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1.
Nano Lett ; 24(34): 10642-10649, 2024 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-39158134

RESUMO

CO poisoning in Pt-based anode catalysts significantly hampers the proton exchange membrane fuel cell (PEMFC) performance. Despite great advances in CO-tolerant catalysts, their effectiveness is often limited to fundamental three-electrode systems, which is inadequate for practical PEMFC applications. Herein, we present a straightforward thermal oxidation strategy for constructing a Ru oxide blocking layer on commercial PtRu/C through a one-step Ru-segregation-and-oxidation process. The resulting 0.7 nm thick Ru oxide layer effectively inhibits CO adsorption while maintaining hydrogen oxidation activity. PtRu@RuO2/C demonstrates exceptional CO tolerance, enduring 1% CO in rotating disk electrode tests, an ∼10-fold improvement compared to that of PtRu/C. Crucially, it retains high HOR activity and CO tolerance in PEMFC, with negligible polarization curve loss in the presence of 100 ppm CO. Notably, 85% HOR activity is retained after a 4 h stability test. This enhancement contributes to the Ru oxide layer decelerating CO adsorption kinetics, rather than promoting CO oxidation via the classic bifunctional mechanism.

2.
Small ; 20(15): e2307164, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-37997555

RESUMO

Nowadays, highly active and stable alkaline bifunctional electrocatalysts toward water electrolysis that can work at high current density (≥1000 mA cm-2) are urgently needed. Herein, Mn-doped RuO2 (MnxRu1-xO2) nanofibers (NFs) are constructed to achieve this object, presenting wonderful hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with the overpotentials of only 269 and 461 mV at 1 A cm-2 in 1 m KOH solution, and remarkably stability under industrial demand with 1 A cm-2, significantly better than the benchmark Pt/C and commercial RuO2 electrocatalysts, respectively. More importantly, the assembled Mn0.05Ru0.95O2 NFs||Mn0.05Ru0.95O2 NFs electrolyzer toward overall water splitting reaches the current density of 10 mA cm-2 with a cell voltage of 1.52 V and also delivers an outstanding stability over 150 h of continuous operation, far surpassing commercial Pt/C||commercial RuO2, RuO2 NFs||RuO2 NFs and most previously reported exceptional electrolyzers. Theoretical calculations indicate that Mn-doping into RuO2 can significantly optimize the electronic structure and weaken the strength of O─H bond to achieve the near-zero hydrogen adsorption free energy (ΔGH*) value for HER, and can also effectively weaken the adsorption strength of intermediate O* at the relevant sites, achieving the higher OER catalytic activity, since the overlapping center of p-d orbitals is closer to the Fermi level.

3.
Small ; 20(22): e2310323, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38109157

RESUMO

Although Ruthenium-based pyrochlore oxides can function as promising catalysts for acidic water oxidation, their limitations in terms of stability and activity still need to be addressed for further application in practical conditions. In this work, the possibility to enhance both oxygen evolution reaction activity and durability of Gd2Ru2O7- δ through partial replacement with Na+ in Gd3+ sites is first offered, leading to the electronic and geometric regulation of active center RuO6. Na+ triggers the emergence of Ru<4+ and the electron rearrangement of active-centered RuO6. Specifically, Ru ions with a negative d-band center after Na+ doping exhibit weaker adsorption energies of *O and result in the conversion of the rate-limiting step from *O/*OOH to *OH/O*, reducing energy barriers for boosting activities. Therefore, the NaxGd2- xRu2O7- δ requires a low overpotential of 260 mV at 10 mA cm-2 in 0.1 m HClO4 electrolyte. Moreover, the higher formation energy of Ru vacancy and less distorted RuO6 enable the as-prepared NaxGd2- xRu2O7- δ to operate steadily at 10 mA cm-2 for 300 h and multi-current chronopotentiometry with current densities from 20 to 100 mA cm-2 for 60 h in acidic proton exchange membrane electrolyzer, respectively.

