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1.
Small ; : e2404702, 2024 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-39367553

RESUMO

Grain boundary (GB) mass transport, and chemistry exert a pronounced influence on both the performance and stability of electrodes for solid oxide electrochemical cells. Lanthanum strontium cobalt ferrite (LSCF6428) is applied as a model mixed ionic and electronic conducting (MIEC) perovskite oxide. The cation-vacancy distribution at the GBs is studied at both single and multi-grain scales using high-resolution characterization techniques and computational approaches. The accumulation of oxygen vacancies ( V O · · $V_O^{ \cdot \cdot }$ ) in the GB region, rather than necessarily at the GB core, results in an enhancement of the oxygen diffusivity by 3 - 4 orders of magnitude along the GBs (Dgb). At 350 °C, the oxygen tracer diffusion coefficient (D*) is measured as 2.5 × 10-14 cm2 s-1. The Dgb is determined to be 2.8 × 10-10 cm2 s-1 assuming a crystallographic GB width (δcrystal) of 1 nm, and 2.5 × 10-11 cm2 s-1 using a chemically measured δchem of 11.10 nm by atom probe tomography (APT). The origin of the concomitant changes in the cation composition is also investigate. In addition to the host cations, strong Na segregation is detected at all the GBs examined. Despite the low (ppm) level of this impurity, its presence can affect the space charge potential (Φ0). This, in turn, will influence the evolution of GB chemistry.

2.
Anat Rec (Hoboken) ; 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39238265

RESUMO

Fibrosis and loss of functional capillary surface area may contribute to renal tissue hypoxia in a range of kidney diseases. However, there is limited quantitative information on the impact of kidney disease on the barriers to oxygen diffusion from cortical peritubular capillaries (PTCs) to kidney epithelial tubules. Here, we used stereological methods to quantify changes in total cortical PTC length and surface area, PTC length and surface densities, and diffusion distances between PTCs and kidney tubules in adenine-induced kidney injury. After 7 days of oral gavage of adenine (100 mg), plasma creatinine was 3.5-fold greater than in vehicle-treated rats, while total kidney weight was 83% greater. The total length of PTCs was similar in adenine-treated (1.47 ± 0.23 km (mean ± standard deviation)) to vehicle-treated (1.24 ± 0.24 km) rats, as was the surface density of PTCs (0.025 ± 0.002 vs. 0.024 ± 0.004 µm2/µm3). The total surface area of PTCs was 69% greater in adenine-treated than vehicle-treated rats. However, the length density of PTCs was 28% less in adenine-treated than vehicle-treated rats. Diffusion distances, from PTCs to the basal membrane of the nearest renal tubule (108%), and to the mid-point of the cytoplasmic height of the nearest tubular epithelial cell (57%), were markedly increased. These findings indicate that, in adenine-induced kidney injury, expansion of the renal cortical interstitium increases the distance required for diffusion of oxygen from PTCs to tubules, rendering the kidney cortex susceptible to hypoxia.

