Ultrabroadband plasmon driving selective photoreforming of methanol under ambient conditions.

Liquid methanol has the potential to be the hydrogen energy carrier and storage medium for the future green economy. However, there are still many challenges before zero-emission, affordable molecular H2 can be extracted from methanol with high performance. Here, we present noble-metal-free Cu-WC/W plasmonic nanohybrids which exhibit unsurpassed solar H2 extraction efficiency from pure methanol of 2,176.7 µmol g-1 h-1 at room temperature and normal pressure. Macro-to-micro experiments and simulations unveil that local reaction microenvironments are generated by the coperturbation of WC/W's lattice strain and infrared-plasmonic electric field. It enables spontaneous but selective zero-emission reaction pathways. Such microenvironments are found to be highly cooperative with solar-broadband-plasmon-excited charge carriers flowing from Cu to WC surfaces for efficient stable CH3OH plasmonic reforming with C3-dominated liquid products and 100% selective gaseous H2. Such high efficiency, without any COx emission, can be sustained for over a thousand-hour operation without obvious degradation.

Genomic Evidence for the Nonpathogenic State in HIV-1-Infected Northern Pig-Tailed Macaques.

HIV-1 is a highly host-specific retrovirus that infects humans but not most nonhuman primates. Thus, the lack of a suitable primate model that can be directly infected with HIV-1 hinders HIV-1/AIDS research. In the previous study, we have found that the northern pig-tailed macaques (NPMs) are susceptible to HIV-1 infection but show a nonpathogenic state. In this study, to understand this macaque-HIV-1 interaction, we assembled a de novo genome and longitudinal transcriptome for this species during the course of HIV-1 infection. Using comparative genomic analysis, a positively selected gene, Toll-like receptor 8, was identified with a weak ability to induce an inflammatory response in this macaque. In addition, an interferon-stimulated gene, interferon alpha inducible protein 27, was upregulated in acute HIV-1 infection and acquired an enhanced ability to inhibit HIV-1 replication compared with its human ortholog. These findings coincide with the observation of persistently downregulated immune activation and low viral replication and can partially explain the AIDS-free state in this macaque following HIV-1 infection. This study identified a number of unexplored host genes that may hamper HIV-1 replication and pathogenicity in NPMs and provided new insights into the host defense mechanisms in cross-species infection of HIV-1. This work will facilitate the adoption of NPM as a feasible animal model for HIV-1/AIDS research.

Marine Bioactive Peptides: Anti-Photoaging Mechanisms and Potential Skin Protective Effects.

Skin photoaging, resulting from prolonged exposure to ultraviolet radiation, is a form of exogenous aging that not only impacts the aesthetic aspect of the skin but also exhibits a strong correlation with the onset of skin cancer. Nonetheless, the safety profile of non-natural anti-photoaging medications and the underlying physiological alterations during the process of photoaging remain inadequately elucidated. Consequently, there exists a pressing necessity to devise more secure interventions involving anti-photoaging drugs. Multiple studies have demonstrated the noteworthy significance of marine biomolecules in addressing safety concerns related to anti-photoaging and safeguarding the skin. Notably, bioactive peptides have gained considerable attention in anti-photoaging research due to their capacity to mitigate the physiological alterations associated with photoaging, including oxidative stress; inflammatory response; the abnormal expression of matrix metalloproteinase, hyaluronidase, and elastase; and excessive melanin synthesis. This review provides a systematic description of the research progress on the anti-photoaging and skin protection mechanism of marine bioactive peptides. The focus is on the utilization of marine bioactive peptides as anti-photoaging agents, aiming to offer theoretical references for the development of novel anti-photoaging drugs and methodologies. Additionally, the future prospects of anti-aging drugs are discussed, providing an initial reference for further research in this field.

In Situ Formation of Iodide Precursor for Perovskite Quantum Dots with Application in Efficient Solar Cells.

Perovskite quantum dots (PQDs) become a kind of competitive material for fabricating high-performance solar cells due to their solution processability and outstanding optoelectronic properties. However, the current synthesis method of PQDs is mostly based on the binary-precursor method, which results in a large deviation of the I/Pb input ratio in the reaction system from the stoichiometric ratio of PQDs. Herein, a ternary-precursor method with an iodide source self-filling ability is reported for the synthesis of the CsPbI3 PQDs with high optoelectronic properties. Systematically experimental characterizations and theoretical calculations are conducted to fundamentally understand the effects of the I/Pb input molar ratio on the crystallographic and optoelectronic properties of PQDs. The results reveal that increasing the I/Pb input molar ratio can obtain ideal cubic structure PQDs with iodine-rich surfaces, which can significantly reduce the surface defects of PQDs and realize high orientation of PQD solids, facilitating charge carrier transport in the PQD solids with diminished nonradiative recombination. Consequently, the PQD solar cells exhibit an impressive efficiency of 15.16%, which is largely improved compared with that of 12.83% for the control solar cell. This work provides a feasible strategy for synthesizing high-quality PQDs for high-performance optoelectronic devices.