4.
Small ; 20(34): e2310464, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38597768

RESUMO

Developing highly active and durable catalysts in acid conditions remains an urgent issue due to the sluggish kinetics of oxygen evolution reaction (OER). Although RuO2 has been a state-of-the-art commercial catalyst for OER, it encounters poor stability and high cost. In this study, the electronic reservoir regulation strategy is proposed to promote the performance of acidic water oxidation via constructing a RuO2/MnO2 heterostructure supported on carbon cloth (CC) (abbreviated as RuO2/MnO2/CC). Theoretical and experimental results reveal that MnO2 acts as an electron reservoir for RuO2. It facilitates electron transfer from RuO2, enhancing its activity prior to OER, and donates electrons to RuO2, improving its stability after OER. Consequently, RuO2/MnO2/CC exhibits better performance compared to commercial RuO2, with an ultrasmall overpotential of 189 mV at 10 mA cm-2 and no signs of deactivation even after 800 h of electrolysis in 0.5 m H2SO4 at 10 mA cm-2. When applied as the anode in a proton exchange membrane water electrolyzer, the cost-efficient RuO2/MnO2/CC catalyst only requires a cell voltage of 1.661 V to achieve the water-splitting current of 1 A cm-2, and the noble metal cost is as low as US$ 0.00962 cm-2, indicating potential for practical applications.

5.
Small ; 20(32): e2400010, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38470199

RESUMO

Rechargeable Li-O2 batteries (LOBs) are considered as one of the most promising candidates for new-generation energy storage devices. One of major impediments is the poor cycle stability derived from the sluggish reaction kinetics of unreliable cathode catalysts, hindering the commercial application of LOBs. Therefore, the rational design of efficient and durable catalysts is critical for LOBs. Optimizing surface electron structure via the negative shift of the d-band center offers a reasonable descriptor for enhancing the electrocatalytic activity. In this study, the construction of Ni-incorporating RuO2 porous nanospheres is proposed as the cathode catalyst to demonstrate the hypothesis. Density functional theory calculations reveal that the introduction of Ni atoms can effectively modulate the surface electron structure of RuO2 and the adsorption capacities of oxygen-containing intermediates, accelerating charge transfer between them and optimizing the growth pathway of discharge products. Resultantly, the LOBs exhibit a large discharge specific capacity of 19658 mA h g-1 at 200 mA g-1 and extraordinary cycle life of 791 cycles. This study confers the concept of d-band center modulation for efficient and durable cathode catalysts of LOBs.

6.
Nanotechnology ; 35(34)2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38788702

RESUMO

As a promising alternative to Ir based acidic oxygen evolution reaction (OER) catalysts, Ru suffers from severe fading issues. Supporting it on robust oxides such as TiO2is a simple and effective way to enhance its lifetime. Here, we find that a simple reduction-oxidation process can further improve both activity and stability of RuO2-TiO2composites at high potentials. In this process, the degree of oxidation was carefully controlled to form Ru/RuO2heterostructure to improve OER activity. Moreover, due to the oxophilicity difference of Ru and Ti, the structure of catalysts was changed from supported to embedded, which enhanced the protective effect of TiO2and mitigated the dissolution of Ru element in acidic electrolyte, making as-prepared Ru/RuO2-TiO2with better durability at all tested potentials.

7.
Molecules ; 29(2)2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38276614

RESUMO

Proton Exchange Membrane Water Electrolysis (PEMWE) under acidic conditions outperforms alkaline water electrolysis in terms of less resistance loss, higher current density, and higher produced hydrogen purity, which make it more economical in long-term applications. However, the efficiency of PEMWE is severely limited by the slow kinetics of anodic oxygen evolution reaction (OER), poor catalyst stability, and high cost. Therefore, researchers in the past decade have made great efforts to explore cheap, efficient, and stable electrode materials. Among them, the RuO2 electrocatalyst has been proved to be a major promising alternative to Ir-based catalysts and the most promising OER catalyst owing to its excellent electrocatalytic activity and high pH adaptability. In this review, we elaborate two reaction mechanisms of OER (lattice oxygen mechanism and adsorbate evolution mechanism), comprehensively summarize and discuss the recently reported RuO2-based OER electrocatalysts under acidic conditions, and propose many advanced modification strategies to further improve the activity and stability of RuO2-based electrocatalytic OER. Finally, we provide suggestions for overcoming the challenges faced by RuO2 electrocatalysts in practical applications and make prospects for future research. This review provides perspectives and guidance for the rational design of highly active and stable acidic OER electrocatalysts based on PEMWE.

