scattering at least as effective as point defects. Our results demonstrate the viability and effectiveness of using reconfigurable DWs to control the thermal conductivity in solid-state devices.

Indications for use and complications associated with canine plasma products in 170 patients.

OBJECTIVES: To describe a population of dogs receiving canine plasma products (PP), report the incidence of transfusion reactions (TR), and to identify whether this is higher when non-type-matched plasma is administered. DESIGN: Retrospective study conducted on dogs receiving canine PP between March 2016 and January 2018. SETTING: Private referral hospital with first opinion emergency clinic. ANIMALS: One hundred and ninety-four privately owned dogs identified from the clinic electronic medical record system that received at least 1 unit of canine PP during the study period; 25 patients were excluded due to incomplete records. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: A search of computerized records was performed, identifying any patients that received canine PP between 2016 and 2018; clinical notes were examined to identify the number and type of TR associated. One hundred and sixty-nine cases were included in the study, receiving a total of 412 PP transfusions. Reactions were noted in 4% (17/412) of transfusions administered, with the vast majority being mild in nature. Of the TR identified, a greater proportion were in type-matched PP transfusions than non-type-matched, although this difference was not statistically significant (P = 0.7989). The number of dogs suffering a TR was higher (13%) when multiple units of plasma were administered than if only 1 unit was transfused (5%), but this was not statistically significant (P = 0.1161). Transfusion reactions were more likely to occur when packed red blood cells were also administered, although this was also not statistically significant (P = 0.07). CONCLUSION: Administration of canine plasma products appears to be a safe procedure that carries a low risk of transfusion reactions. Type-matching of canine PP appears unnecessary and does not reduce incidence of TR in dogs.

Non-linear nanoscale piezoresponse of single ZnO nanowires affected by piezotronic effect.

Zinc oxide (ZnO) nanowires (NWs) as semiconductor piezoelectric nanostructures have emerged as material of interest for applications in energy harvesting, photonics, sensing, biomedical science, actuators or spintronics. The expression for the piezoelectric properties in semiconductor materials is concealed by the screening effect of the available carriers and the piezotronic effect, leading to complex nanoscale piezoresponse signals. Here, we have developed a metal-semiconductor-metal model to simulate the piezoresponse of single ZnO NWs, demonstrating that the apparent non-linearity in the piezoelectric coefficient arises from the asymmetry created by the forward and reversed biased Schottky barriers at the semiconductor-metal junctions. By directly measuring the experimental I-V characteristics of ZnO NWs with conductive atomic force microscope together with the piezoelectric vertical coefficient by piezoresponse force microscopy, and comparing them with the numerical calculations for our model, effective piezoelectric coefficients in the range d 33eff ∼ 8.6 pm V-1-12.3 pm V-1 have been extracted for ZnO NWs. We have further demonstrated via simulations the dependence between the effective piezoelectric coefficient d 33eff and the geometry and physical dimensions of the NW (radius to length ratio), revealing that the higher d 33eff is obtained for thin and long NWs due to the tensor nature proportionality between electric fields and deformation in NW geometries. Moreover, the non-linearity of the piezoresponse also leads to multiharmonic electromechanical response observed at the second and higher harmonics that indeed is not restricted to piezoelectric semiconductor materials but can be generalized to any type of asymmetric voltage drops on a piezoelectric structure as well as leaky wide band-gap semiconductor ferroelectrics.

Strain-Engineered Ferroelastic Structures in PbTiO3 Films and Their Control by Electric Fields.

We study the interplay between epitaxial strain, film thickness, and electric field in the creation, modification, and design of distinct ferroelastic structures in PbTiO3 thin films. Strain and thickness greatly affect the structures formed, providing a two-variable parameterization of the resulting self-assembly. Under applied electric fields, these strain-engineered ferroelastic structures are highly malleable, especially when a/c and a1/a2 superdomains coexist. To reconfigure the ferroelastic structures and achieve self-assembled nanoscale-ordered morphologies, pure ferroelectric switching of individual c-domains within the a/c superdomains is essential. The stability, however, of the electrically written ferroelastic structures is in most cases ephemeral; the speed of the relaxation process depends sensitively on strain and thickness. Only under low tensile strain-as is the case for PbTiO3 on GdScO3-and below a critical thickness do the electrically created a/c superdomain structures become stable for days or longer, making them relevant for reconfigurable nanoscale electronics or nonvolatile electromechanical applications.

Ferroelectric Domain Walls in PbTiO3 Are Effective Regulators of Heat Flow at Room Temperature.

Achieving efficient spatial modulation of phonon transmission is an essential step on the path to phononic circuits using "phonon currents". With their intrinsic and reconfigurable interfaces, domain walls (DWs), ferroelectrics are alluring candidates to be harnessed as dynamic heat modulators. This paper reports the thermal conductivity of single-crystal PbTiO3 thin films over a wide variety of epitaxial-strain-engineered ferroelectric domain configurations. The phonon transport is proved to be strongly affected by the density and type of DWs, achieving a 61% reduction of the room-temperature thermal conductivity compared to the single-domain scenario. The thermal resistance across the ferroelectric DWs is obtained, revealing a very high value (≈5.0 × 10-9 K m2 W-1), comparable to grain boundaries in oxides, explaining the strong modulation of the thermal conductivity in PbTiO3. This low thermal conductance of the DWs is ascribed to the structural mismatch and polarization gradient found between the different types of domains in the PbTiO3 films, resulting in a structural inhomogeneity that extends several unit cells around the DWs. These findings demonstrate the potential of ferroelectric DWs as efficient regulators of heat flow in one single material, overcoming the complexity of multilayers systems and the uncontrolled distribution of grain boundaries, paving the way for applications in phononics.