3.
Phys Med Biol ; 69(15)2024 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-38959905

RESUMO

Objective.Oxygen depletion is generally believed to play an important role in the FLASH effect-a differential reduction of the radiosensitivity of healthy tissues, relative to that of the tumour under ultra-high dose-rate (UHDR) irradiation conditions. In proton therapy (PT) with pencil-beam scanning (PBS), the deposition of dose, and, hence, the degree of (radiolytic) oxygen depletion varies both spatially and temporally. Therefore, the resulting oxygen concentration and the healthy-tissue sparing effect through radiation-induced hypoxia varies both spatially and temporally as well.Approach.We propose and numerically solve a physical oxygen diffusion model to study these effects and their dependence on tissue parameters and the scan pattern in pencil-beam delivery. Since current clinical FLASH PT (FLASH-PT) is based on 250 MeV shoot-through (transmission) beams, for which dose and dose rate (DR) hardly vary with depth compared to the variation transverse to the beam axis, we focus on the two-dimensional case. We numerically integrate the model to obtain the oxygen concentration in each voxel as a function of time and extract voxel-based and spatially and temporarily integrated metrics for oxygen (FLASH) enhanced dose. Furthermore, we evaluate the impact on oxygen enhancement of standard pencil-beam delivery patterns and patterns that were optimised on dose-rate. Our model can contribute to the identification of tissue properties and pencil-beam delivery parameters that are critical for FLASH-PT and it may be used for the optimisation of FLASH-PT treatment plans and their delivery.Main results.(i) the diffusive properties of oxygen are critical for the steady state concentration and therefore the FLASH effect, even more so in two dimensions when compared to one dimension. (ii) The FLASH effect through oxygen depletion depends primarily on dose and less on other parameters. (iii) At a fixed fraction dose there is a slight dependence on DR. (iv) Scan patterns optimised on DR slightly increase the oxygen induced FLASH effect.Significance.To our best knowledge, this is the first study assessing the impact of scan-pattern optimization (SPO) in FLASH-PT with PBS on a biological FLASH model. While the observed impact of SPO is relatively small, a larger effect is expected for larger target volumes. A better understanding of the FLASH effect and the role of oxygen (depletion) therein is essential for the further development of FLASH-PT with PBS, and SPO.


Assuntos
Modelos Biológicos , Oxigênio , Terapia com Prótons , Dosagem Radioterapêutica , Terapia com Prótons/métodos , Oxigênio/metabolismo , Difusão , Humanos , Doses de Radiação
4.
bioRxiv ; 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38854036

RESUMO

An oxygen sensor-mounted fine-needle biopsy tool was used for in vivo measurement of oxygen levels in tumor xenografts. The system provides a means of measuring the oxygen content in harvested tumor tissue from specific locations. Oxygen in human tumor xenografts in a murine model was observed for over 1 min. Tissues were mapped in relation to oxygen tension (pO2) readings and sampled for conventional cytological examination. Careful modeling of the pO2 readings over 60 seconds yielded a diffusion coefficient for oxygen at the sensor tip, providing additional diagnostic information about the tissue before sampling. Oxygen level measurement may provide a useful adjunct to the use of biomarkers in tumor diagnosis.

5.
Int J Mol Sci ; 25(5)2024 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-38474234

RESUMO

Developmental engineering (DE) involves culturing various cells on modular scaffolds (MSs), yielding modular tissues (MTs) assembled into three-dimensional (3D) tissues, mimicking developmental biology. This study employs an integrated approach, merging experimental and mathematical methods to investigate the biological processes in MT cultivation and assembly. Human dermal fibroblasts (HDFs) were cultured on tissue culture plastics, poly(lactic acid) (PLA) discs with regular open structures, or spherical poly(methyl methacrylate) (PMMA) MSs, respectively. Notably, HDFs exhibited flattened spindle shapes when adhered to solid surfaces, and complex 3D structures when migrating into the structured voids of PLA discs or interstitial spaces between aggregated PMMA MSs, showcasing coordinated colonization of porous scaffolds. Empirical investigations led to power law models simulating density-dependent cell growth on solid surfaces or voids. Concurrently, a modified diffusion model was applied to simulate oxygen diffusion within tissues cultured on solid surfaces or porous structures. These mathematical models were subsequently combined to explore the influences of initial cell seeding density, culture duration, and oxygen diffusion on MT cultivation and assembly. The findings underscored the intricate interplay of factors influencing MT design for tissue assembly. The integrated approach provides insights into mechanistic aspects, informing bioprocess design for manufacturing MTs and 3D tissues in DE.


