Bithiophene-Functionalized Infrared Two-Photon Absorption Metal Complexes as Single-Molecule Platforms for Synergistic Photodynamic, Photothermal, and Chemotherapy.

A planar conjugated ligand functionalized with bithiophene and its Ru(II), Os(II), and Ir(III) complexes have been constructed as single-molecule platform for synergistic photodynamic, photothermal, and chemotherapy. The complexes have significant two-photon absorption at 808 nm and remarkable singlet oxygen and superoxide anion production in aqueous solution and cells when exposed to 808 nm infrared irradiation. The most potent Ru(II) complex Ru7 enters tumor cells via the rare macropinocytosis, locates in both nuclei and mitochondria, and regulates DNA-related chemotherapeutic mechanisms intranuclearly including DNA topoisomerase and RNA polymerase inhibition and their synergistic effects with photoactivated apoptosis, ferroptosis and DNA cleavage. Ru7 exhibits high efficacy in vivo for malignant melanoma and cisplatin-resistant non-small cell lung cancer tumors, with a 100% survival rate of mice, low toxicity to normal cells and low residual rate. Such an infrared two-photon activatable metal complex may contribute to a new generation of single-molecule-based integrated diagnosis and treatment platform to address drug resistance in clinical practice and phototherapy for large, deeply located solid tumors.

The Inhibition Mechanisms of Three Structurally Different Salvianolic Acids on the Non-Enzymatic Glycation of Bovine Serum Albumin.

The antiglycation mechanisms of three structurally different salvianolic acids (Sals) including salvianolic acid A (Sal-A), salvianolic acid B (Sal-B) and salvianolic acid C (Sal-C) were investigated using the bovine serum albumin (BSA)-fructose model. The results showed that the three compounds could inhibit the formation of glycation products, maintain protein structural stability, mitigate the development of amyloid fibrils and scavenge radicals. Notably, Sal-A possessed the highest anti-glycated activity compared with Sal-B and Sal-C. This may be related to the fact that Sal-A contained the most molecules of caffeic acid (Sal-A, Sal-B, and Sal-C possessing two, one, and zero caffeic acid units, respectively), and caffeic acid played a leading role in the antiglycation properties relative to Danshensu. Moreover, these compounds quenched the intrinsic fluorescence intensity of BSA in a static mode, with the binding constants in the order of Sal-A > Sal-B > Sal-C. Obviously, Sal-A possessed the strongest binding affinity among these compounds, which may be one of the reasons why it exhibited the optimal antiglycation capability. Furthermore, molecular docking demonstrated that the three Sals exerted protective effects on BSA by preventing glycation modification of lysine and arginine residues. These findings would provide valuable insights into the potential application of Sals for alleviating non-enzymatic glycation of protein.

Optimizing Intermediate Adsorption over PdM (M=Fe, Co, Ni, Cu) Bimetallene for Boosted Nitrate Electroreduction to Ammonia.

Electrochemical reduction of nitrate to ammonia (NO3RR) is a promising and eco-friendly strategy for ammonia production. However, the sluggish kinetics of the eight-electron transfer process and poor mechanistic understanding strongly impedes its application. To unveil the internal laws, herein, a library of Pd-based bimetallene with various transition metal dopants (PdM (M=Fe, Co, Ni, Cu)) are screened to learn their structure-activity relationship towards NO3RR. The ultra-thin structure of metallene greatly facilitates the exposure of active sites, and the transition metals dopants break the electronic balance and upshift its d-band center, thus optimizing intermediates adsorption. The anisotropic electronic characteristics of these transition metals make the NO3RR activity in the order of PdCu>PdCo≈PdFe>PdNi>Pd, and a record-high NH3 yield rate of 295 mg h-1 mgcat -1 along with Faradaic efficiency of 90.9 % is achieved in neutral electrolyte on PdCu bimetallene. Detailed studies further reveal that the moderate N-species (*NO3 and *NO2) adsorption ability, enhanced *NO activation, and reduced HER activity facilitate the NH3 production. We believe our results will give a systematic guidance to the future design of NO3RR catalysts.

MRI-based tumor shrinkage patterns after early neoadjuvant therapy in breast cancer: correlation with molecular subtypes and pathological response after therapy.

