ABSTRACT
Many Mendelian disorders, such as Huntington's disease (HD) and spinocerebellar ataxias, arise from expansions of CAG trinucleotide repeats. Despite the clear genetic causes, additional genetic factors may influence the rate of those monogenic disorders. Notably, genome-wide association studies discovered somewhat expected modifiers, particularly mismatch repair genes involved in the CAG repeat instability, impacting age at onset of HD. Strikingly, FAN1, previously unrelated to repeat instability, produced the strongest HD modification signals. Diverse FAN1 haplotypes independently modify HD, with rare genetic variants diminishing DNA binding or nuclease activity of the FAN1 protein, hastening HD onset. However, the mechanism behind the frequent and the most significant onset-delaying FAN1 haplotype lacking missense variations has remained elusive. Here, we illustrated that a microRNA acting on 3'-UTR (untranslated region) SNP rs3512, rather than transcriptional regulation, is responsible for the significant FAN1 expression quantitative trait loci signal and allelic imbalance in FAN1 messenger ribonucleic acid (mRNA), accounting for the most significant and frequent onset-delaying modifier haplotype in HD. Specifically, miR-124-3p selectively targets the reference allele at rs3512, diminishing the stability of FAN1 mRNA harboring that allele and consequently reducing its levels. Subsequent validation analyses, including the use of antagomir and 3'-UTR reporter vectors with swapped alleles, confirmed the specificity of miR-124-3p at rs3512. Together, these findings indicate that the alternative allele at rs3512 renders the FAN1 mRNA less susceptible to miR-124-3p-mediated posttranscriptional regulation, resulting in increased FAN1 levels and a subsequent delay in HD onset by mitigating CAG repeat instability.
Subject(s)
Huntington Disease , MicroRNAs , Humans , 3' Untranslated Regions/genetics , Endodeoxyribonucleases , Exodeoxyribonucleases/genetics , Genome-Wide Association Study , Huntington Disease/genetics , MicroRNAs/genetics , Multifunctional EnzymesABSTRACT
Genome-wide association studies (GWASs) of Huntington disease (HD) have identified six DNA maintenance gene loci (among others) as modifiers and implicated a two step-mechanism of pathogenesis: somatic instability of the causative HTT CAG repeat with subsequent triggering of neuronal damage. The largest studies have been limited to HD individuals with a rater-estimated age at motor onset. To capitalize on the wealth of phenotypic data in several large HD natural history studies, we have performed algorithmic prediction by using common motor and cognitive measures to predict age at other disease landmarks as additional phenotypes for GWASs. Combined with imputation with the Trans-Omics for Precision Medicine reference panel, predictions using integrated measures provided objective landmark phenotypes with greater power to detect most modifier loci. Importantly, substantial differences in the relative modifier signal across loci, highlighted by comparing common modifiers at MSH3 and FAN1, revealed that individual modifier effects can act preferentially in the motor or cognitive domains. Individual components of the DNA maintenance modifier mechanisms may therefore act differentially on the neuronal circuits underlying the corresponding clinical measures. In addition, we identified additional modifier effects at the PMS1 and PMS2 loci and implicated a potential second locus on chromosome 7. These findings indicate that broadened discovery and characterization of HD genetic modifiers based on additional quantitative or qualitative phenotypes offers not only the promise of in-human validated therapeutic targets but also a route to dissecting the mechanisms and cell types involved in both the somatic instability and toxicity components of HD pathogenesis.