Assuntos
Engenharia Tecidual , Alicerces Teciduais , Humanos , Alicerces Teciduais/química , Engenharia Tecidual/métodos , Polimetil Metacrilato/química , Poliésteres , Oxigênio
6.
Front Physiol ; 15: 1359119, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38444762

RESUMO

Few formulas have been used in exercise physiology as extensively as the Fick formula, which calculates the rate of oxygen consumption (i.e., V.O2) as the product of cardiac output (Q.) and the difference in oxygen content in arterial and mixed venous blood (Δav¯O2). Unfortunately, the physiology of maximum V.O2 (V.O2MAX) is often misinterpreted due to a lack of appreciation for the limitations represented by the oft-ignored superscript annotations in the Fick formula. The purpose of this perspective is to explain the meaning of the superscript annotations and highlight how such annotations influence proper interpretation of V.O2MAX physiology with the Fick formula. First, we explain the significance of the overdots above V.O2 and Q., which indicate a measure per unit of time. As we will show, the presence of an overdot above Q. and lack of one above Δav¯O2 denotes they are different types of ratios and should be interpreted in the context of one another-not in contrast to each other as is commonplace. Second, we discuss the significance of the overline above the "v¯" in Δav¯O2, which indicates the venous sample is an average of blood that comes from mixed sources. The mixed nature of the venous sample has major implications for interpreting the influence of oxygen diffusion and blood flow heterogeneity on V.O2MAX. Ultimately, we give recommendations and insights for using the Fick formula to calculate V.O2 and interpret V.O2MAX physiology.

7.
Small Methods ; 8(1): e2300871, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37800990

RESUMO

Internal strain and its distribution within the crystal lattice play crucial roles in modulating dislocation activities, thereby affecting mechanical properties of materials. Through the synergistic application of integrated differential phase contrast, in situ transmission electron microscopy characterizations, and computational simulations, a method is unveiled for homogenizing dislocation pinning in NiCoCr multi-principal element alloy (MPEA) through the introduction of a high concentration of oxygen atoms with high diffusion mobility. The doping of massive oxygen atoms creates a high density of strong local pinning points for dislocation motion. Notably, oxygen interstitials exhibit remarkable diffusion and mobility across different octahedral and tetrahedral sites within the distorted crystal lattice of NiCoCrO alloy, even at room temperature. The capability allows for the release of severe stress concentrations arising from dislocation entanglement and the establishment of new strong local pinning points at alternative locations in a uniform way, enabling the material with high strength and outstanding deformability. These findings suggest that interstitial atoms can exhibit significant mobility, even at ambient temperature, in complex MPEAs with spreading lattice distortion, opening new possibilities for dislocation engineering.

8.
Adv Exp Med Biol ; 1438: 135-145, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37845452

RESUMO

Cancers are complex, heterogeneous, dynamic and aggressive diseases exhibiting a series of characteristic biophysical traits which complement the original biological hallmarks of cancers favouring progressive growth, metastasis, and contributing to immune evasion and treatment resistance. One of the prevalent differences between most solid tumors and their corresponding, healthy tissues is a significantly higher water content (hyperhydration) in cancers. As a consequence, cancers have distinctly higher (Fick's) diffusion coefficients D [cm2 s-1] for the respiratory gases O2 and CO2, the key substrate glucose, and for the oncometabolite lactate. In addition, cancers have (a) clearly increased specific heat capacities cp [J g-1 K-1], thus representing high-capacity-tissues upon therapeutic heating induced by electromagnetic irradiation, and (b) higher thermal conductivities k [W m-1 K-1], i.e., increased abilities to conduct heat. Therefore, in diffusion analyses (e.g., when describing critical O2 and glucose supplies or CO2 removal, and the development of hypoxic subvolumes) and for modeling temperature distributions in hyperthermia treatment planning, these specific cancer-related data must be considered in order to reliably reflect oncologic thermo-radiotherapy settings.