8.
Molecules ; 29(4)2024 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-38398537

RESUMO

Proton exchange membrane water electrolysis is hindered by the sluggish kinetics of the anodic oxygen evolution reaction. RuO2 is regarded as a promising alternative to IrO2 for the anode catalyst of proton exchange membrane water electrolyzers due to its superior activity and relatively lower cost compared to IrO2. However, the dissolution of Ru induced by its overoxidation under acidic oxygen evolution reaction (OER) conditions greatly hinders its durability. Herein, we developed a strategy for stabilizing RuO2 in acidic OER by the incorporation of high-valence metals with suitable ionic electronegativity. A molten salt method was employed to synthesize a series of high-valence metal-substituted RuO2 with large specific surface areas. The experimental results revealed that a high content of surface Ru4+ species promoted the OER intrinsic activity of high-valence doped RuO2. It was found that there was a linear relationship between the ratio of surface Ru4+/Ru3+ species and the ionic electronegativity of the dopant metals. By regulating the ratio of surface Ru4+/Ru3+ species, incorporating Re, with the highest ionic electronegativity, endowed Re0.1Ru0.9O2 with exceptional OER activity, exhibiting a low overpotential of 199 mV to reach 10 mA cm-2. More importantly, Re0.1Ru0.9O2 demonstrated outstanding stability at both 10 mA cm-2 (over 300 h) and 100 mA cm-2 (over 25 h). The characterization of post-stability Re0.1Ru0.9O2 revealed that Re promoted electron transfer to Ru, serving as an electron reservoir to mitigate excessive oxidation of Ru sites during the OER process and thus enhancing OER stability. We conclude that Re, with the highest ionic electronegativity, attracted a mass of electrons from Ru in the pre-catalyst and replenished electrons to Ru under the operating potential. This work spotlights an effective strategy for stabilizing cost-effective Ru-based catalysts for acidic OER.

9.
Molecules ; 29(5)2024 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-38474694

RESUMO

In this study, the performance of a zero-gap flow-through reactor with three-dimensional (3D) porous Ti/RuO2-TiO2@Pt anodes was systematically investigated for the electrocatalytic oxidation of phenolic wastewater, considering phenol and 4-nitrophenol (4-NP) as the target pollutants. The optimum parameters for the electrochemical oxidation of phenol and 4-NP were examined. For phenol degradation, at an initial concentration of 50 mg/L, initial pH of 7, NaCl concentration of 10.0 g/L, current density of 10 mA/cm2, and retention time of 30 min, the degradation efficiency achieved was 95.05%, with an energy consumption of 15.39 kWh/kg; meanwhile, for 4-NP, the degradation efficiency was 98.42% and energy consumption was 19.21 kWh/kg (at an initial concentration of 40 mg/L, initial pH of 3, NaCl concentration of 10.0 g/L, current density of 10 mA/cm2, and retention time of 30 min). The electrocatalytic oxidation of phenol and 4-NP conformed to the pseudo-first-order kinetics model, and the k values were 0.2562 min-1 and 0.1736 min-1, respectively, which are 1.7 and 3.6-times higher than those of a conventional electrolyzer. Liquid chromatography-mass spectrometry (LC-MS) was used to verify the intermediates formed during the degradation of phenol or 4-NP and a possible degradation pathway was provided. The extremely narrow electrode distance and the flow-through configuration of the zero-gap flow-through reactor were thought to be essential for its lower energy consumption and higher mass transfer efficiency. The zero-gap flow-through reactor with a novel 3D porous Ti/RuO2-TiO2@Pt electrode is a superior alternative for the treatment of industrial wastewater.

10.
Angew Chem Int Ed Engl ; 63(18): e202402018, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38390636

RESUMO

Developing ruthenium-based heterogeneous catalysts with an efficient and stable interface is essential for enhanced acidic oxygen evolution reaction (OER). Herein, we report a defect-rich ultrathin boron nitride nanosheet support with relatively independent electron donor and acceptor sites, which serves as an electron reservoir and receiving station for RuO2, realizing the rapid supply and reception of electrons. Through precisely controlling the reaction interface, a low OER overpotential of only 180 mV (at 10 mA cm-2) and long-term operational stability (350 h) are achieved, suggesting potential practical applications. In situ characterization and theoretical calculations have validated the existence of a localized electronic recycling between RuO2 and ultrathin BN nanosheets (BNNS). The electron-rich Ru sites accelerate the adsorption of water molecules and the dissociation of intermediates, while the interconnection between the O-terminal and B-terminal edge establishes electronic back-donation, effectively suppressing the over-oxidation of lattice oxygen. This study provides a new perspective for constructing a stable and highly active catalytic interface.