BACKGROUND: MRI-based tumor shrinkage patterns (TSP) after neoadjuvant therapy (NAT) have been associated with pathological response. However, the understanding of TSP after early NAT remains limited. We aimed to analyze the relationship between TSP after early NAT and pathological response after therapy in different molecular subtypes. METHODS: We prospectively enrolled participants with invasive ductal breast cancers who received NAT and performed pretreatment DCE-MRI from September 2020 to August 2022. Early-stage MRIs were performed after the first (1st-MRI) and/or second (2nd-MRI) cycle of NAT. Tumor shrinkage patterns were categorized into four groups: concentric shrinkage, diffuse decrease (DD), decrease of intensity only (DIO), and stable disease (SD). Logistic regression analysis was performed to identify independent variables associated with pathologic complete response (pCR), and stratified analysis according to tumor hormone receptor (HR)/human epidermal growth factor receptor 2 (HER2) disease subtype. RESULTS: 344 participants (mean age: 50 years, 113/345 [33%] pCR) with 345 tumors (1 bilateral) had evaluable 1st-MRI or 2nd-MRI to comprise the primary analysis cohort, of which 244 participants with 245 tumors had evaluable 1st-MRI (82/245 [33%] pCR) and 206 participants with 207 tumors had evaluable 2nd-MRI (69/207 [33%] pCR) to comprise the 1st- and 2nd-timepoint subgroup analysis cohorts, respectively. In the primary analysis, multivariate analysis showed that early DD pattern (OR = 12.08; 95% CI 3.34-43.75; p < 0.001) predicted pCR independently of the change in tumor size (OR = 1.37; 95% CI 0.94-2.01; p = 0.106) in HR+/HER2- subtype, and the change in tumor size was a strong pCR predictor in HER2+ (OR = 1.61; 95% CI 1.22-2.13; p = 0.001) and triple-negative breast cancer (TNBC, OR = 1.61; 95% CI 1.22-2.11; p = 0.001). Compared with the change in tumor size, the SD pattern achieved a higher negative predictive value in HER2+ and TNBC. The statistical significance of complete 1st-timepoint subgroup analysis was consistent with the primary analysis. CONCLUSION: The diffuse decrease pattern in HR+/HER2- subtype and stable disease in HER2+ and TNBC after early NAT could serve as additional straightforward and comprehensible indicators of treatment response. TRIAL REGISTRATION: Trial registration at https://www.chictr.org.cn/ . REGISTRATION NUMBER: ChiCTR2000038578, registered September 24, 2020.

Rational design of antibodies and development of a novel method for (1-3)-ß-D glucan detection as an alternative to Limulus amebocyte lysate assay.

With advances in medicine, increasing medical interventions have increased the risk of invasive fungal disease development. (1-3)-ß-D glucan (BDG) is a common fungal biomarker in serological tests. However, the scarcity of Limulus resources for BDG detection poses a challenge. This study addresses the need for an alternative to Limulus amebocyte lysate by using BDG mutant antibody for chemiluminescence detection. The wild-type BDG antibody was obtained by immunizing rabbits. An optimal V52HI/N34L Y mutant antibody, which has increased 3.7-fold of the testing efficiency compared to the wild-type antibody, was first achieved by mutating "hot-spot" residues that contribute to strong non-covalent bonds, as determined by alanine scanning and molecular dynamics simulation. The mutant was then applied to develop the magnetic particle chemiluminescence method. 574 clinical samples were tested using the developed method, with a cutoff value of 95 pg/mL set by Limulus amebocyte lysate. The receiver operating characteristic curve demonstrated an area under the curve of 0.905 (95% CI: 0.880-0.929). Chemiluminescence detected an antigen concentration of 89.98 pg/mL, exhibiting a sensitivity of 83.33% and specificity of 89.76%. In conclusion, the results showed a good agreement with Limulus amebocyte lysate and demonstrated the feasibility of using BDG mutant antibodies for invasive fungal disease diagnosis. The new method based on chemiluminescence for detecting BDG could shorten the sample-to-result time to approximately 30 min, rescue Limulus from being endangered and is resource efficient in terms of equipment and the non-use of a skilled technician.

