Hydrogen Promotes the Growth of Platinum Pyramidal Nanocrystals by Size-Dependent Symmetry Breaking.

The growth of pyramidal platinum nanocrystals is studied by a combination of synthesis/characterization experiments and density functional theory calculations. It is shown that the growth of pyramidal shapes is due to a peculiar type of symmetry breaking, which is caused by the adsorption of hydrogen on the growing nanocrystals. Specifically, the growth of pyramidal shapes is attributed to the size-dependent adsorption energies of hydrogen atoms on {100} facets, whose growth is hindered only if they are sufficiently large. The crucial role of hydrogen adsorption is further confirmed by the absence of pyramidal nanocrystals in experiments where the reduction process does not involve hydrogen.

Catalytic Bioswitch of Platinum Nanozymes: Mechanistic Insights of Reactive Oxygen Species Scavenging in the Neurovascular Unit.

Oxidative stress is known to be the cause of several neurovascular diseases, including neurodegenerative disorders, since the increase of reactive oxygen species (ROS) levels can lead to cellular damage, blood-brain barrier leaking, and inflammatory pathways. Herein, we demonstrate the therapeutic potential of 5 nm platinum nanoparticles (PtNPs) to effectively scavenge ROS in different cellular models of the neurovascular unit. We investigated the mechanism underlying the PtNP biological activities, analyzing the influence of the evolving biological environment during particle trafficking and disclosing a key role of the protein corona, which elicited an effective switch-off of the PtNP catalytic properties, promoting their selective in situ activity. Upon cellular internalization, the lysosomal environment switches on and boosts the enzyme-like activity of the PtNPs, acting as an intracellular "catalytic microreactor" exerting strong antioxidant functionalities. Significant ROS scavenging was observed in the neurovascular cellular models, with an interesting protective mechanism of the Pt-nanozymes along lysosomal-mitochondrial axes.

Nanozymes based on octahedral platinum nanocrystals with {111} surface facets: glucose oxidase mimicking activity in electrochemical sensors.

The ability of shape-controlled octahedral Pt nanoparticles to act as nanozyme mimicking glucose oxidase enzyme is reported. Extended {111} particle surface facets coupled with a size comparable to natural enzymes and easy-to-remove citrate coating give high affinity for glucose, comparable to the enzyme as proven by the steady-state kinetics of glucose electrooxidation. The easy and thorough removal of the citrate coating, demonstrated by X-ray photoelectron spectroscopy analysis, allows a highly stable deposition of the nanozymes on the electrode. The glucose electrochemical detection (at -0.2 V vs SCE) shows a linear response between 0.36 and 17 mM with a limit of detection of 110 µM. A good reproducibility has been achieved, with an average relative standard deviation (RSD) value of 9.1% (n = 3). Similarly, a low intra-sensor variability has been observed, with a RSD of 6.6% (n = 3). Moreover, the sensor shows a long-term stability with reproducible performances for at least 2 months (RSD: 7.8%). Tests in saliva samples show the applicability of Pt nanozymes to commercial systems for non-invasive monitoring of hyperglycemia in saliva, with recoveries ranging from 92 to 98%.

Audiological Evaluation of Vestibular Schwannoma Patients with Normal Hearing.

OBJECTIVE: To evaluate the audiological aspects of vestibular schwannoma (VS) patients with normal hearing. STUDY DESIGN: Retrospective study. SETTING: Quaternary referral center for skull base pathologies. PATIENTS: The records on 4,000 patients who had been diagnosed with VS between 1986 and December 2017 were retrospectively reviewed. The patients included in the study were the ones who complied with the strict audiological normality criteria, as follows: a pure tone hearing threshold (at the 6-octave-spaced frequencies from 250 to 8,000 Hz) ≤25 dBHL; a word recognition score >90%; and interaural differences ≤10 dB at each frequency. INTERVENTIONS: Auditory brainstem response (ABR) testing and radiological imaging. MAIN OUTCOME MEASURES: The incidence of normal objective hearing among VS patients, and the diagnostic utility of the ABR and the effect of tumor size and site on the response. RESULTS: The incidence of normal hearing among VS patients was 4.2%. Tinnitus and vertigo were the most common symptoms across tumor grades; 5.6% of the tumors were large and giant tumors. The ABR yielded a sensitivity of 73.6%, with a false negative rate of 26.3% using a cutoff point of 0.2 ms for interaural latency differences. CONCLUSIONS: The diagnosis of VS should not be based on audiometric thresholds alone. Alarming signs of VS should be clear to the physician in order not to miss or delay the diagnosis of the disease. The ABR is useful in the diagnosis of VS, but normal results do not exclude the occurrence of the disease in patients with normal hearing.