11.
Angew Chem Int Ed Engl ; 63(28): e202405798, 2024 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-38659324

RESUMO

RuO2 has been considered as the most likely acidic oxygen evolution reaction (OER) catalyst to replace IrO2, but its performance, especially long-term stability under harsh acidic conditions, is still unacceptable. Here, we propose a grain boundary (GB) engineering strategy by fabricating the ultrathin porous RuO2 nanosheet with abundant of grain boundaries (GB-RuO2) as an efficient acid OER catalyst. The involvement of GB induces significant tensile stress and creates an unsaturated coordination environment, effectively optimizing the adsorption of intermediates and stabilizing active site structure during OER process. Notably, the GB-RuO2 not only exhibits a low overpotential (η10=187 mV) with an ultra-low Tafel slope (34.5 mV dec-1), but also steadily operates for over 550 h in 0.1 M HClO4. Quasi in situ/operando methods confirm that the improved stability is attributed to GB preventing Ru dissolution and greatly inhibiting the lattice oxygen oxidation mechanism (LOM). A proton exchange membrane water electrolysis (PEMWE) using the GB-RuO2 catalyst operates a low voltage of 1.669 V at 2 A cm-2 and operates stably for 100 h at 100 mA cm-2.

12.
Angew Chem Int Ed Engl ; : e202413653, 2024 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-39133139

RESUMO

In proton exchange membrane water electrolysis (PEMWE), the anode oxygen evolution reaction (OER) catalysts rely heavily on the expensive and scarce iridium-based materials. Ruthenium dioxide (RuO2) with lower price and higher OER activity, has been explored for the similar task, but has been restricted by the poor stability. Herein, we developed an anion modification strategy to improve the OER performance of RuO2 in acidic media. The designed multicomponent catalyst based on sulfate anchored on RuO2/MoO3 displays a low overpotential of 190 mV at 10 mA cm-2 and stably operates for 500 hours with a very low degradation rate of 20 µV h-1. When assembled in a PEMWE cell, this catalyst as an anode shows an excellent stability at 500 mA cm-2 for 150 h. Experimental and theoretical results revealed that MoO3 could stabilize sulfate anion on RuO2 surface to suppress its leaching during OER. Such MoO3-anchored sulfate not only reduces the formation energy of *OOH intermediate on RuO2, but also impedes both the surface Ru and lattice oxygen loss, thereby achieving the high OER activity and exceptional durability.

13.
Small ; 19(45): e2303057, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37434100

RESUMO

Ferroptosis, as a non-apoptotic cell death pathway, has attracted increasing attention for cancer therapy. However, the clinical application of ferroptosis-participated modalities is severely limited by the low efficiency owing to the intrinsic intracellular regulation pathways. Herein, chlorin e6 (Ce6) and N-acetyl-l-cysteine-conjugated bovine serum albumin-ruthenium dioxide is elaborately designed and constructed for ultrasound-triggered peroxynitrite-mediated ferroptosis. Upon ultrasound stimulation, the sonosensitizers of Ce6 and RuO2 exhibit highly efficient singlet oxygen (1 O2 ) generation capacity, which is sequentially amplified by superoxide dismutase and catalase-mimicking activity of RuO2 with hypoxia relief. Meanwhile, the S-nitrosothiol group in BCNR breaks off to release nitric oxide (NO) on-demand, which then reacts with 1 O2 forming highly cytotoxic peroxynitrite (ONOO- ) spontaneously. Importantly, BCNR nanozyme with glutathione peroxidase-mimicking activity can consume glutathione (GSH), along with the generated ONOO- downregulates glutathione reductase, avoiding GSH regeneration. The two-parallel approach ensures complete depletion of GSH within the tumor, resulting in the boosted ferroptosis sensitization of cancer cells. Thus, this work presents a superior paradigm for designing peroxynitrite-boosted ferroptosis sensitization cancer therapeutic.


Assuntos
Antineoplásicos , Ferroptose , Neoplasias , Humanos , Ácido Peroxinitroso/farmacologia , Antineoplásicos/farmacologia , Ultrassonografia , Óxido Nítrico/metabolismo , Glutationa/metabolismo , Linhagem Celular Tumoral , Espécies Reativas de Oxigênio/metabolismo
14.
Small ; 19(16): e2206768, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36683212