Depicting the genetic and metabolic panorama of chemical diversity in the tea plant.

As a frequently consumed beverage worldwide, tea is rich in naturally important bioactive metabolites. Combining genetic, metabolomic and biochemical methodologies, here, we present a comprehensive study to dissect the chemical diversity in tea plant. A total of 2837 metabolites were identified at high-resolution with 1098 of them being structurally annotated and 63 of them were structurally identified. Metabolite-based genome-wide association mapping identified 6199 and 7823 metabolic quantitative trait loci (mQTL) for 971 and 1254 compounds in young leaves (YL) and the third leaves (TL), respectively. The major mQTL (i.e., P < 1.05 × 10-5, and phenotypic variation explained (PVE) > 25%) were further interrogated. Through extensive annotation of the tea metabolome as well as network-based analysis, this study broadens the understanding of tea metabolism and lays a solid foundation for revealing the natural variations in the chemical composition of the tea plant. Interestingly, we found that galloylations, rather than hydroxylations or glycosylations, were the largest class of conversions within the tea metabolome. The prevalence of galloylations in tea is unusual, as hydroxylations and glycosylations are typically the most prominent conversions of plant specialized metabolism. The biosynthetic pathway of flavonoids, which are one of the most featured metabolites in tea plant, was further refined with the identified metabolites. And we demonstrated the further mining and interpretation of our GWAS results by verifying two identified mQTL (including functional candidate genes CsUGTa, CsUGTb, and CsCCoAOMT) and completing the flavonoid biosynthetic pathway of the tea plant.

Correction: First-principles calculations of interfacial thermal transport properties between SiC/Si substrates and compounds of boron with selected group V elements.

Correction for 'First-principles calculations of interfacial thermal transport properties between SiC/Si substrates and compounds of boron with selected group V elements' by Zhehao Sun et al., Phys. Chem. Chem. Phys., 2019, 21, 6011-6020, https://doi.org/10.1039/C8CP07516F.

Radiomics of pericoronary adipose tissue on computed tomography angiography predicts coronary heart disease in patients with type 2 diabetes mellitus.

BACKGROUND: Diabetes is a common chronic metabolic disease. The progression of the disease promotes vascular inflammation and the formation of atherosclerosis, leading to cardiovascular disease. The coronary artery perivascular adipose tissue attenuation index based on CCTA is a new noninvasive imaging biomarker that reflects the spatial changes in perivascular adipose tissue attenuation in CCTA images and the inflammation around the coronary arteries. In this study, a radiomics approach is proposed to extract a large number of image features from CCTA in a high-throughput manner and combined with clinical diagnostic data to explore the predictive ability of vascular perivascular adipose imaging data based on CCTA for coronary heart disease in diabetic patients. METHODS: R language was used for statistical analysis to screen the variables with significant differences. A presegmentation model was used for CCTA vessel segmentation, and the pericoronary adipose region was screened out. PyRadiomics was used to calculate the radiomics features of pericoronary adipose tissue, and SVM, DT and RF were used to model and analyze the clinical data and radiomics data. Model performance was evaluated using indicators such as PPV, FPR, AAC, and ROC. RESULTS: The results indicate that there are significant differences in age, blood pressure, and some biochemical indicators between diabetes patients with and without coronary heart disease. Among 1037 calculated radiomic parameters, 18.3% showed significant differences in imaging omics features. Three modeling methods were used to analyze different combinations of clinical information, internal vascular radiomics information and pericoronary vascular fat radiomics information. The results showed that the dataset of full data had the highest ACC values under different machine learning models. The support vector machine method showed the best specificity, sensitivity, and accuracy for this dataset. CONCLUSIONS: In this study, the clinical data and pericoronary radiomics data of CCTA were fused to predict the occurrence of coronary heart disease in diabetic patients. This provides information for the early detection of coronary heart disease in patients with diabetes and allows for timely intervention and treatment.