Assuntos
Neoplasias , Intoxicação por Água , Humanos , Dióxido de Carbono , Ácido Láctico , Neoplasias/terapia , Temperatura
9.
Pediatr Pulmonol ; 58(11): 3054-3062, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37594147

RESUMO

BACKGROUND: Small-for-gestational-age (SGA) preterm infants are at increased risk of developing bronchopulmonary dysplasia (BPD). There is limited information on pulmonary oxygen diffusion of SGA preterm infants, particularly in those without BPD. OBJECTIVE: To compare the pulmonary oxygen diffusion of SGA to that of appropriate-for-gestational-age (AGA) preterm infants without BPD. STUDY DESIGN: Preterm infants with a gestational age (GA) between 24.0 and 31.6 weeks were studied. The oxygen saturation (SpO2 ), fraction to inspired oxygen (FiO2 ), and the SpO2 to FiO2 ratio (SFR) were compared between SGA and AGA infants. The association between SGA and SFR at 36 weeks was assessed using a multiple regression analysis. In the subgroup without BPD, SGA were match-paired for GA and gender with AGA infants. RESULTS: We analyzed 1189 infants surviving at 36 weeks: 194 (16%) were SGA and 995 (84%) AGA. The incidence of BPD was significantly higher in SGA than AGA infants (32% vs. 13%; p = .000). Out of the 995 infants without BPD, 132 (13%) were SGA and 863 (87%) AGA. SGA was negatively associated with the SFR value at 36 weeks, independently from BPD. SGA infants without BPD had significantly higher (better) SFR at birth, but lower (worse) SpO2 and SFR and from 33 to 36 weeks than their matched AGA counterpart. At 36 weeks, median SpO2 and SFR values were 97.7 versus 98.4 (p = .006) and 465 versus 468 (p = .010) in match-paired SGA and AGA, respectively. CONCLUSION: Among preterm infants of less than 32 weeks and without BPD, SGA infants had a reduced pulmonary oxygen diffusion at 36 weeks in comparison with AGA infants.


Assuntos
Displasia Broncopulmonar , Lactente , Recém-Nascido , Humanos , Displasia Broncopulmonar/epidemiologia , Displasia Broncopulmonar/etiologia , Recém-Nascido Prematuro , Oxigênio , Recém-Nascido Pequeno para a Idade Gestacional , Idade Gestacional
10.
Int J Mol Sci ; 24(16)2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37629194

RESUMO

The mixed ionic and electronic oxide LaNi0.6Fe0.4O3-δ (LNF) is a promising ceramic cathode material for solid oxide fuel cells. Since the reaction rate of oxygen interaction with the cathode material is extremely important, the present work considers the oxygen exchange mechanism between O2 and LNF oxide. The kinetic dependence of the oxygen/oxide interaction has been determined by two isotopic methods using 18O-labelled oxygen. The application of the isotope exchange with the gas phase equilibrium (IE-GPE) and the pulsed isotope exchange (PIE) has provided information over a wide range of temperatures (350-800 °C) and oxygen pressures (10-200 mbar), as each method has different applicability limits. Applying mathematical models to treat the kinetic relationships, the oxygen exchange rate (rH, atom × cm-2 × s-1) and the diffusion coefficient (D, cm2/s) were calculated. The values of rH and D depend on both temperature and oxygen pressure. The activation energy of the surface exchange rate is 0.73 ± 0.05 eV for the PIE method at 200 mbar, and 0.48 ± 0.02 eV for the IE-GPE method at 10-20 mbar; for the diffusion coefficient, the activation energy equals 0.62 ± 0.01 eV at 10-20 mbar for the IE-GPE method. Differences in the mechanism of oxygen exchange and diffusion on dense and powder samples are observed due to the different microstructure and surface morphology of the samples. The influence of oxygen pressure on the ratio of contributions of different exchange types to the total oxygen exchange rate is demonstrated. For the first time, the rate-determining step in the oxygen exchange process for LNF material has been identified. This paper discusses the reasons for the difference in the mechanisms of oxygen exchange and diffusion.