RESUMO

Developing efficient oxygen evolution reaction (OER) electrocatalysts for seawater electrolysis is still a big challenge. Herein, a facile one-pot approach is reported to synthesize RuO2 -incorporated NiFe-metal organic framework (RuO2 /NiFe-MOF) with unique nanobrick-nanosheet heterostructure as precatalyst. Driven by electric field, the RuO2 /NiFe-MOF dynamically reconstructs into RuO2 nanoparticles-anchored NiFe oxy/hydroxide nanosheets (RuO2 /NiFeOOH) with coherent interface, during which the dissolution and redeposition of RuO2 are witnessed. Owing to the synergistic interaction between RuO2 and NiFeOOH, the as-reconstructed RuO2 /NiFeOOH exhibits outstanding alkaline OER activity with an ultralow overpotential of 187.6 mV at 10 mA cm-2 and a small Tafel slope of 31.9 mV dec-1 and excellent durability at high current densities of 840 and 1040 mA cm-2 in 1 m potassium hydroxide (KOH). When evaluated for seawater oxidation, the RuO2 /NiFeOOH only needs a low overpotential of 326.2 mV to achieve 500 mA cm-2 and can continuously catalyze OER at 500 mA cm-2 for 100 h with negligible activity degradation. Density function theory calculations reveal that the presence of strong interaction and enhanced charge transfer along the coherent interface between RuO2 and NiFeOOH ensures improved OER activity and stability.

15.
Small ; 19(38): e2208202, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37222629

RESUMO

Pursuing highly active and long-term stable ruthenium (Ru) based oxygen evolution reaction (OER) catalyst for water electrolysis under acidic conditions is of great significance yet a tremendous challenge to date. To solve the problem of serious Ru corrosion in an acid medium, the trace lattice sulfur (S) inserted RuO2 catalyst is prepared. The optimized catalyst (Ru/S NSs-400) has shown a record stability of 600 h for the solely containing Ru (iridium-free) nanomaterials. In the practical proton exchange membrane device, the Ru/S NSs-400 can even sustain more than 300 h without obvious decay at the high current density of 250 mA cm-2 . The detailed investigations reveal that S doping not only changes the electronic structure of Ru via forming RuS coordination for high adsorption of reaction intermediates but also stabilizes Ru from over-oxidation. This strategy is also effective for improving the stability of commercial Ru/C and homemade Ru-based nanoparticles. This work offers a highly effective strategy to design high-performance OER catalysts for water splitting and beyond.

16.
Small ; 19(4): e2204889, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36420939

RESUMO

Exquisite design of RuO2 -based catalysts to simultaneously improve activity and stability under harsh conditions and reduce the Ru dosage is crucial for advancing energy conversion involving oxygen evolution reaction (OER). Herein, a distinctive cobalt-doped RuOx framework is constructed on Co3 O4 nanocones (Co3 O4 @CoRuOx ) as a promising strategy to realize above urgent desires. Extensive experimental characterization and theoretical analysis demonstrate that cobalt doped in RuOx lattice brings the oxygen vacancies and lattice contraction, which jointly redistribute the electron configuration of RuOx . The optimized d-band center balances the adsorption energies of oxygenated intermediates, lowing the thermodynamical barrier of the rate-determining step; and meanwhile, the over-oxidation and dissolution of Ru species are restrained because of the p-band down-shifting of the lattice oxygen. Co3 O4 @CoRuOx with 3.7 wt.% Ru delivers the extremely low OER overpotentials at 10 mA cm-2 in alkaline (167 mV), neutral (229 mV), and acidic electrolytes (161 mV), and super operating stability over dozens of hours. The unprecedented activity ranks first in all pH-universal OER catalysts reported so far. These findings provide a route to produce robust low-loading Ru catalysts and an engineering approach for regulating the central active metal through synergy of co-existing defects to improve the catalytic performance and stability.

17.
Small ; 19(29): e2207170, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37021723

RESUMO

Electrochemical oxidization and thermodynamic instability agglomeration are a primary challenge in triggering metal-support interactions (MSIs) by immobilizing metal atoms on a carrier to achieve efficient oxygen evolution reactions (OER). Herein, Ru clusters anchored to the VS2 surface and the VS2 nanosheets embedded vertically in carbon cloth (Ru-VS2 @CC) are deliberately designed to realize high reactivity and exceptional durability. In situ Raman spectroscopy reveals that the Ru clusters are preferentially electro-oxidized to form RuO2 chainmail, both affording sufficient catalytic sites and protecting the internal Ru core with VS2 substrates for consistent MSIs. Theoretical calculations elucidate that electrons across the Ru/VS2 interface aggregate toward the electro-oxidized Ru clusters, while the electronic coupling of Ru 3p and O 2p orbitals boosts a positive shift in the Fermi energy level of Ru, optimizing the adsorption capacity of the intermediates and diminishing the migration barriers of the rate-determining steps. Therefore, the Ru-VS2 @CC catalyst demonstrated ultra-low overpotentials of 245 mV at 50 mA cm-2 , while the zinc-air battery maintained a narrow gap (0.62 V) after 470 h of reversible operation. This work has transformed the corrupt into the miraculous and paved a new way for the development of efficient electrocatalysts.