Subject(s)
Huntington Disease , Cognition , DNA , Genome-Wide Association Study , Humans , Huntingtin Protein/genetics , Huntington Disease/genetics , Huntington Disease/pathology , Trinucleotide Repeat ExpansionABSTRACT
In recent decades, significant progress has been achieved in rational developments of electrocatalysts through constructing novel atomistic structures and modulating catalytic surface topography, realizing substantial enhancement in electrocatalytic activities. Numerous advanced catalysts were developed for electrochemical energy conversion, exhibiting low overpotential, high intrinsic activity, and selectivity. Yet, maintaining the high catalytic performance under working conditions with high polarization and vigorous microkinetics that induce intensive degradation of surface nanostructures presents a significant challenge for commercial applications. Recently, advanced operando and computational techniques have provided comprehensive mechanistic insights into the degradation of surficial functional structures. Additionally, various innovative strategies have been devised and proven effective in sustaining electrocatalytic activity under harsh operating conditions. This review aims to discuss the most recent understanding of the degradation microkinetics of catalysts across an entire range of anodic to cathodic polarizations, encompassing processes such as oxygen evolution and reduction, hydrogen reduction, and carbon dioxide reduction. Subsequently, innovative strategies adopted to stabilize the materials' structure and activity are highlighted with an in-depth discussion of the underlying rationale. Finally, we present conclusions and perspectives regarding future research and development. By identifying the research gaps, this review aims to inspire further exploration of surface degradation mechanisms and rational design of durable electrocatalysts, ultimately contributing to the large-scale utilization of electroconversion technologies.
ABSTRACT
In this study, we identify the local structures of ex-solved nanoparticles using machine-learned potentials (MLPs). We develop a method for training machine-learned potentials by sampling local structures of heterointerface configurations as a training set with its efficacy tested on the Ni/MgO system, illustrating that the error in interface energy is only 0.004 eV/Å2. Using the developed scheme, we train an MLP for the Ni/La0.5Ca0.5TiO3 ex-solution system and identify the local structures for both exo- and endo-type particles. The established model aligns well with the experimental observations, accurately predicting a nucleation size of 0.45 nm. Lastly, the density functional theory calculations on the established atomistic model verify that the kinetic barrier for the dry reforming of methane are substantially reduced by 0.49 eV on the ex-solved catalysts compared to that on the impregnated catalysts. Our findings offer insights into the local structures, growth mechanisms, and underlying origin of the catalytic properties of ex-solved nanoparticles.
ABSTRACT
Electrochemical nitrogen reduction reaction (eNRR) offers a sustainable route for ammonia synthesis; however, current electrocatalysts are limited in achieving optimal performance within narrow potential windows. Herein, inspired by the heliotropism of sunflowers, we present a biomimetic design of Ru-VOH electrocatalyst, featuring a dynamic Ru-O-V pyramid electron bridge for eNRR within a wide potential range. In situ spectroscopy and theoretical investigations unravel the fact that the electrons are donated from Ru to V at lower overpotentials and retrieved at higher overpotentials, maintaining a delicate balance between N2 activation and proton hydrogenation. Moreover, N2 adsorption and activation were found to be enhanced by the Ru-O-V moiety. The catalyst showcases an outstanding Faradaic efficiency of 51.48% at -0.2 V (vs RHE) with an NH3 yield rate exceeding 115 µg h-1 mg-1 across the range of -0.2 to -0.4 V (vs RHE), along with impressive durability of over 100 cycles. This dynamic M-O-V pyramid electron bridge is also applicable to other metals (M = Pt, Rh, and Pd).
ABSTRACT
The design of high-energy facets in electrocatalysts has attracted significant attention due to their potential to enhance electrocatalytic activity. In this review, the significance of high-energy facets in various electrochemical reactions are highlighted, including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), and carbon dioxide reduction reaction (CRR). Their importance in various electrochemical reactions and present strategies for constructing high-energy facets are discussed, including alloying, heterostructure formation, selective etching, capping agents, and coupling with substrates. These strategies enable control over crystallographic orientation and surface morphology, fine-tuning electrocatalytic properties. This study also addresses future directions and challenges, emphasizing the need to better understand fundamental mechanisms. Overall, high-energy facets offer exciting opportunities for advancing electrocatalysis.