Virtual water flows and drivers in the international trade of agricultural products of the regional comprehensive economic partnership.

The regional comprehensive economic partnership (RCEP) is today the largest free trade area in the world. This paper examines agricultural trade in the RCEP from 2010 to 2019 through the perspective of virtual water. And the drivers of the virtual water flow between China and the RCEP are also explored. The results are as follows: the virtual water flow during the study period was 2,576.51 billion m3. From a temporal perspective, the annual virtual water flow over the study period is characterized by a slow rise-significant fall-slow rise. It has the characteristics of concentration in spatial distribution and water resources and product structure. However, the concentration degree showed a downward trend during the study period. Then, we have divided the major trading into four categories based on whether there is a shortage of water on both sides of the trade. In terms of the drivers of virtual water flows between China and the RCEP, we have used the gravity model to arrive at the following findings: crop yields, bilateral economic scale, and agricultural labor resources are the main drivers. Our research results have reference values for adjusting bilateral agricultural trade and water conservation.

Molecular Coupling Strategy Achieving In Situ Synthesis of Agglomeration-Free Solid Composite Electrolytes.

Solid composite electrolytes (SCEs) synergize inorganic and polymer merits for viable commercial application. However, inferior filler-polymer interfacial stability ultimately leads to the agglomeration of inorganic particles and greatly impedes Li+ migration. Herein, triethoxyvinylsilane (VTEO) is employed to form a strong chemical interaction between poly(vinylene carbonate) (PVC) and montmorillonite (MMT) via in situ solidification, which eliminates the agglomeration and improves interfacial compatibility. Consequently, the obtained solid composite electrolytes (PVC-s-MMT) achieve increased Li+ conductivity (0.4 mS cm-1 at 25 °C), enhanced transference number (0.74), and increased oxidation potential (5.2 V). The Li/PVC-s-MMT/LiFePO4 cells exhibit outstanding cycling performance (>99.5% after 600 cycles) at 1C at room temperature. Moreover, density functional theory (DFT) calculations are applied to uncover the fast interfacial conducting channels of PVC-s-MMT. Our work provides a feasible in situ synthesis method to prepare agglomeration-free SCEs, which is highly compatible with existing battery production processes of liquid electrolytes.

Extending Ring-Chain Coupling Empirical Law to Lithium-Mediated Electrochemical Ammonia Synthesis.

With its efficient nitrogen fixation kinetics, electrochemical lithium-mediated nitrogen reduction reaction (LMNRR) holds promise for replacing Haber-Bosch process and realizing sustainable and green ammonia production. However, the general interface problem in lithium electrochemistry seriously impedes the further enhancement of LMNRR performance. Inspired by the development history of lithium battery electrolytes, here, we extend the ring-chain solvents coupling law to LMNRR system to rationally optimize the interface during the reaction process, achieving nearly a two-fold Faradaic efficiency up to 54.78±1.60 %. Systematic theoretical simulations and experimental analysis jointly decipher that the anion-rich Li+ solvation structure derived from ring tetrahydrofuran coupling with chain ether successfully suppresses the excessive passivation of electrolyte decomposition at the reaction interface, thus promoting the mass transfer of active species and enhancing the nitrogen fixation kinetics. This work offers a progressive insight into the electrolyte design of LMNRR system.

Structural connectivity from DTI to predict mild cognitive impairment in de novo Parkinson's disease.