Renal histology of Fanconi syndrome associated with adefovir dipivoxil: A case report.

A sporadic occurrence of Fanconi syndrome associated with adefovir dipivoxil (ADV) has been reported, particularly when confirmed by renal biopsy. This study presents the case of a 53-year-old man who had been taking ADV 10 mg daily for 10 years to treat chronic hepatitis B (CHB) and subsequently developed Fanconi syndrome. The clinical manifestations included hypophosphatemic osteomalacia, glucosuria, renal tubular acidosis, low-molecular-weight proteinuria, and renal insufficiency. Renal biopsy revealed significant injury to proximal tubular epithelial cells, including vacuolar degeneration and regeneration of tubular epithelial cells. The ultrastructural pathology indicated severe morphological abnormalities of mitochondria, such as densely packed and enlarged mitochondria, with loss, blunting, and disordered arrangement of cristae. Following discontinuation of ADV and supplementation with oral phosphate, hypophosphatemia, glucosuria, and proteinuria were resolved. These findings support the previous hypothesis that ADV-induced nephrotoxicity may involve mitochondrial injury.

LPS-induced senescence of macrophages aggravates calcification and senescence of vascular smooth muscle cells via IFITM3.

BACKGROUND: Cellular senescence, macrophages infiltration, and vascular smooth muscle cells (VSMCs) osteogenic transdifferentiation participate in the pathophysiology of vascular calcification in chronic kidney disease (CKD). Senescent macrophages are involved in the regulation of inflammation in pathological diseases. In addition, senescent cells spread senescence to neighboring cells via Interferon-induced transmembrane protein3 (IFITM3). However, the role of senescent macrophages and IFITM3 in VSMCs calcification remains unexplored. AIMS: To explore the hypothesis that senescent macrophages contribute to the calcification and senescence of VSMCs via IFITM3. METHODS: Here, the macrophage senescence model was established using Lipopolysaccharides (LPS). The VSMCs were subjected to supernatants from macrophages (MCFS) or LPS-induced macrophages (LPS-MCFS) in the presence or absence of calcifying media (CM). Senescence-associated ß-galactosidase (SA-ß-gal), Alizarin red (AR), immunofluorescent staining, and western blot were used to identify cell senescence and calcification. RESULTS: The expression of IFITM3 was significantly increased in LPS-induced macrophages and the supernatants. The VSMCs transdifferentiated into osteogenic phenotype, expressing higher osteogenic differentiation markers (RUNX2) and lower VSMCs constructive makers (SM22α) when cultured with senescent macrophages supernatants. Also, senescence markers (p16 and p21) in VSMCs were significantly increased by senescent macrophages supernatants treated. However, IFITM3 knockdown inhibited this process. CONCLUSIONS: Our study showed that LPS-induced senescence of macrophages accelerated the calcification of VSMCs via IFITM3. These data provide a new perspective linking VC and aging, which may provide clues for diagnosing and treating accelerated vascular aging in patients with CKD.

Dipolar Chemical Bridge Induced CsPbI3 Perovskite Solar Cells with 21.86 % Efficiency.

CsPbI3 perovskite receives tremendous attention for photovoltaic applications due to its ideal band gap and good thermal stability. However, CsPbI3 perovskite solar cells (PSCs) significantly suffer from photovoltage deficits because of serious interfacial energy losses within the PSCs, which to a large extent affects the photovoltaic performance of PSCs. Herein, a dipolar chemical bridge (DCB) is constructed between the perovskite and TiO2 layers to lower interfacial energy losses and thus improve the charge extraction of PSCs. The results reveal that the DCB could form a beneficial interfacial dipole between the perovskite and TiO2 layers, which could optimize the interfacial energetics of perovskite/TiO2 layers and thus improve the energy level alignment within the PSCs. Meanwhile, the constructed DCB could also simultaneously passivate the surface defects of perovskite and TiO2 layers, greatly lowering interfacial recombination. Consequently, the photovoltage deficit of CsPbI3 PSCs is largely reduced, leading to a record efficiency of 21.86 % being realized. Meanwhile, the operation stability of PSCs is also largely improved due to the high-quality perovskite films with released interfacial tensile strain being obtained after forming the DCB within the PSCs.

A 5-channel local B0 shimming coil combined with a 3-channel RF receiver coil for rat brain imaging at 3 T.