ABSTRACT
It is a great demand to develop high-performance electrodes for metal-air batteries to boost cathodic oxygen reduction/evolution dynamics and avoid anodic dendrites. The optimization of catalysis at electrode can be conducted by increasing effective surface exposure, active site density, and unsaturated coordination, via using metal clusters or atomic catalysts, along with conductive or defective supports. Herein, the polarized and synergistic cooperation between dual single atom sites (Fe-N4/Co-N4) are developed through electrolytical exfoliation of defect-enriched π-conjugated macrocyclic polyphthalocyanines to expose more active sites on hollow carbonized shells (HCS). Such FeCo-N4/HCS exhibits outstanding performance in oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), to achieve high-performance in an aqueous zinc battery (AZB) with a high discharge capacity (763.6 mAhg-1) after 750 cycles at 10 mA cm-2, showing stable discharge voltage and excellent durability. It also possesses high performance in a lithium-O2 battery owing to abundant defects, synergistic Fe-N4/Co-N4 active sites, reduced energy barriers, and boosted charge and mass transfer and reaction kinetics. This study provides novel perspectives to expand dual single-metal catalysts on macrocycles in the exploration of efficient, durable, and eco-friendly energy devices.
ABSTRACT
The demand for the exploration of highly active and durable electro/photocatalysts for renewable energy conversion has experienced a significant surge in recent years. Metal-organic frameworks (MOFs), by virtue of their high porosity, large surface area, and modifiable metal centers and ligands, have gained tremendous attention and demonstrated promising prospects in electro/photocatalytic energy conversion. However, the small pore sizes and limited active sites of 3D bulk MOFs hinder their wide applications. Developing 2D MOFs with tailored thickness and large aspect ratio has emerged as an effective approach to meet these challenges, offering a high density of exposed active sites, better mechanical stability, better assembly flexibility, and shorter charge and photoexcited state transfer distances compared to 3D bulk MOFs. In this review, synthesis methods for the most up-to-date 2D MOFs are first overviewed, highlighting their respective advantages and disadvantages. Subsequently, a systematic analysis is conducted on the identification and electronic structure modulation of catalytic active sites in 2D MOFs and their applications in renewable energy conversion, including electrocatalysis and photocatalysis (electro/photocatalysis). Lastly, the current challenges and future development of 2D MOFs toward highly efficient and practical electro/photocatalysis are proposed.
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BACKGROUND: High-risk stage III colon cancer has a considerably poorer prognosis than stage II and low-risk stage III colon cancers. Nevertheless, most guidelines recommend similar adjuvant treatment approaches for all these stages despite the dearth of research focusing on high-risk stage III colon cancer and the potential for improved prognosis with intensive adjuvant treatment. Given the the proven efficacy of triplet chemotherapy in metastatic colorectal cancer treatment, the goal of this study is to evaluate the oncologic efficacy and safety of mFOLFIRINOX in comparison to those of the current standard of care, mFOLFOX 6, as an adjuvant treatment for patients diagnosed with high-risk stage III colon cancer after radical resection. METHODS: This multicenter, randomized (1:1), open-label, phase II trial will assess and compare the effectiveness and toxicity of mFOLFIRINOX and mFOLFOX 6 in patients with high-risk stage III colon cancer after radical resection. The goal of the trial is to enroll 312 eligible patients, from 11 institutes, aged between 20 and 70 years, with an Eastern Cooperative Oncology Group (ECOG) performance status of 0-2, or between 70 and 75 with an ECOG performance status of 0. Patients will be randomized into two arms - Arm A, the experimental arm, and Arm B, the reference arm - and will receive 12 cycles of mFOLFIRINOX and mFOLFOX 6 every 2 weeks, respectively. The primary endpoint of this study is the 3-year disease-free survival, and secondary endpoints include the 3-year overall survival and treatment toxicity. DISCUSSION: The Frost trial would help determine the oncologic efficacy and safety of adjuvant triplet chemotherapy for high-risk stage III colon cancers and ultimately improve prognoses. TRIAL REGISTRATION: ClinicalTrials.gov NCT05179889, registered on 17 December 2021.