Periodicity-Doubling Cascades: Direct Observation in Ferroelastic Materials.

Very sensitive responses to external forces are found near phase transitions. However, transition dynamics and preequilibrium phenomena are difficult to detect and control. We have observed that the equilibrium domain structure following a phase transition in ferroelectric and ferroelastic BaTiO_{3} is attained by halving of the domain periodicity multiple times. The process is reversible, with periodicity doubling as temperature is increased. This observation is reminiscent of the period-doubling cascades generally observed during bifurcation phenomena, and, thus, it conforms to the "spatial chaos" regime earlier proposed by Jensen and Bak [Phys. Scr. T 9, 64 (1985)PHSTER0281-184710.1088/0031-8949/1985/T9/009] for systems with competing spatial modulations.

Surface charged species and electrochemistry of ferroelectric thin films.

The combination of scanning probe microscopy and ambient pressure X-ray photoelectron spectroscopy opens up new perspectives for the study of combined surface chemical, electrochemical and electromechanical properties at the nanoscale, providing both nanoscale resolution of physical information and the chemical sensitivity required to identify surface species and bulk ionic composition. In this work, we determine the nature and evolution over time of surface chemical species obtained after water-mediated redox reactions on Pb(Zr0.2,Ti0.8)O3 thin films with opposite as-grown polarization states. Starting with intrinsically different surface chemical composition on the oppositely polarized films (as a result of their ferroelectric-dominated interaction with environmental water), we identify the reversible and irreversible electrochemical reactions under an external electric field, distinguishing switching and charging events. We find that while reversible ionic displacements upon polarization switching dominate screening in the bulk of the sample, polarization dependent irreversible redox reactions determine surface chemical composition, which reveals itself as a characteristic fingerprint of the ferroelectric polarization switching history.

Signal enhancement on gold nanoparticle-based lateral flow tests using cellulose nanofibers.

Lateral flow paper-based biosensors merge as powerful tools in point-of-care diagnostics since they are cheap, portable, robust, selective, fast and easy to use. However, the sensitivity of this type of biosensors is not always as high as required, often not permitting a clear quantification. To improve the colorimetric response of standard lateral flow strips (LFs), we have applied a new enhancement strategy that increases the sensitivity of LFs based on the use of cellulose nanofibers (CNF). CNF penetrate inside the pores of LFs nitrocellulose paper, compacting the pore size only in the test line, particularly near the surface of the strip. This modification retains the bioreceptors (antibodies) close to the surface of the strips, and thus further increasing the density of selectively attached gold nanoparticles (AuNPs) in the top part of the membrane, in the test line area, only when the sample is positive. This effect boosts in average a 36.6% the sensitivity of the LFs. The optical measurements of the LFs were carried out with a mobile phone camera whose imaging resolution was improved by attaching microscopic lens on the camera objective. The characterization of CNF into paper and their effect was analyzed using atomic force microscope (AFM) and scanning electron microscope (SEM) imaging techniques.

Converse flexoelectricity yields large piezoresponse force microscopy signals in non-piezoelectric materials.

Converse flexoelectricity is a mechanical stress induced by an electric polarization gradient. It can appear in any material, irrespective of symmetry, whenever there is an inhomogeneous electric field distribution. This situation invariably happens in piezoresponse force microscopy (PFM), which is a technique whereby a voltage is delivered to the tip of an atomic force microscope in order to stimulate and probe piezoelectricity at the nanoscale. While PFM is the premier technique for studying ferroelectricity and piezoelectricity at the nanoscale, here we show, theoretically and experimentally, that large effective piezoelectric coefficients can be measured in non-piezoelectric dielectrics due to converse flexoelectricity.

Water adsorption, dissociation and oxidation on SrTiO3 and ferroelectric surfaces revealed by ambient pressure X-ray photoelectron spectroscopy.

Water dissociation on oxides is of great interest because its fundamental aspects are still not well understood and it has implications in many processes, from ferroelectric polarization screening phenomena to surface catalysis and surface chemistry on oxides. In situ water dissociation and redox processes on metal oxide perovskites which easily expose TiO2-terminated surfaces, such as SrTiO3, BaTiO3 or Pb(Zr,Ti)O3, are studied by ambient pressure XPS, as a function of water vapour pressure. From the analysis of the O1s spectrum, we determine the presence of different types of oxygen based species, from hydroxyl groups, either bound to Ti4+ and metal sites or lattice oxygen, to different peroxide compounds, and propose a model for the adsorbate layer composition, valid for environmental conditions. From the XPS analysis, we describe the existing surface redox reactions for metal oxide perovskites, occurring at different water vapour pressures. Among them, peroxide species resulting from surface oxidative reactions are correlated with the presence of Ti4+ ions, which are observed to specifically promote surface oxidation and water dissociation as compared to other metals. Finally, surface peroxidation is enhanced by X-ray beam irradiation, leading to a higher coverage of peroxide species after beam overexposure and by ferroelectric polarization, demonstrating the enhancement of the reactivity of the surfaces of ferroelectric materials due to the effect of internal electric fields.