PURPOSE: We aimed to improve B0 magnetic field homogeneity and minimize the interference between RF coils and local B0 shimming coils with few channel numbers. METHODS: To design and construct the prototype for B0 shimming of the rat brain, we first evaluated the interferences of single shimming loops on RF receiver loops. Then, B0 shimming of the whole rat brain was implemented using an optimization procedure. The positions and currents of the local shimming coils with channel numbers from 3 to 6 were optimized to improve shimming performance. Based on the simulation results, a 5-channel local shimming coil, combined with a 3-channel RF receiver coil, was constructed and evaluated by animal experiments. RESULTS: There was marginal SNR loss within 5% after integrating the local shimming coil into the RF receiver coil. With respect to the Siemens standard shims up to second order, the B0 inhomogeneity in one whole rat brain was reduced from 39.6 Hz to 24.7 Hz by using the local shimming coil. A large portion of the EPI distortions was recovered after using the 5-channel local shimming coil. The temporal SNR using the local shimming coil was higher than that using the Siemens standard shims up to second order, with an improvement of more than 24%. CONCLUSIONS: The local shimming coil can improve B0 magnetic field homogeneity despite minor effects on the RF coil and can benefit a variety of applications that are sensitive to B0 inhomogeneity. Nevertheless, EPI for rat brain is still very challenging.

SuperMAP: Deep ultrafast MR relaxometry with joint spatiotemporal undersampling.

PURPOSE: To develop an ultrafast and robust MR parameter mapping network using deep learning. THEORY AND METHODS: We design a deep learning framework called SuperMAP that directly converts a series of undersampled (both in k-space and parameter-space) parameter-weighted images into several quantitative maps, bypassing the conventional exponential fitting procedure. We also present a novel technique to simultaneously reconstruct T1rho and T2 relaxation maps within a single scan. Full data were acquired and retrospectively undersampled for training and testing using traditional and state-of-the-art techniques for comparison. Prospective data were also collected to evaluate the trained network. The performance of all methods is evaluated using the parameter qualification errors and other metrics in the segmented regions of interest. RESULTS: SuperMAP achieved accurate T1rho and T2 mapping with high acceleration factors (R = 24 and R = 32). It exploited both spatial and temporal information and yielded low error (normalized mean square error of 2.7% at R = 24 and 2.8% at R = 32) and high resemblance (structural similarity of 97% at R = 24 and 96% at R = 32) to the gold standard. The network trained with retrospectively undersampled data also works well for the prospective data (with a slightly lower acceleration factor). SuperMAP is also superior to conventional methods. CONCLUSION: Our results demonstrate the feasibility of generating superfast MR parameter maps through very few undersampled parameter-weighted images. SuperMAP can simultaneously generate T1rho and T2 relaxation maps in a short scan time.

Macrophages release IL11-containing filopodial tip vesicles and contribute to renal interstitial inflammation.

Macrophage filopodia, which are dynamic nanotube-like protrusions, have mainly been studied in the context of pathogen clearance. The mechanisms by which they facilitate intercellular communication and mediate tissue inflammation remain poorly understood. Here, we show that macrophage filopodia produce a unique membrane structure called "filopodial tip vesicle" (FTV) that originate from the tip of macrophages filopodia. Filopodia tip-derived particles contain numerous internal-vesicles and function as cargo storage depots via nanotubular transport. Functional studies indicate that the shedding of FTV from filopodia tip allows the delivery of many molecular signalling molecules to fibroblasts. We observed that FTV derived from M1 macrophages and high glucose (HG)-stimulated macrophages (HG/M1-ftv) exhibit an enrichment of the chemokine IL11, which is critical for fibroblast transdifferentiation. HG/M1-ftv induce renal interstitial fibrosis in diabetic mice, while FTV inhibition or targeting FTV IL11- alleviates renal interstitial fibrosis, suggesting that the HG/M1-ftvIL11 pathway may be a novel mechanism underlying renal fibrosis in diabetic nephropathy. Collectively, FTV release could represent a novel function by which filopodia contribute to cell biological processes, and FTV is potentially associated with macrophage filopodia-related fibrotic diseases. Video Abstract.

Soft phonon modes lead to suppressed thermal conductivity in Ag-based chalcopyrites under high pressure.