BACKGROUND: Early detection of Parkinson's disease (PD) patients at high risk for mild cognitive impairment (MCI) can help with timely intervention. White matter structural connectivity is considered an early and sensitive indicator of neurodegenerative disease. OBJECTIVES: To investigate whether baseline white matter structural connectivity features from diffusion tensor imaging (DTI) of de novo PD patients can help predict PD-MCI conversion at an individual level using machine learning methods. METHODS: We included 90 de novo PD patients who underwent DTI and 3D T1-weighted imaging. Elastic net-based feature consensus ranking (ENFCR) was used with 1000 random training sets to select clinical and structural connectivity features. Linear discrimination analysis (LDA), support vector machine (SVM), K-nearest neighbor (KNN) and naïve Bayes (NB) classifiers were trained based on features selected more than 500 times. The area under the ROC curve (AUC), accuracy (ACC), sensitivity (SEN) and specificity (SPE) were used to evaluate model performance. RESULTS: A total of 57 PD patients were classified as PD-MCI nonconverters, and 33 PD patients were classified as PD-MCI converters. The models trained with clinical data showed moderate performance (AUC range: 0.62-0.68; ACC range: 0.63-0.77; SEN range: 0.45-0.66; SPE range: 0.64-0.84). Models trained with structural connectivity (AUC range, 0.81-0.84; ACC range, 0.75-0.86; SEN range, 0.77-0.91; SPE range, 0.71-0.88) performed similar to models that were trained with both clinical and structural connectivity data (AUC range, 0.81-0.85; ACC range, 0.74-0.85; SEN range, 0.79-0.91; SPE range, 0.70-0.89). CONCLUSIONS: Baseline white matter structural connectivity from DTI is helpful in predicting future MCI conversion in de novo PD patients.

In situ observation of a stepwise [2 + 2] photocycloaddition process using fluorescence spectroscopy.

Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms. However, investigating the early stages of solid-state reactions/transformations is still challenging. Here we introduce in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer platform. The structural changes and kinetics of each step under ultraviolet light irradiation versus time are accompanied by the gradual increase-decrease of intensity and blue-shift of the fluorescence spectra from the crystals. Monitoring the fluorescence behavior using a laser scanning confocal microscope can directly visualize the inhomogeneity of the photocycloaddition reaction in a single crystal. Theoretical calculations allow us to rationalize the fluorescence behavior of these compounds. We provide a convenient strategy for visualizing the solid-state photocycloaddition dynamics using fluorescence spectroscopy and open an avenue for kinetic studies of a variety of fast reactions.

Correlation between synthetic MRI relaxometry and apparent diffusion coefficient in breast cancer subtypes with different neoadjuvant therapy response.

BACKGROUND: To evaluate the correlation between synthetic MRI (syMRI) relaxometry and apparent diffusion coefficient (ADC) maps in different breast cancer subtypes and treatment response subgroups. METHODS: Two hundred sixty-three neoadjuvant therapy (NAT)-treated breast cancer patients with baseline MRI were enrolled. Tumor annotations were obtained by drawing regions of interest (ROIs) along the lesion on T1/T2/PD and ADC maps respectively. Histogram features from T1/T2/PD and ADC maps were respectively calculated, and the correlation between each pair of identical features was analyzed. Meanwhile, features between different NAT treatment response groups were compared, and their discriminatory power was evaluated. RESULTS: Among all patients, 20 out of 27 pairs of features weakly correlated (r = - 0.13-0.30). For triple-negative breast cancer (TNBC), features from PD map in the pathological complete response (pCR) group (r = 0.60-0.86) showed higher correlation with ADC than that of the non-pCR group (r = 0.30-0.43), and the mean from the ADC and PD maps in the pCR group strongly correlated (r = 0.86). For HER2-positive, few correlations were found both in the pCR and non-pCR groups. For luminal HER2-negative, T2 map correlated more with ADC than T1 and PD maps. Significant differences were seen in T2 low percentiles and median in the luminal-HER2 negative subtype, yielding moderate AUCs (0.68/0.72/0.71). CONCLUSIONS: The relationship between ADC and PD maps in TNBC may indicate different NAT responses. The no-to-weak correlation between the ADC and syMRI suggests their complementary roles in tumor microenvironment evaluation. CRITICAL RELEVANCE STATEMENT: The relationship between ADC and PD maps in TNBC may indicate different NAT responses, and the no-to-weak correlation between the ADC and syMRI suggests their complementary roles in tumor microenvironment evaluation. KEY POINTS: • The relationship between ADC and PD in TNBC indicates different NAT responses. • The no-to-weak correlations between ADC and syMRI complementarily evaluate tumor microenvironment. • T2 low percentiles and median predict NAT response in luminal-HER2-negative subtype.

Molecular Imprinting Technology Enables Proactive Capture of Nitrogen for Boosted Ammonia Synthesis under Ambient Conditions.