Assuntos
Gases , Oxigênio , Cerâmica , Difusão , Óxidos
11.
ACS Sens ; 8(7): 2713-2720, 2023 07 28.
Artigo em Inglês | MEDLINE | ID: mdl-37428950

RESUMO

Molecular and physical probes have been widely employed to investigate physicochemical properties and mechanisms of interfaces due to their ability to provide accurate measurements with temporal and spatial resolution. However, the direct measurement of electroactive species diffusion in ion-selective electrode (ISE) membranes and quantification of the water layer have been challenging due to the high impedance and optical opacity of polymer membranes. In the present work, carbon nanoelectrodes with ultrathin insulating encapsulation and good geometrical structure are reported as physical probes for direct electrochemical measurement of the water layer. The scanning electrochemical microscopy experiment exhibits positive feedback at the interface of the fresh ISE, and negative feedback after conditioning for 3 h. The thickness of the water layer was estimated to be ca. 13 nm. For the first time, we provide direct evidence that, during conditioning, the water molecules diffuse through the chloride ion selective membrane (Cl-ISM) until a water layer establishes at almost 3 h. Furthermore, the diffusion coefficient and concentration of oxygen molecules in the Cl-ISM are also directly electrochemical measured by introducing ferrocene (Fc) as a redox molecule probe. The oxygen concentration in the Cl-ISM decreases during conditioning, suggesting the diffusion of oxygen from ISM to the water layer. The proposed method can be used for the electrochemical measurement of solid contact, providing theoretical guidance and advice for the performance optimization of ISEs.


Assuntos
Carbono , Eletrodos Seletivos de Íons , Carbono/química , Polímeros/química , Oxirredução , Água/química
12.
Food Res Int ; 170: 112973, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37316056

RESUMO

Oxygen diffusion played an important role in the lipid oxidation of food emulsions. In this study, a simple method was developed to quantitatively observe the oxygen diffusion in the oil-water biphasic system, and it was further applied to investigate the relationship between the oxygen diffusion and lipid oxidation in O/W emulsions. Various factors that related to the emulsion oxidation were considered, from their influence on the oxygen diffusion and lipid oxidation in the emulsions. Results showed that there was obvious correlation between the oxygen diffusion and lipid oxidation in O/W emulsions, which reveals the inhibition of oxygen diffusion could apparently slow down the lipid oxidation. Moreover, the changes of oil phase, water phase and interfacial layer of the emulsions, which were related to the oxygen diffusion, could improve the oxidative stability of the emulsions effectively. Our findings are helpful for deep understanding the mechanisms of the lipid oxidation in food emulsions.


Assuntos
Metabolismo dos Lipídeos , Oxigênio , Emulsões , Água , Lipídeos
13.
Front Chem ; 11: 1217565, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37351518

RESUMO

One way to address the cost issue of polymer electrolyte membrane fuel cells (PEMFCs) is to reduce the amount of platinum used in the cathode catalyst layers (CLs). The oxygen mass transfer resistance of the cathode CLs is the main bottleneck limiting the polarization performance of low Pt-loading membrane electrodes at high current densities. Pt nanoparticles, ionomers, carbon supports, and water in cathode CLs can all affect their oxygen mass transfer resistance. From the perspective of carbon supports, this paper changed the texture of CLs by adding carbon nanotubes (CNTs) or graphene oxide (GO) into carbon black (XC72) and studied its impact on the oxygen mass transfer resistance. A mathematical model was adopted to correlate total mass transfer resistance and internal diffusion efficiency factor with CL structure parameters in order to determine the dominant textural effect of a CL. The results show that adding 30%CNT or 20GO to carbon black of XC72 improved the electrocatalytic performance and mass transfer capability of the composite carbon-supported Pt catalyst layers during oxygen reduction reaction. The study further reveals that the smaller particle-sized carbon material with tiny Pt nanoparticles deposition can minimize the internal oxygen diffusion resistance. A less dense CL structure can reduce the oxygen transfer resistance through the secondary pores. The conclusion obtained can provide guidance for the rational design of optimal cathode CLs of PEMFCs.