Ultrastructural regenerating features of nasal mucosa following microdebrider-assisted turbinoplasty are related to clinical recovery.

BACKGROUND: The nasal mucosa plays a key role in conditioning the inhaled air and in regulating the immune response. These functions led many authors to recommend mucosal sparing techniques for the surgical management of inferior turbinate hypertrophy. However, the histological modifications of chronic diseases retain the inflammatory activity and prevent the nasal physiology restoration. It has been proved that the basal cells of the nasal mucosa are able to proliferate and to repair after cold-knife incision. The aim of this study was to demonstrate that the healing process after removal of the inferior turbinate mucosa with cold techniques results in a complete structural restoration. METHODS: A prospective study was performed in 18 patients who underwent Microdebrider inferior turbinoplasty (cold technique). Subjective and objective improvement of nasal patency was evaluated with visual analogue scale, rhinomanometry, videoendoscopy and mucociliary transport test. Pre- and post-operative biopsy specimens were taken from 7 patients to evaluate the healing process. Two samples were taken from two healthy patients as control. The specimens were processed for transmission electron microscopy analysis. RESULTS: Videoendoscopy showed reduction of lower turbinate after surgery. Nasal patency augmented and no adverse consequences were observed. After 4 months the nasal mucosa showed normal appearance, with restoration of the pseudostratified ciliated pattern, intercellular connections and normal cellular morphology. Fibrosis and submucosal edema disappeared. At longer time after operation (4 years) clinical improvement was confirmed. CONCLUSIONS: The total removal of the nasal mucosa with cold techniques results in a complete restoration of the normal structure and permanent resolution of the chronic inflammation typical of hypertrophic rhinopathy.

Stainless Steel Activation for Efficient Alkaline Oxygen Evolution in Advanced Electrolyzers.

Designing robust and cost-effective electrocatalysts for efficient alkaline oxygen evolution reaction (OER) is of great significance in the field of water electrolysis. In this study, an electrochemical strategy to activate stainless steel (SS) electrodes for efficient OER is introduced. By cycling the SS electrode within a potential window that encompasses the Fe(II)↔Fe(III) process, its OER activity can be enhanced to a great extent compared to using a potential window that excludes this redox reaction, decreasing the overpotential at current density of 100 mA cm-2 by 40 mV. Electrochemical characterization, Inductively Coupled Plasma - Optical Emission Spectroscopy, and operando Raman measurements demonstrate that the Fe leaching at the SS surface can be accelerated through a Fe → γ-Fe2O3 → Fe3O4 or FeO → Fe2+ (aq.) conversion process, leading to the sustained exposure of Cr and Ni species. While Cr leaching occurs during its oxidation process, Ni species display higher resistance to leaching and gradually accumulate on the SS surface in the form of OER-active Fe-incorporated NiOOH species. Furthermore, a potential-pulse strategy is also introduced to regenerate the OER-activity of 316-type SS for stable OER, both in the three-electrode configuration (without performance decay after 300 h at 350 mA cm-2) and in an alkaline water electrolyzer (≈30 mV cell voltage increase after accelerated stress test-AST). The AST-stabilized cell can still reach 1000 and 4000 mA cm-2 at cell voltages of 1.69 and 2.1 V, which makes it competitive with state-of-the-art electrolyzers based on ion-exchange membrane using Ir-based anodes.

Coexistence of Redox-Active Metal and Ligand Sites in Copper-based 2D Conjugated Metal-Organic Frameworks for Battery-Supercapacitor hybrid systems.