18.
Chemphyschem ; 24(5): e202200429, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36377406

RESUMO

Magnetic exchange force microscopy (MExFM) is an important experimental technique for mapping the magnetic structure of surfaces with atomic resolution relying on the spin-dependent short-range exchange interaction between a magnetic tip and a magnetic surface. RuO2 is a significant compound with applications in heterogeneous catalysis and electrocatalysis. It has been characterized recently as an antiferromagnetic (AFM) material, and its magnetism has been predicted somewhat surprisingly to play an important role in its catalytic properties. In the current study, we explore theoretically whether MExFM can visualize the magnetic surface structure of RuO2 . We use density functional theory (DFT) calculations to extract the exchange interactions between a ferromagnetic Fe tip interacting with an AFM RuO2 (110) surface, as a function of tip-surface distance and the position of the tip over the surface. Mimicking the MExFM experiment, these data are then used to calculate the normalized frequency shift of an oscillating cantilever tip versus the minimum tip-surface distance, and construct corrugation height line profiles. It is found that the exchange interaction between tip and surface is strongest for a parallel configuration of the spins of the tip and of the surface; it is weakest for an anti-parallel orientation. In a corrugation profile, this gives rise to a sizable height difference of 25 pm between the spin-up and spin-down Ru atoms in the RuO2 (110) surface at a normalized frequency shift γ ${\gamma }$ =-10.12 fNm1/2 . The O atoms in the surface are not or hardly visible in the corrugation profile.

19.
Clin Chem Lab Med ; 61(4): 608-626, 2023 03 28.
Artigo em Inglês | MEDLINE | ID: mdl-36716120

RESUMO

The EU In-Vitro Diagnostic Device Regulation (IVDR) aims for transparent risk-and purpose-based validation of diagnostic devices, traceability of results to uniquely identified devices, and post-market surveillance. The IVDR regulates design, manufacture and putting into use of devices, but not medical services using these devices. In the absence of suitable commercial devices, the laboratory can resort to laboratory-developed tests (LDT) for in-house use. Documentary obligations (IVDR Art 5.5), the performance and safety specifications of ANNEX I, and development and manufacture under an ISO 15189-equivalent quality system apply. LDTs serve specific clinical needs, often for low volume niche applications, or correspond to the translational phase of new tests and treatments, often extremely relevant for patient care. As some commercial tests may disappear with the IVDR roll-out, many will require urgent LDT replacement. The workload will also depend on which modifications to commercial tests turns them into an LDT, and on how national legislators and competent authorities (CA) will handle new competences and responsibilities. We discuss appropriate interpretation of ISO 15189 to cover IVDR requirements. Selected cases illustrate LDT implementation covering medical needs with commensurate management of risk emanating from intended use and/or design of devices. Unintended collateral damage of the IVDR comprises loss of non-profitable niche applications, increases of costs and wasted resources, and migration of innovative research to more cost-efficient environments. Taking into account local specifics, the legislative framework should reduce the burden on and associated opportunity costs for the health care system, by making diligent use of existing frameworks.


Assuntos
Serviços de Laboratório Clínico , Kit de Reagentes para Diagnóstico , Humanos , Kit de Reagentes para Diagnóstico/normas , União Europeia , Serviços de Laboratório Clínico/legislação & jurisprudência
20.
Nano Lett ; 22(14): 5689-5697, 2022 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-35839312

RESUMO

Ca2RuO4 is a transition-metal oxide that exhibits a Mott insulator-metal transition (IMT) concurrent with a symmetry-preserving Jahn-Teller distortion (JT) at 350 K. The coincidence of these two transitions demonstrates a high level of coupling between the electronic and structural degrees of freedom in Ca2RuO4. Using spectroscopic measurements with nanoscale spatial resolution, we interrogate the interplay of the JT and IMT through the temperature-driven transition. Then, we introduce photoexcitation with subpicosecond temporal resolution to explore the coupling of the JT and IMT via electron-hole injection under ambient conditions. Through the temperature-driven IMT, we observe phase coexistence in the form of a stripe phase existing at the domain wall between macroscopic insulating and metallic domains. Through ultrafast carrier injection, we observe the formation of midgap states via enhanced optical absorption. We propose that these midgap states become trapped by lattice polarons originating from the local perturbation of the JT.

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