Ferroelectrics as Smart Mechanical Materials.

The mechanical properties of materials are insensitive to space inversion, even when they are crystallographically asymmetric. In practice, this means that turning a piezoelectric crystal upside down or switching the polarization of a ferroelectric should not change its mechanical response. Strain gradients, however, introduce an additional source of asymmetry that has mechanical consequences. Using nanoindentation and contact-resonance force microscopy, this study demonstrates that the mechanical response to indentation of a uniaxial ferroelectric (LiNbO3 ) does change when its polarity is switched, and use this mechanical asymmetry both to quantify its flexoelectricity and to mechanically read the sign of its ferroelectric domains.

Lateral Magnetically Modulated Multilayers by Combining Ion Implantation and Lithography.

The combination of lithography and ion implantation is demonstrated to be a suitable method to prepare lateral multilayers. A laterally, compositionally, and magnetically modulated microscale pattern consisting of alternating Co (1.6 µm wide) and Co-CoO (2.4 µm wide) lines has been obtained by oxygen ion implantation into a lithographically masked Au-sandwiched Co thin film. Magnetoresistance along the lines (i.e., current and applied magnetic field are parallel to the lines) reveals an effective positive giant magnetoresistance (GMR) behavior at room temperature. Conversely, anisotropic magnetoresistance and GMR contributions are distinguished at low temperature (i.e., 10 K) since the O-implanted areas become exchange coupled. This planar GMR is principally ascribed to the spatial modulation of coercivity in a spring-magnet-type configuration, which results in 180° Néel extrinsic domain walls at the Co/Co-CoO interfaces. The versatility, in terms of pattern size, morphology, and composition adjustment, of this method offers a unique route to fabricate planar systems for, among others, spintronic research and applications.

Identification of HIV-1-Based Virus-like Particles by Multifrequency Atomic Force Microscopy.

Virus-like particles (VLPs) have become a promising platform for vaccine production. VLPs are formed by structural viral proteins that inherently self-assemble when expressed in a host cell. They represent a highly immunogenic and safe vaccine platform, due to the absence of the viral genome and its high protein density. One of the most important parameters in vaccine production is the quality of the product. A related bottleneck in VLP-based products is the presence of cellular vesicles as a major contaminant in the preparations, which will require the set up of techniques allowing for specific discrimination of VLPs from host vesicular bodies. In this work novel, to our knowledge, multifrequency (MF) atomic force microscopy (AFM) has permitted full structural nanophysical characterization by its access to the virus capsid of the HIV-based VLPs. The assessment of these particles by advanced amplitude modulation-frequency modulation (AM-FM) viscoelastic mapping mode has enhanced the imaging resolution of their nanomechanical properties, opening a new window for the study of the biophysical attributes of VLPs. Finally, the identification and differentiation of HIV-based VLPs from cellular vesicles has been performed under ambient conditions, providing, to our knowledge, novel methodology for the monitoring and quality control of VLPs.

Monolithic integration of room-temperature multifunctional BaTiO3-CoFe2O4 epitaxial heterostructures on Si(001).

The multifunctional (ferromagnetic and ferroelectric) response at room temperature that is elusive in single phase multiferroic materials can be achieved in a proper combination of ferroelectric perovskites and ferrimagnetic spinel oxides in horizontal heterostructures. In this work, lead-free CoFe2O4/BaTiO3 bilayers are integrated with Si(001) using LaNiO3/CeO2/YSZ as a tri-layer buffer. They present structural and functional properties close to those achieved on perovskite substrates: the bilayers are fully epitaxial with extremely flat surface, and exhibit robust ferromagnetism and ferroelectricity at room temperature.

Spontaneous formation of spiral-like patterns with distinct periodic physical properties by confined electrodeposition of Co-In disks.

Spatio-temporal patterns are ubiquitous in different areas of materials science and biological systems. However, typically the motifs in these types of systems present a random distribution with many possible different structures. Herein, we demonstrate that controlled spatio-temporal patterns, with reproducible spiral-like shapes, can be obtained by electrodeposition of Co-In alloys inside a confined circular geometry (i.e., in disks that are commensurate with the typical size of the spatio-temporal features). These patterns are mainly of compositional nature, i.e., with virtually no topographic features. Interestingly, the local changes in composition lead to a periodic modulation of the physical (electric, magnetic and mechanical) properties. Namely, the Co-rich areas show higher saturation magnetization and electrical conductivity and are mechanically harder than the In-rich ones. Thus, this work reveals that confined electrodeposition of this binary system constitutes an effective procedure to attain template-free magnetic, electric and mechanical surface patterning with specific and reproducible shapes.