14.
Int J Mol Sci ; 24(3)2023 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-36768746

RESUMO

Recent research on the use of physical mixtures In2O3-ZrO2 has raised interesting questions as to how their combination enhances catalytic activity and selectivity. Specifically, the relationship between oxygen diffusion and defect formation and the epitaxial tension in the mixture should be further investigated. In this study, we aim to clarify some of these relationships through a molecular dynamics approach. Various potentials for the two oxides are compared and selected to describe the physical mixture of In2O3 and ZrO2. Different configurations of each single crystal and their physical mixture are simulated, and oxygen defect formation and diffusion are measured and compared. Significant oxygen defect formation is found in both crystals. In2O3 seems to be stabilized by the mixture, while ZrO2 is destabilized. Similar results were found for the ZrO2 doping with In and ln2O3 doping with Zr. The results explain the high activity and selectivity catalyst activity of the mixture for the production of isobutylene from ethanol.


Assuntos
Simulação de Dinâmica Molecular , Zircônio , Zircônio/química , Óxidos/química , Catálise , Oxigênio
15.
Nanomaterials (Basel) ; 12(23)2022 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-36500888

RESUMO

Batteries and supercapacitors, both governed by electrochemical processes, operate by different electrochemical mechanisms which determine their characteristic energy and power densities. Battery materials store large amounts of energy by ion intercalation. Electrical double-layer capacitors store charge through surface-controlled ion adsorption which leads to high power and rapid charging, but much smaller amounts of energy stored. Pseudocapacitive materials offer the promise to combine these properties by storing charge through surface-controlled, battery-like redox reactions but at high rates approaching those of electrochemical double-layer capacitors. This work compares the pseudo-capacitive charge storage characteristics of self-organized titanium dioxide (TiO2-x) nanotubes (NTs) to flat TiO2-x surface films to further elucidate the proposed charge storage mechanism within the formed surface films. By comparing TiO2-x NTs to flat TiO2-x surface films, having distinctively different oxide mass and surface area ratios, it is shown that NaO2 and Na2O2 formation, which constitutes the active surface film material, is governed by the metal oxide bulk. Our results corroborate that oxygen diffusion from the lattice oxide is key to NaO2 and Na2O2 formation.

16.
Cells ; 11(22)2022 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-36429039

RESUMO

In conventional assisted reproductive technologies (ARTs), oocytes are in vitro cultured in static conditions. Instead, dynamic systems could better mimic the physiological in vivo environment. In this study, a millifluidic in vitro oocyte maturation (mIVM) system, in a transparent bioreactor integrated with 3D printed supports, was investigated and modeled thanks to computational fluid dynamic (CFD) and oxygen convection-reaction-diffusion (CRD) models. Cumulus-oocyte complexes (COCs) from slaughtered lambs were cultured for 24 h under static (controls) or dynamic IVM in absence (native) or presence of 3D-printed devices with different shapes and assembly modes, with/without alginate filling. Nuclear chromatin configuration, mitochondria distribution patterns, and activity of in vitro matured oocytes were assessed. The native dynamic mIVM significantly reduced the maturation rate compared to the static group (p < 0.001) and metaphase II (MII) oocytes showed impaired mitochondria distribution (p < 0.05) and activity (p < 0.001). When COCs were included in a combination of concave+ring support, particularly with alginate filling, oocyte maturation and mitochondria pattern were preserved, and bioenergetic/oxidative status was improved (p < 0.05) compared to controls. Results were supported by computational models demonstrating that, in mIVM in biocompatible inserts, COCs were protected from shear stresses while ensuring physiological oxygen diffusion replicating the one occurring in vivo from capillaries.


Assuntos
Técnicas de Maturação in Vitro de Oócitos , Ovário , Feminino , Ovinos , Animais , Técnicas de Maturação in Vitro de Oócitos/métodos , Oócitos/fisiologia , Oxigênio , Alginatos/farmacologia
17.
Nano Lett ; 22(23): 9306-9312, 2022 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-36395459

RESUMO

As an analogue of charged electron flows, the ionic flow could be controlled by the electronic band alignment due to the ambipolar nature of diffusion in the ionic crystal. Here, we demonstrate the active control of the anionic diffusion across heterointerfaces through remote electron doping in the capping layers. In contrast to the spontaneous ionic flux from the underlying VO2 layers to the undoped TiO2 capping layers, the activated Nb dopants in the TiO2 capping layers substantially restrict the ionic flux, despite identical growth conditions. The increase of Fermi level by Nb donors in TiO2 prevents electron flux from being generated across the interfaces by the heightening of a Schottky barrier; this electron shortage generates a kinetic close valve for the flow of negatively charged oxygen ions. Thus, these results demonstrate the importance of electron supply on charged ionic flow, thereby suggesting an unprecedented strategy for ionic-defect-induced emergent properties at interfaces.