Two-dimensional (2D) conjugated metal-organic frameworks (c-MOFs) are promising materials for supercapacitor (SC) electrodes due to their high electrochemically accessible surface area coupled with superior electrical conductivity compared to traditional MOFs. Here, porous and non-porous HHB-Cu (HHB=hexahydroxybenzene), derived through surfactant-assisted synthesis, are studied as representative 2D c-MOF models, showing different reversible redox reactions with Na+ and Li+ in aqueous and organic electrolytes, respectively. We deployed these redox activities to design negative electrodes for hybrid SCs (HSCs), combining the battery-like property of HHB-Cu as negative electrode and the high capacitance and robust cyclic stability of activated carbon (AC) as positive electrode. In organic electrolyte, porous HHB-Cu-based HSC achieves a maximum cell specific capacity (Cs) of 22.1 mAhg-1 at 0.1 Ag-1, specific energy (Es) of 15.55 Whkg-1 at specific power (Ps) of 70.49 Wkg-1, and 77% cyclic stability after 3000 gravimetric charge-discharge (GCD) cycles at 1 Ag-1 (calculated on the mass of both electrode materials). In the aqueous electrolyte, porous HHB-Cu-based HSC displays a Cs of 13.9 mAhg-1 at 0.1 Ag-1, Es of 6.13 Whkg-1 at 44.05 Wkg-1, and 72.3% Cs retention after 3000 GCD cycles. The non-porous sample shows lower Es performance but better rate capability compared to the porous one.

Hydrogen-Assisted Thermal Treatment of Electrode Materials for Electrochemical Double-Layer Capacitors.

The capacitance of electrode materials used in electrochemical double-layer capacitors (EDLCs) is currently limited by several factors, including inaccessible isolated micropores in high-surface area carbons, the finite density of states resulting in a quantum capacitance in series to Helmholtz double-layer capacitance, and the presence of surface impurities, such as functional groups and adsorbed species. To unlock the full potential of EDLC active materials and corresponding electrodes, several post-production treatments are commonly proposed to improve their capacitance and, thus, the energy density of the corresponding devices. In this work, we report a systematic study of the effect of a prototypical treatment, namely H2-assisted thermal treatment, on the chemical, structural, and thermal properties of activated carbon and corresponding electrodes. By combining multiple characterization techniques, we clarify the actual origins of the improvement of the performance (e.g., > +35% energy density for the investigated power densities in the 0.5-45 kW kg-1 range) of the EDLCs based on treated electrodes compared to the case based on the pristine electrodes. Contrary to previous works supporting a questionable graphitization of the activated carbon at temperatures <1000 °C, we found that a "surface graphitization" of the activated carbon, detected by spectroscopic analysis, is mainly associated with the desorption of surface contaminants. The elimination of surface impurities, including adsorbed species, improves the surface capacitance of the activated carbon (CsurfAC) by +37.1 and +36.3% at specific currents of 1 and 10 A g-1, respectively. Despite the presence of slight densification of the activated carbon upon the thermal treatment, the latter still improves the cell gravimetric capacitance normalized on the mass of the activated carbon only (CgAC), e.g., + 28% at 1 A g-1. Besides, our holistic approach identifies the change in the active material and binder contents as a concomitant cause of the increase of cell gravimetric capacitance (Cg), accounting for the mass of all of the electrode materials measured for treated electrodes compared to pristine ones. Overall, this study provides new insights into the relationship between the modifications of the electrode materials induced by H2-assisted thermal treatments and the performance of the resulting EDLCs.

Inter-Organelle Contact Sites Mediate the Intracellular Antioxidant Activity of Platinum Nanozymes: A New Perspective on Cell-Nanoparticle Interaction and Signaling.

The catalytic and antioxidant properties of platinum nanoparticles (PtNPs) make them promising candidates for several applications in nanomedicine. However, an open issue, still shared among most nanomaterials, is the understanding on how internalized PtNPs, which are confined within endo-lysosomal compartments, can exert their activities. To address this problem, here we study the protective effect of 5 nm PtNPs on a human hepatic (HepG2) cell line exposed to dichlorodiphenylethylene (DDE) as a model of oxidative stress. Our results indicate that PtNPs are very efficient to reduce DDE-induced damage in HepG2 cells, in an extent that depends on DDE dose. PtNPs can contrast the unbalance of mitochondrial dynamics induced by DDE and increase the expression of the SOD2 mitochondrial enzyme that recovers cells from oxidative stress. Interestingly, in cells treated with PtNPs─alone or in combination with DDE─mitochondria form contact sites with a rough endoplasmic reticulum and endo-lysosomes containing nanoparticles. These findings indicate that the protective capability of PtNPs, through their intrinsic antioxidant properties and modulating mitochondrial functionality, is mediated by an inter-organelle crosstalk. This study sheds new light about the protective action mechanisms of PtNPs and discloses a novel nano-biointeraction mechanism at the intracellular level, modulated by inter-organelle communication and signaling.