Pressure is a powerful way to modulate physical properties. Understanding the effect of pressure on the thermal transport properties of thermoelectric materials is of great importance for the efficient design and optimization of thermoelectric performance. In this work, based on first-principles calculations and phonon Boltzmann transport theory, we find that the lattice thermal conductivities of Ag-based chalcopyrites AgXY2 (X = Al, Ga, and In; Y = S, Se, and Te) are dramatically suppressed by applying pressure. The inherent distorted tetrahedral configuration together with highly delocalized p-orbital electrons promotes the formation of metavalent bonding. The fact of metavalent bonding with a single bonding electron and small electron transfer between neighboring atoms leads to soft low-frequency optical phonons. With the increase of pressure, the softening of acoustic and low-frequency optical phonons induces enhanced anharmonicity and scattering channels. Such strong acoustic-optical phonon coupling results in larger phonon scattering rates and thus lowers the lattice thermal conductivity. These findings not only help unveil the underlying physical mechanisms for the anomalous thermal transport behaviors under high pressure, but also pave the way for the pressure tuning of high-performance Ag-based thermoelectric materials.

Multiple test procedures of disease prevalence based on stratified partially validated series in the presence of a gold standard.

This paper discusses the problem of disease prevalence in clinical studies, focusing on multiple comparisons based on stratified partially validated series in the presence of a gold standard. Five test statistics, including two Wald-type test statistics, the inverse hyperbolic tangent transformation test statistic, likelihood ratio test statistic, and score test statistic, are proposed to conduct multiple comparisons. To control the overall type I error rate, several adjustment procedures are developed, namely the Bonferroni, Single-step adjusted MaxT, Single-step adjusted MinP, Holm's Step-down, and Hochberg's step-up procedures, based on these test statistics. The performance of the proposed methods is evaluated through simulation studies in terms of the empirical type I error rate and empirical power. Simulation results show that the Single-step adjusted MaxT procedure and Single-step adjusted MinP procedure generally outperform the other three procedures, and these two test procedures based on all test statistics have satisfactory performance. Notably, the Single-step adjusted MinP procedure tends to exhibit higher empirical power than the Single-step adjusted MaxT procedure. Furthermore, the Step-down and Step-up procedures show greater power compared to the Bonferroni method. The study also observes that as the validated ratio increases, the empirical type I errors of all test procedures approach the nominal level while maintaining higher power. Two real examples are presented to illustrate the proposed methods.

Clinical features and outcomes of calciphylaxis in Chinese patients with chronic kidney disease.

AIM: Calciphylaxis is a rare disease, predominantly in chronic kidney disease (CKD), characterized by high morbidity and mortality. Data from the Chinese population have been an invaluable resource for a better understanding of natural history, optimal treatments and outcomes of calciphylaxis. METHODS: A retrospective study was conducted in 51 Chinese patients diagnosed with calciphylaxis at Zhong Da Hospital affiliated to Southeast University from December 2015 to September 2020. RESULTS: Between 2015 and 2020, 51 cases of calciphylaxis were registered in The China Calciphylaxis Registry (http://www.calciphylaxis.com.cn), which was developed by Zhong Da Hospital. The mean age of the cohort was 52.02 ± 14.09 years, and 37.3% were female. Forty-three patients (84.3%) were on haemodialysis, with a median dialysis vintage of 88 months. Eighteen patients (35.3%) had a resolution of calciphylaxis and 20 patients (39.2%) died. Patients in later stages had higher overall mortality than those in earlier stages. Delay from skin lesions onset to diagnosis and calciphylaxis-related infections were risk factors in both early and overall mortality. Additionally, dialysis vintage and infections were significant risk factors in calciphylaxis-specific mortality. Among therapeutic strategies, only the use of sodium thiosulfate (STS) ≥3 courses (14 injections) was significantly associated with decreased hazard of death in both early and overall mortality. CONCLUSION: For Chinese patients with calciphylaxis, delay from skin lesions onset to diagnosis and infections secondary to wounds are risk factors for the prognosis of patients with calciphylaxis. Additionally, patients in earlier stages have better survival and early continuous use of STS is highly suggested.

Early diagnosis strategy of calciphylaxis in dialysis patients.

Calciphylaxis, a rapidly progressive and potentially life-threatening vascular calcification syndrome that clinically presents with persistently painful, ulcerative, or necrotizing skin lesions in multiple parts of the body, is predominantly observed in patients treated with dialysis. Early diagnosis of calciphylaxis is a key measure for reducing high disability and mortality. At present, there is no unified diagnostic standard for calciphylaxis, and there is a lack of effective early screening strategies. This paper summarized and discussed the diagnostic accuracy of calciphylaxis based on the latest research worldwide. We propose a modified strategy for the early diagnosis of calciphylaxis, which is suitable for dialysis patients to help clinicians better identify such disease and improve prognosis.