18.
Proc Natl Acad Sci U S A ; 119(47): e2206291119, 2022 11 22.
Artigo em Inglês | MEDLINE | ID: mdl-36375074

RESUMO

Legumes establish endosymbiotic associations with nitrogen-fixing rhizobia, which they host inside root nodules. Here, specific physiological and morphological adaptations, such as the production of oxygen-binding leghemoglobin proteins and the formation of an oxygen diffusion barrier in the nodule periphery, are essential to protect the oxygen-labile bacterial nitrogenase enzyme. The molecular basis of the latter process remains elusive as the identification of required genes is limited by the epistatic effect of nodule organogenesis over nodule infection and rhizobia accommodation. We overcame this by exploring the phenotypic diversity of Lotus japonicus accessions that uncouple nodule organogenesis from nodule infection when inoculated with a subcompatible Rhizobium strain. Using comparative transcriptomics, we identified genes with functions associated with oxygen homeostasis and deposition of lipid polyesters on cell walls to be specifically up-regulated in infected compared to noninfected nodules. As hydrophobic modification of cell walls is pivotal for creating diffusion barriers like the root endodermis, we focused on two Fatty acyl-CoA Reductase genes that were specifically activated in the root and/or in the nodule endodermis. Mutant lines in a Fatty acyl-CoA Reductase gene expressed exclusively in the nodule endodermis had decreased deposition of polyesters on this cell layer and increased nodule permeability compared to wild-type plants. Oxygen concentrations were significantly increased in the inner cortex of mutant nodules, which correlated with reduced nitrogenase activity, and impaired shoot growth. These results provide the first genetic evidence for the formation of the nodule oxygen diffusion barrier, a key adaptation enabling nitrogen fixation in legume nodules.


Assuntos
Lotus , Rhizobium , Lotus/metabolismo , Nódulos Radiculares de Plantas/metabolismo , Oxigênio/metabolismo , Poliésteres , Regulação da Expressão Gênica de Plantas , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Rhizobium/genética , Fixação de Nitrogênio/genética , Simbiose/genética , Nitrogenase/metabolismo , Lipídeos
20.
Small ; 18(47): e2204109, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36228095

RESUMO

Perovskite oxides are intriguing electrocatalysts for the oxygen evolution reaction, but both surface (e.g., composition) and bulk (e.g., lattice oxygen) properties should be optimized to maximize their participation in offering favorable activity and durability. In this work, it is demonstrated that through introducing exogenous Fe3+ ( Fe exo 3 + ${\rm{Fe}}_{{\rm{exo}}}^{3 + }$ ) into the liquid electrolyte, not only is the reconstructed surface stabilized and optimized, but the lattice oxygen diffusion is also accelerated. As a result, compared to that in Fe-free 0.1 m KOH, PrBa0.5 Sr0.5 Co2 O5+δ in 0.1 m KOH + 0.1 mm Fe3+ demonstrates a tenfold increment in activity, an extremely low Tafel slope of ≈50 mV dec-1 , and outstanding stability at 10.0 mA cm-2  for 10 h. The superior activity and stability are further demonstrated in Zn-air batteries by presenting high open-circuit voltage, narrow potential gap, high power output, and long-term cycle stability (500 cycles). Based on experimental and theoretical calculations, it is discovered that the dynamical interaction between the Co hydr(oxy)oxide from surface reconstruction and intentional Fe3+ from the electrolyte plays an important role in the enhanced activity and durability, while the generation of a perovskite-hydr(oxy)oxide heterostructure improves the lattice oxygen diffusion to facilitate lattice oxygen participation and enhances the stability.

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