Platinum Nanozymes Counteract Photoreceptor Degeneration and Retina Inflammation in a Light-Damage Model of Age-Related Macular Degeneration.

Degeneration of photoreceptors in age-related macular degeneration (AMD) is associated with oxidative stress due to the intense aerobic metabolism of rods and cones that if not properly counterbalanced by endogenous antioxidant mechanisms can precipitate photoreceptor degeneration. In spite of being a priority eye disease for its high incidence in the elderly, no effective treatments for AMD exist. While systemic administration of antioxidants has been unsuccessful in slowing down degeneration, locally administered rare-earth nanoparticles were shown to be effective in preventing retinal photo-oxidative damage. However, because of inherent problems of dispersion in biological media, limited antioxidant power, and short lifetimes, these NPs are still confined to the preclinical stage. Here we propose platinum nanoparticles (PtNPs), potent antioxidant nanozymes, as a therapeutic tool for AMD. PtNPs exhibit high catalytic activity at minimal concentrations and protect primary neurons against oxidative insults and the ensuing apoptosis. We tested the efficacy of intravitreally injected PtNPs in preventing or mitigating light damage produced in dark-reared albino Sprague-Dawley rats by in vivo electroretinography (ERG) and ex vivo retina morphology and electrophysiology. We found that both preventive and postlesional treatments with PtNPs increased the amplitude of ERG responses to light stimuli. Ex vivo recordings demonstrated the selective preservation of ON retinal ganglion cell responses to light stimulation in lesioned retinas treated with PtNPs. PtNPs administered after light damage significantly preserved the number of photoreceptors and inhibited the inflammatory response to degeneration, while the preventive treatment had a milder effect. The data indicate that PtNPs can effectively break the vicious cycle linking oxidative stress, degeneration, and inflammation by exerting antioxidant and anti-inflammatory actions. The increased photoreceptor survival and visual performances in degenerated retinas, together with their high biocompatibility, make PtNPs a potential strategy to cure AMD.

From a Chemotherapeutic Drug to a High-Performance Nanocatalyst: A Fast Colorimetric Test for Cisplatin Detection at ppb Level.

A rapid point-of-care method for the colorimetric detection of cisplatin was developed, exploiting the efficient conversion of the chemotherapeutic drug into a high-performance nanocatalyst with peroxidase enzyme mimics. This assay provides high specificity and ppb-detection sensitivity with the naked eye or a smartphone-based readout, outperforming many standard laboratory-based techniques. The nanocatalyst-enabled colorimetric assay can be integrated with machine-learning methods, providing accurate quantitative measurements. Such a combined approach opens interesting perspectives for the on-site monitoring of both chemotherapeutic patients to achieve optimal treatments and healthcare workers to prevent their unsafe exposure.

Ultrasmall, Coating-Free, Pyramidal Platinum Nanoparticles for High Stability Fuel Cell Oxygen Reduction.

Ultrasmall (<5 nm diameter) noble metal nanoparticles with a high fraction of {111} surface domains are of fundamental and practical interest as electrocatalysts, especially in fuel cells; the nanomaterial surface structure dictates its catalytic properties, including kinetics and stability. However, the synthesis of size-controlled, pure Pt-shaped nanocatalysts has remained a formidable chemical challenge. There is an urgent need for an industrially scalable method for their production. Here, a one-step approach is presented for the preparation of single-crystal pyramidal nanocatalysts with a high fraction of {111} surface domains and a diameter below 4 nm. This is achieved by harnessing the shape-directing effect of citrate molecules, together with the strict control of oxidative etching while avoiding polymers, surfactants, and organic solvents. These catalysts exhibit significantly enhanced durability while, providing equivalent current and power densities to highly optimized commercial Pt/C catalysts at the beginning of life (BOL). This is even the case when they are tested in full polymer electrolyte membrane fuel cells (PEMFCs), as opposed to rotating disk experiments that artificially enhance electrode kinetics and minimize degradation. This demonstrates that the {111} surface domains in pyramidal Pt nanoparticles (as opposed to spherical Pt nanoparticles) can improve aggregation/corrosion resistance in realistic fuel cell conditions, leading to a significant improvement in membrane electrode assembly (MEA) stability and lifetime.