Subject(s)
Antineoplastic Combined Chemotherapy Protocols , Colonic Neoplasms , Adult , Aged , Humans , Middle Aged , Young Adult , Antineoplastic Combined Chemotherapy Protocols/adverse effects , Chemotherapy, Adjuvant , Clinical Trials, Phase II as Topic , Colonic Neoplasms/pathology , Disease-Free Survival , Multicenter Studies as Topic , Progression-Free Survival , Randomized Controlled Trials as Topic , Fluorouracil/therapeutic useABSTRACT
OBJECTIVE: To investigate pathologic complete response (pCR) and recurrence outcomes using various progestin treatment strategies in patients with atypical hyperplasia/endometrial intraepithelial neoplasia (AH/EIN). METHODS: Medical records of patients diagnosed with AH/EIN and undergoing follow-up endometrial biopsy after progestin treatment between 2011 and 2020 were retrospectively reviewed. Clinical factors and treatment outcomes were analyzed according to initial progestin treatment (oral progestin [OP], levonorgestrel-releasing intrauterine device [LNG-IUD], and combination), OP dose, and maintenance treatment using Pearson's χ2, Fisher's exact test, and Kaplan-Meier analysis. RESULTS: Of 124 patients included, 74, 37, and 13 were in the OP, LNG-IUD, and combination groups, respectively. The pCR rate was 79.8% and recurrence rate was 21.2%. The pCR rates within 3 and 6 months were significantly higher in the OP group than in the LNG-IUD group, but were not significantly different within 12 and 24 months. Recurrence rate was significantly higher in the OP group than in the LNG-IUD group. The pCR rate and recurrence rate had no significant differences between the combination group and the other groups. Excluding the LNG-IUD group, 53 and 34 patients received low- and high-dose OP, respectively. The pCR and recurrence rates were comparable between the low- and high-dose OP groups. Maintenance therapy was significantly associated with lower recurrence rate. CONCLUSIONS: Although OP alone achieved more short-term pCR than the other groups, more recurrences occurred after pCR than LNG-IUD alone. High-dose OP as well as combination of OP and LNG-IUD did not increase pCR or reduce recurrence. Maintenance therapy may reduce the recurrence rate after pCR.
Subject(s)
Endometrial Hyperplasia , Endometrial Neoplasms , Levonorgestrel , Progestins , Humans , Female , Retrospective Studies , Middle Aged , Endometrial Hyperplasia/drug therapy , Endometrial Hyperplasia/pathology , Adult , Progestins/administration & dosage , Levonorgestrel/administration & dosage , Endometrial Neoplasms/drug therapy , Endometrial Neoplasms/pathology , Treatment Outcome , Neoplasm Recurrence, Local/drug therapy , Neoplasm Recurrence, Local/pathology , Intrauterine Devices, Medicated , Aged , Carcinoma in Situ/drug therapy , Carcinoma in Situ/pathologyABSTRACT
BACKGROUND: Venous malformations (VMs) are distinguished from lymphatic malformations (LMs) when specific diagnostic skin lesions are present. In the deep type, this is difficult by clinico-radiologic evaluation alone. We aimed to investigate the usefulness of lymphatic vessel endothelial cell (LEC) markers for the differential diagnosis of the deep VMs and LMs. METHODS: A retrospective study was conducted based on the medical records of patients with VMs and LMs who underwent biopsy with both D2-40 and PROX-1 immunohistochemistry. We compared the initial clinico-radiological diagnosis with the final pathological diagnosis and identified which ones showed a difference. RESULTS: From 261 patients who had VMs and LMs, 111 remained after the exclusion of those who showed definite surface diagnostic features. After pathological diagnosis with the expressions of D2-40 and PROX-1, 38 of 111 (34.2%) patients' final diagnoses were changed. Among these 38 cases, diagnosis was not changed by D2-40 positivity alone, but changed by PROX-1 positivity alone (52.6%) or by both (47.4%). The diagnostic changes were more frequent in the deep category (43.7%) than in the superficial category. CONCLUSIONS: Identifying the expression of D2-40, and especially PROX-1, in the differential diagnosis of VMs and LMs may provide important treatment guidelines and understanding their natural course.
