Contralateral renal change in a unilateral ureteral obstruction rat model using intravoxel incoherent motion diffusion-weighted imaging.

OBJECTIVES: Most functional magnetic resonance research has primarily examined alterations in the affected kidney, often neglecting the contralateral kidney. Our study aims to investigate whether imaging parameters accurately depict changes in both the renal cortex and medulla in a unilateral ureteral obstruction rat model, thereby showcasing the utility of intravoxel incoherent motion (IVIM) in evaluating contralateral renal changes. METHODS: Six rats underwent MR scans and were subsequently sacrificed for baseline histological examination. Following the induction of left ureteral obstruction, 48 rats were scanned, and the histopathological examinations were conducted on days 3, 7, 10, 14, 21, 28, 35, and 42. The apparent diffusion coefficient (ADC), pure molecular diffusion (D), pseudodiffusion (D*), and perfusion fraction (f) values were measured using IVIM. RESULTS: On the 10th day of obstruction, both cortical and medullary ADC values differed significantly between the UUO10 group and the sham group (p < 0.01). The cortical D values showed statistically significant differences between UUO3 group and sham group (p < 0.01) but not among UUO groups at other time point. Additionally, the cortical and medullary f values were statistically significant between the UUO21 group and the sham group (p < 0.01). Especially, the cortical f values exhibited significant differences between the UUO21 group and the UUO groups with shorter obstruction time (at time point of 3, 7, 10, 14 day) (p < 0.01). CONCLUSIONS: Significant hemodynamic alterations were observed in the contralateral kidney following renal obstruction. IVIM accurately captures changes in the unobstructed kidney. Particularly, the cortical f value exhibits the highest potential for assessing contralateral renal modifications.

Unraveling the Activity Trends and Design Principles of Single-Atom Catalysts for Nitrate Electrocatalytic Reduction.

Electrocatalytic nitrate (NO3-) reduction represents one of the most promising approaches to mitigate NO3- pollution and yield NH3, but it is still challenged by the atomic economy and selectivity issues of substantial active sites. Here, we describe a comprehensive investigation on a series of single-atom catalysts (SACs) using nitrogen-doped carbon as substrate (metal/NC). The essence of activity is related to the extent of the electron transfer capacity (SAs → NO3-). Among these examined SACs, the Cu/NC presents good performance toward NH3 synthesis, i.e., a maximum NH3 Faradaic efficiency of 100% with a high NH3 yield rate of up to 32,300 µg h-1 mgcat.-1. X-ray absorption fine structure spectra and density functional theory calculations provide evidence that the electronic structure of Cu-N4 coordination prohibits the formation of N2, N2O, and H2 and facilitates the orbital hybridization between the 2p orbitals of NO3- and 3d orbitals of Cu single-atom sites. Our study is believed to provide fundamental guidance for the future design of highly efficient electrocatalysts in NO3- reduction to NH3.

Understanding the Activity Trends in Electrocatalytic Nitrate Reduction to Ammonia on Cu Catalysts.

Cu-based catalysts possess great potential in the electrocatalytic nitrate (NO3-) reduction reaction for ammonia (NH3) synthesis. However, the low atomic economy limits their further application. Here we report a Cu single-atom (SA) incorporated in nitrogen-doped carbon (Cu SA/NC) with high atomic economy, which exhibits superior NH3 Faradaic efficiency (FE) of 100% along with an impressive NH3 yield rate of 7480 µg h-1 mgcat.-1. As counterparts, Cus+n/NC, with mixed SA and nanoparticles (NPs), shows decreasing NH3 FE with decreasing SA content, but the production of N2 and N2O increases gradually, which reaches the maximum on pure Cu NPs. In situ characterizations and theoretical calculations reveal that a higher NH3 FE of Cu SA/NC is ascribed to a lower free energy of the rate-limiting step (HNO* → N*) and effective inhibition for the N-N coupled process. This work provides the intuitive activity trends of Cu-based catalysts, opening an avenue for subsequent catalysts design.

Incorporating Ni-Polyoxometalate into the S-Scheme Heterojunction to Accelerate Charge Separation and Resist Photocorrosion for Promoting Photocatalytic Activity and Stability.