Green chemistry and first-principles theory enhance catalysis: synthesis and 6-fold catalytic activity increase of sub-5 nm Pd and Pt@Pd nanocubes.

Synthesizing metal nanoparticles with fine control of size, shape and surface properties is of high interest for applications such as catalysis, nanoplasmonics, and fuel cells. In this contribution, we demonstrate that the citrate-coated surfaces of palladium (Pd) and platinum (Pt)@Pd nanocubes with a lateral length <5 nm and low polydispersity in shape achieve superior catalytic properties. The synthesis achieves great control of the nanoparticle's physico-chemical properties by using only biogenic reagents and bromide ions in water while being fast, easy to perform and scalable. The role of the seed morphology is pivotal as Pt single crystal seeds are necessary to achieve low polydispersity in shape and prevent nanorods formation. In addition, electrochemical measurements demonstrate the abundancy of Pd{100} surface facets at a macroscopic level, in line with information inferred from TEM analysis. Quantum density functional theory calculations indicate that the kinetic origin of cubic Pd nanoshapes is facet-selective Pd reduction/deposition on Pd(111). Moreover, we underline both from an experimental and theoretical point of view that bromide alone does not induce nanocube formation without the synergy with formic acid. The superior performance of these highly controlled nanoparticles to perform the catalytic reduction of 4-nitrophenol was proved: polymer-free and surfactant-free Pd nanocubes outperform state-of-the-art materials by a factor >6 and a commercial Pd/C catalyst by more than one order of magnitude.

Relevance of Modified Bondy Mastoidectomy in Pediatric Cholesteatoma.

Modified Bondy mastoidectomy is a type of canal wall down mastoidectomy well described in literature for adult patients. We present our experience with the use of modified Bondy mastoidectomy in pediatric population. Using retrospective chart review, pediatric patients, who underwent modified Bondy procedure for attic cholesteatoma between 1983 and 2015 at our quaternary referral center for otology and lateral skull base surgery, were analyzed after obtaining permission from institutional review board. The demographic data, air-bone gap before and after surgery (at a follow up of 1 month, 6 months, 2 year and 5 years), intraoperative findings and postoperative outcomes were recorded. A total of 36 (5.8%) pediatric cholesteatoma patients underwent Modified Bondy procedure. Out of these, 5-year follow up was available for 31 patients and they were included in audiological analysis. Air-bone gap was maintained at preoperative levels or improve in all the patients during follow up and there were no incidences of sensorineural hearing loss. Two patients (5.5%) were found to harbor residual cholesteatoma and two patients (6.4%) of the 31 patients who had follow up of 5 years, developed recurrent disease during follow up. Modified Bondy procedure, when done in appropriately selected patients, is a reliable, effective and reasonably safe technique for pediatric cholesteatoma.

Synthesis of Citrate-Coated Penta-twinned Palladium Nanorods and Ultrathin Nanowires with a Tunable Aspect Ratio.

Green and scalable methodologies for the preparation of metal nanoparticles with fine control of shape and size are of high interest in many areas including catalysis, nanomedicine, and nanodiagnostics. In this contribution, we describe a new synthetic method for the production of palladium (Pd) penta-twinned nanowires and nanorods utilizing sodium citrate, formic acid, ascorbic acid, and potassium bromide (KBr) in water, without the use of surfactants or polymers. The synthesis is green, fast, and without the need of complex setups. Interestingly, a microwave-assisted scale-up process has been developed. The combination of a synthetic protocol for seeds and the seed-mediated growth process allows us to synthesize nanorods and nanowires by modulating the concentration of KBr. The synthesized nanomaterials have been physicochemically characterized. High-resolution transmission electron microscopy shows that the nanorods and nanowires have a penta-twinned structure enclosed by {100} lateral facets. Moreover, the absence of sticky molecules or toxic byproducts guarantees the biocompatibility of the nanomaterials, while leaving the surface clean to perform enzymatic activities.