Subject(s)
Lymphatic Vessels , Skin Diseases , Vascular Malformations , Humans , Immunohistochemistry , Retrospective Studies , Vascular Malformations/diagnosis , Vascular Malformations/metabolism , Skin , Skin Diseases/metabolismABSTRACT
BACKGROUND: Biomarkers that predict the treatment response in patients with knee osteoarthritis are scarce. This study aimed to investigate the potential role of synovial fluid cell counts and their ratios as biomarkers of primary knee osteoarthritis. METHODS: This retrospective study investigated 96 consecutive knee osteoarthritis patients with knee effusion who underwent joint fluid aspiration analysis and received concomitant intra-articular corticosteroid injections and blood tests. The monocyte-to-lymphocyte ratio (MLR) and neutrophil-to-lymphocyte ratio (NLR) were calculated. After 6 months of treatment, patients were divided into two groups: the responder group showing symptom resolution, defined by a visual analog scale (VAS) score of ≤ 3, without additional treatment, and the non-responder group showing residual symptoms, defined by a VAS score of > 3 and requiring further intervention, such as additional medication, repeated injections, or surgical treatment. Unpaired t-tests and univariate and multivariate logistic regression analyses were conducted between the two groups to predict treatment response after conservative treatment. The predictive value was calculated using the area under the receiver operating characteristic curve, and the optimal cutoff value was determined. RESULTS: Synovial fluid MLR was significantly higher in the non-responder group compared to the responder group (1.86 ± 1.64 vs. 1.11 ± 1.37, respectively; p = 0.02). After accounting for confounding variables, odds ratio of non-responder due to increased MLR were 1.63 (95% confidence interval: 1.11-2.39). The optimal MLR cutoff value for predicting patient response to conservative treatment was 0.941. CONCLUSIONS: MLR may be a potential biomarker for predicting the response to conservative treatment in patients with primary knee osteoarthritis.
Subject(s)
Conservative Treatment , Lymphocytes , Monocytes , Osteoarthritis, Knee , Synovial Fluid , Humans , Osteoarthritis, Knee/therapy , Osteoarthritis, Knee/diagnosis , Retrospective Studies , Male , Female , Synovial Fluid/cytology , Middle Aged , Aged , Treatment Outcome , Conservative Treatment/methods , Injections, Intra-Articular , Biomarkers/analysis , Biomarkers/blood , Predictive Value of Tests , Leukocyte CountABSTRACT
BACKGROUND: This study aimed to investigate the clinical outcomes of fixed-bearing medial unicompartmental knee arthroplasty (UKA) for tibia vara knees and the associated changes in joint space malalignment (JSM) and joint line obliquity (JLO). METHODS: We retrospectively analyzed a consecutive group of 100 patients who underwent fixed-bearing medial UKA with a preoperative medial proximal tibia angle (MPTA) ≥86° (n = 50) and MPTA <86° (n = 50) and who had a minimum 5-year follow-up. Radiological parameters, including the hip-knee-ankle angle, MPTA, and the postoperative JSM and JLO, were measured. Functional evaluation was performed using the range of motion, visual analog scale, Knee Society Knee Score, Knee Society Function Score, and Western Ontario and McMaster Universities Osteoarthritis Index score. RESULTS: The MPTA <86° group showed significantly higher postoperative JLO (91.8 versus 90.4°, respectively; P = .002) and JSM (6.1 versus 4.2°, respectively; P = .026) compared to the MPTA ≥86° group. Functional outcomes, including range of motion, visual analog scale, Knee Society Knee Score, Knee Society Function Score, and Western Ontario and McMaster Universities Osteoarthritis Index scores, were not significantly different between the 2 groups. CONCLUSIONS: Fixed-bearing medial UKA is a safe and effective surgical option for patients who have tibia vara knees, as an increase in JLO and JSM postoperatively does not have a clinically relevant impact, even after a minimum 5-year follow-up.