The emerging polyoxometalate (POM) nanomaterials are transition metal oxygen anion clusters with d0 electronic configurations, which could be attractive and potential photocatalysts. Hence, a nickel (Ni)-substituted polyoxometalate K6Na4[Ni4(H2O)2(PW9O34)2]·32H2O (Ni4POM)-incorporating step (S)-scheme heterojunction was developed to promote photocatalytic activity and stability in H2 and H2O2 production. The multielectron transfer through variable valence metal centers in Ni4POM would facilitate the recombination of invalid charges through the S-scheme pathway. Moreover, incorporating Ni4POM into the S-scheme heterojunction can broaden the light absorption range and meanwhile lead to resistance to photocorrosion to promote the optical and chemical stability of Cd0.5Zn0.5S (CZS). The optimized CZSNi-70 exhibited a H2 evolution rate of 42.32 mmol g-1 h-1 under visible-light irradiation with an apparent quantum yield of 32.27% at 420 nm and a H2O2 production rate of 295.4 µmol L-1 h-1 under 420 nm light-emitting diode irradiation. This work can provide a new view for the development of transition metal-substituted POM-based stable and efficient S-scheme photocatalysts.

Boosting Interfacial Charge Transfer with a Giant Internal Electric Field in a TiO2 Hollow-Sphere-Based S-Scheme Heterojunction for Efficient CO2 Photoreduction.

The construction of an S-scheme charge transfer pathway is considered to be a powerful way to inhibit charge recombination and maintain photogenerated carriers with high redox capacity to meet the kinetic requirements of the carbon dioxide (CO2) photoreduction reaction. For an S-scheme heterojunction, an internal electric field (IEF) is regarded as the main driving force for accelerating the interfacial spatial transfer of photogenerated charges. Herein, we designed a TiO2 hollow-sphere (TH)-based S-scheme heterojunction for efficient CO2 photoreduction, in which WO3 nanoparticles (WP) were applied as an oxidation semiconductor to form an intimate interfacial contact with the TH. The S-scheme charge transfer mode driven by a strong IEF for the TH/WP composite was confirmed by in situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. As a result, abundant photogenerated electrons with strong reducing ability would take part in the CO2 reduction reaction. The combination of surface photovoltage spectra and transient photocurrent experiments disclosed that the IEF intensity and charge separation efficiency of the fabricated TH/WP composite were nearly 16.80- and 1.42-fold higher, respectively, than those of the pure TH. Furthermore, sufficient active sites provided by the hollow-sphere structure also enhanced the kinetics of the catalytic reaction. Consequently, the optimized TH/WP composite showed a peak level of CO production of 14.20 µmol g-1 in 3 h without the addition of any sacrificial agent. This work provides insights into the kinetic studies of the S-scheme charge transfer pathway for realizing high-performance CO2 photoreduction.

A 2D bimetallic Ni-Co hydroxide monolayer cocatalyst for boosting photocatalytic H2 evolution.

Here, we report two-dimensional (2D) Ni-Co hydroxide monolayers (NiCo-HMs) as a highly active cocatalyst for enhancing the photocatalytic H2 evolution of 2D g-C3N4 nanosheets. The NiCo-HMs can expand the interface of electron migration, promote the separation of photogenerated carriers, provide synergistic Co-Ni active sites, and optimize atomic hydrogen adsorption to improve the kinetics of the catalytic reaction. The resulting 2D/2D NiCo-HMs/g-C3N4 heterojunction displays a high photocatalytic H2 evolution of 3.58 mmol g-1 h-1.

A computational model predicts genetic nodes that allow switching between species-specific responses in a conserved signaling network.

Cell signaling networks regulate a variety of developmental and physiological processes, and changes in their response to external stimuli are often implicated in disease initiation and progression. To elucidate how different responses can arise from conserved signaling networks, we have developed a mathematical model of the well-characterized Caenorhabditis vulval development network involving EGF, Wnt and Notch signaling that recapitulates biologically observed behaviors. We experimentally block a specific element of the EGF pathway (MEK), and find different behaviors in vulval development in two Caenorhabditis species, C. elegans and C. briggsae. When we separate our parameters into subsets that correspond to these two responses, they yield model behaviors that are consistent with observed experimental results, despite the initial parameter grouping based on perturbation in a single node of the EGF pathway. Finally, our analysis predicts specific parameters that may be critical for the theoretically and experimentally observed differences, suggesting modifications that might allow intentional switching between the two species' responses. Our results indicate that all manipulations within a signal transduction pathway do not yield the same outcome, and provide a framework to identify the specific genetic perturbations within a conserved network that will confer unique behaviors on the network.