Vascular, valvular and kidney calcification manifested in mouse models of adenine-induced chronic kidney disease.

BACKGROUND: Ectopic calcification (EC) involves multiple organ systems in chronic kidney disease (CKD). Previous CKD-animal models primarily focused on a certain histological abnormality but did not show the correlation with calcified development among various tissues. This study compared calcified deposition in various tissues during CKD progression in mice. METHODS: Male 8-week-old C57BL/6J mice were randomly allocated to the seven groups: a basic, adenine, high-phosphorus, or adenine and high-phosphorus diet for 12-16 weeks (Ctl16, A12, P16, or AP16, respectively); an adenine diet for 4-6 weeks; and a high-phosphorus or adenine and high-phosphorus diet for 10-12 weeks (A6 + P10, A4 + P12, or A4 + AP12, respectively). RESULTS: Compared to the Ctl16 mice, the P16 mice only displayed a slight abnormality in serum calcium and phosphorus; the A12 mice had the most serious kidney impairment; the A4 + P12 and A6 + P10 mice had similar conditions of CKD, mineral abnormalities, and mild calcification in the kidney and aortic valves; the A4 + AP12 and AP16 groups had severe kidney impairment, mineral abnormalities and calcification in the kidneys, aortic valves and aortas. Furthermore, calcium-phosphate particles were deposited not only in the tubulointerstitial compartment but in the glomerular and tubular basement membrane. The elemental composition of EC in various tissues matched the calcification of human cardiovascular tissue as determined by energy dispersive spectroscopy. CONCLUSIONS: The severity of CKD was unparalleled with the progression of mineral metabolism disorder and EC. Calcification was closely related in different tissues and observed in the glomerular and tubular basement membranes.

Previous CKD-animal models primarily focused on a certain histological abnormality but lacked investigations of the interplay of EC in various tissues. This study compared calcified deposition in several tissues during CKD progression in mice, which was closely related. The severity of CKD was unparalleled with the development of ectopic calcification. Glomerular and tubular basement membrane calcification was detected in CKD mice, which has been considered extremely rare in clinical.

Scale-Hybrid Group Distillation with Knowledge Disentangling for Continual Semantic Segmentation.

Continual semantic segmentation (CSS) aims to learn new tasks sequentially and extract object(s) and stuff represented by pixel-level maps of new categories while preserving the original segmentation capabilities even when the old class data is absent. Current CSS methods typically preserve the capacities of segmenting old classes via knowledge distillation, which encounters the limitations of insufficient utilization of the semantic knowledge, i.e., only distilling the last layer of the feature encoder, and the semantic shift of background caused by directly distilling the entire feature map of the decoder. In this paper, we propose a novel CCS method based on scale-hybrid distillation and knowledge disentangling to address these limitations. Firstly, we propose a scale-hybrid group semantic distillation (SGD) method for encoding, which transfers the multi-scale knowledge from the old model's feature encoder with group pooling refinement to improve the stability of new models. Then, the knowledge disentangling distillation (KDD) method for decoding is proposed to distillate feature maps with the guidance of the old class regions and reduce incorrect guides from old models towards better plasticity. Extensive experiments are conducted on the Pascal VOC and ADE20K datasets. Competitive performance compared with other state-of-the-art methods demonstrates the effectiveness of our proposed method.

Expediting Oxygen Evolution by Optimizing Cation and Anion Complexity in Electrocatalysts Based on Metal Phosphorous Trichalcogenides.

Purposely changing the rate-determining step (RDS) of oxygen evolution reaction (OER) remains a major challenge for enhancing the energy efficiency of electrochemical splitting of water. Here we show that the OER RDS can be regulated by simply varying the cation and anion complexity in a family of the metal phosphorous trichalcogenide electrocatalysts (MPT3 , where M=Fe, Ni; T=S, Se), achieving an exceptionally high OER activity in (Ni,Fe)P(S,Se)3 , as demonstrated by its ultra-low Tafel slope (34 mV dec-1 ) and a very low overpotential compared to many relevant OER catalysts. This is strongly supported by density functional theory calculations, which showed that this catalyst has a nearly optimal OER activity descriptor value of ΔG(O*)-ΔG(OH*)=1.5 eV. We also found that the activity descriptor is proportional to a newly proposed cation/anion complexity index that consists of pairwise contributions from cation-anion bonds in a catalyst compound, revealing the pivotal role of the cation-anion interactions in determining the catalyst performance and providing a simple way for predicting catalytic activities.