Subject(s)
Arthroplasty, Replacement, Knee , Bone Diseases, Developmental , Osteoarthritis, Knee , Osteochondrosis/congenital , Humans , Arthroplasty, Replacement, Knee/methods , Osteoarthritis, Knee/surgery , Follow-Up Studies , Retrospective Studies , Knee Joint/surgery , Tibia/surgeryABSTRACT
The electrochemical nitrogen reduction reaction is a crucial process for the sustainable production of ammonia for energy and agriculture applications. However, the reaction's efficiency is highly dependent on the activation of the inert N≡N bond, which is hindered by the electron back-donation to the π* orbitals of the N≡N bond, resulting in low eNRR capacity. Herein, we report a main-group metal-non-metal (O-In-S) eNRR catalyst featuring a dynamic proton bridge, with In-S serving as the polarization pair and O functioning as the dynamic electron pool. In-situ spectroscopic analysis and theoretical calculations reveal that the In-S polarization pair acts as asymmetric dual-sites, polarizing the N≡N bond by concurrently back-donating electrons to both the πx* and πy* orbitals of N2, thereby overcoming the significant band gap limitations, while inhibiting the competitive hydrogen evolution reaction. Meanwhile, the O dynamic electron pool acts as a "repository" for electron storage and donation to the In-S polarization pair. As a result, the O-In-S dynamic proton bridge exhibits exceptional NH3 yield rates and Faradaic efficiencies (FEs) across a wide potential window of 0.3 V, with an optimal NH3 yield of 80.07 ± 4.25 µg h-1 mg-1 and an FE of 38.01 ± 2.02%, outperforming most previously reported catalysts.
ABSTRACT
Huntington's disease (HD) is a devastating neurogenetic disorder whose familial nature and progressive course were first described in the 19th century but for which no disease-modifying treatment is yet available. Through the active participation of HD families, this disorder has acted as a flagship for the application of human molecular genetic strategies to identify disease genes, understand pathogenesis and identify rational targets for development of therapies.
Subject(s)
Disease Susceptibility , Huntington Disease/etiology , Alleles , Animals , Biomarkers , Disease Management , Genetic Association Studies , Genetic Linkage , Genetic Predisposition to Disease , Humans , Huntington Disease/diagnosis , Huntington Disease/therapy , Models, BiologicalABSTRACT
Huntington's disease pathogenesis involves a genetic gain-of-function toxicity mechanism triggered by the expanded HTT CAG repeat. Current therapeutic efforts aim to suppress expression of total or mutant huntingtin, though the relationship of huntingtin's normal activities to the gain-of-function mechanism and what the effects of huntingtin-lowering might be are unclear. Here, we have re-investigated a rare family segregating two presumed HTT loss-of-function (LoF) variants associated with the developmental disorder, Lopes-Maciel-Rodan syndrome (LOMARS), using whole-genome sequencing of DNA from cell lines, in conjunction with analysis of mRNA and protein expression. Our findings correct the muddled annotation of these HTT variants, reaffirm they are the genetic cause of the LOMARS phenotype and demonstrate that each variant is a huntingtin hypomorphic mutation. The NM_002111.8: c.4469+1G>A splice donor variant results in aberrant (exon 34) splicing and severely reduced mRNA, whereas, surprisingly, the NM_002111.8: c.8157T>A NP_002102.4: Phe2719Leu missense variant results in abnormally rapid turnover of the Leu2719 huntingtin protein. Thus, although rare and subject to an as yet unknown LoF intolerance at the population level, bona fide HTT LoF variants can be transmitted by normal individuals leading to severe consequences in compound heterozygotes due to huntingtin deficiency.
Subject(s)
Gene Expression Regulation , Huntingtin Protein/genetics , Mutation , Neurodevelopmental Disorders/genetics , Amino Acid Sequence , Cell Line , Child , Child, Preschool , Female , Humans , Huntingtin Protein/chemistry , Huntingtin Protein/metabolism , Loss of Function Mutation , Male , Mutation, Missense , Neurodevelopmental Disorders/metabolism , Pedigree , Phenotype , RNA Splicing , RNA, Messenger/genetics , RNA, Messenger/metabolism , Sequence Alignment , Sequence Analysis, DNAABSTRACT
A recent genome-wide association study of Huntington disease (HD) implicated genes involved in DNA maintenance processes as modifiers of onset, including multiple genome-wide significant signals in a chr15 region containing the DNA repair gene Fanconi-Associated Nuclease 1 (FAN1). Here, we have carried out detailed genetic, molecular, and cellular investigation of the modifiers at this locus. We find that missense changes within or near the DNA-binding domain (p.Arg507His and p.Arg377Trp) reduce FAN1's DNA-binding activity and its capacity to rescue mitomycin C-induced cytotoxicity, accounting for two infrequent onset-hastening modifier signals. We also idenified a third onset-hastening modifier signal whose mechanism of action remains uncertain but does not involve an amino acid change in FAN1. We present additional evidence that a frequent onset-delaying modifier signal does not alter FAN1 coding sequence but is associated with increased FAN1 mRNA expression in the cerebral cortex. Consistent with these findings and other cellular overexpression and/or suppression studies, knockout of FAN1 increased CAG repeat expansion in HD-induced pluripotent stem cells. Together, these studies support the process of somatic CAG repeat expansion as a therapeutic target in HD, and they clearly indicate that multiple genetic variations act by different means through FAN1 to influence HD onset in a manner that is largely additive, except in the rare circumstance that two onset-hastening alleles are present. Thus, an individual's particular combination of FAN1 haplotypes may influence their suitability for HD clinical trials, particularly if the therapeutic agent aims to reduce CAG repeat instability.
Subject(s)
Endodeoxyribonucleases/genetics , Exodeoxyribonucleases/genetics , Huntington Disease/genetics , Multifunctional Enzymes/genetics , Cell Line , Genome-Wide Association Study/methods , HEK293 Cells , Haplotypes/genetics , Humans , Polymorphism, Single Nucleotide/geneticsABSTRACT
Janus architectures have garnered great research efforts in recent years, leading to outstanding advances in electrocatalysis. Benefiting from the synergistic combination of their anisotropy which endows the manifestation of various co-existing electrochemical properties, and their compartmentalized structure that enables each functional domain to retain its inherent activity, with little to no interference from other domains, Janus architectures show great potential as exceptionally versatile electrocatalysts to complement a plethora of electrocatalytic processes. Thus, coupled with the growing interest in Janus architectures for electrocatalysis, it is imperative to investigate and reconsider their design strategies and future directions.
ABSTRACT
Designing robust electrocatalysts for water-splitting is essential for sustainable hydrogen generation, yet difficult to accomplish. In this study, a fast and facile two-step technique to synthesize Ru/RuO2 aerogels for catalyzing overall water-splitting under alkaline conditions is reported. Benefiting from the synergistic combination of high porosity, heterointerface, and tensile strain effects, the Ru/RuO2 aerogel exhibits low overpotential for oxygen evolution reaction (189 mV) and hydrogen evolution reaction (34 mV) at 10 mA cm-2 , surpassing RuO2 (338 mV) and Pt/C (53 mV), respectively. Notably, when the Ru/RuO2 aerogels are applied at the anode and cathode, the resultant water-splitting cell reflected a low potential of 1.47 V at 10 mA cm-2 , exceeding the commercial Pt/C||RuO2 standard (1.63 V). X-ray adsorption spectroscopy and theoretical studies demonstrate that the heterointerface of Ru/RuO2 optimizes charge redistribution, which reduces the energy barriers for hydrogen and oxygen intermediates, thereby enhancing oxygen and hydrogen evolution reaction kinetics.
ABSTRACT
Metal-organic frameworks (MOFs) and their derivatives have attracted much attention in the field of photo/electrocatalysis owing to their ultrahigh porosity, tunable properties, and superior coordination ability. Regulating the valence electronic structure and coordination environment of MOFs is an effective way to enhance their intrinsic catalytic performance. Rare earth (RE) elements with 4f orbital occupancy provide an opportunity to evoke electron rearrangement, accelerate charged carrier transport, and synergize the surface adsorption of catalysts. Therefore, the integration of RE with MOFs makes it possible to optimize their electronic structure and coordination environment, resulting in enhanced catalytic performance. In this review, progress in current research on the use of RE-modified MOFs and their derivatives for photo/electrocatalysis is summarized and discussed. First, the theoretical advantages of RE in MOF modification are introduced, with a focus on the roles of 4f orbital occupancy and RE ion organic coordination ligands. Then, the application of RE-modified MOFs and their derivatives in photo/electrocatalysis is systematically discussed. Finally, research challenges, future opportunities, and prospects for RE-MOFs are also discussed.