Electrochemical nitrogen reduction reaction (NRR) is a burgeoning field for green and sustainable ammonia production, in which numerous potential catalysts emerge endlessly. However, satisfactory performances are still not realized under practical applications due to the limited solubility and sluggish diffusion of nitrogen at the interface. Herein, molecular imprinting technology is adopted to construct an adlayer with abundant nitrogen imprints on the electrocatalyst, which is capable of selectively recognizing and proactively aggregating high-concentrated nitrogen at the interface while hindering the access of overwhelming water simultaneously. With this favorable microenvironment, nitrogen can preferentially occupy the active surface, and the NRR equilibrium can be positively shifted to facilitate the reaction kinetics. Approximately threefold improvements in both ammonia production rate (185.7 µg h-1 mg-1 ) and Faradaic efficiency (72.9%) are achieved by a metal-free catalyst compared with the bare one. It is believed that the molecular imprinting strategy should be a general method to find further applicability in numerous catalysts or even other reactions facing similar challenges.

2 A cm-2 Level Large-Scale Production of Hydrogen Enabled by Constructing Higher Capacity of Interface "Electron Pocket".

The batch production of high-purity hydrogen is a key problem that restricts the progress of fuel cells and the blueprint for achieving carbon neutrality. Transition-metal chalcogenide heterojunctions exhibit certain activity toward electrochemical overall water splitting (EOWS), but their high-current-density catalytic performances are still unsatisfactory due to the slow kinetic progression (H* or *O → *OOH). Inspired by the "electron pocket" theory, we designed a Ni-Mo bimetallic disulfide interface heterojunction electrocatalyst system (NM-IHJ-V) with high electronic storage capacity around the Fermi level (-0.5 eV, +0.5 eV) (e-DFE), which injects more power into the kinetic progression processes of intermediate species in the EOWS process. Consequently, it achieves a superhigh current density of 2 A cm-2 level for EOWS (only 1.98 V voltage is needed), which is 11.23-fold higher than that of the benchmarked Pt/C//IrO2 (178 mA cm-2@1.98 V), as well as an excellent long-term stability of 200 h. Most strikingly, NM-IHJ-V can efficiently produce hydrogen at currents up to 5 A. Our proposed strategy of constructing catalysts to produce hydrogen at superhigh current density through the electron pocket theory will supply valuable insights for the designing other catalytic systems.

Mechanisms of Rostellularia procumbens (L.) Nees on treating chronic glomerulonephritis explored by network pharmacology, RNA-seq, and in vitro experiments.

BACKGROUND: The purpose of this study was to demonstrate the in vitro anti-nephritis activity of Rostellularia procumbens (L.) Nees (R. procumbens) extract and to make a preliminary investigation of its anti-nephritis mechanism. METHODS: A prediction network was built that describes the relationship between R. procumbens and CGN. Then, the potential targets for R. procumbens against CGN were imported into the DAVID database for Gene Ontology (GO) biological annotation analysis and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis. A lipopolysaccharide (LPS)-stimulated rat mesangial cell HBZY-1 model in vitro was used to examine the anti-inflammatory activity of R. procumbens extract. RNA-seq was utilized to investigate differentially expressed genes (DEGs) and enriched signaling pathways between groups. Finally, qPCR was used for the validation analysis of the experimental results. RESULTS: The results of network pharmacology showed that R. procumbens exerts its therapeutic effect on CGN through the AGE-RAGE signaling pathway in diabetic complications, PI3K-Akt, IL-17 signaling pathway, and so on. R. procumbens n-butanol extract (J-NE) can effectively relieve inflammation in HBZY-1. The results of KEGG pathway enrichment suggest that J-NE attenuated CGN was associated with the IL-17 signaling pathway, and the results of RNA-seq were consistent with network pharmacology. Targets enriched in the IL-17 signaling pathway, including Chemokine (C-C motif) ligand 7 (CCL7), Lipocalin 2 (LCN2), Chemokine (C-C motif) ligand 2 (CCL2), and Chemokine (C-X-C motif) ligand 1 (CXCL1), have been identified as crucial targets attenuating CGN by J-NE. CONCLUSION: R. procumbens is a promising pharmacological candidate for the treatment of CGN in the present era.

Eliminating Concentration Polarization with Cationic Covalent Organic Polymer to Promote Effective Overpotential of Nitrogen Fixation.

Electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the conventional Haber-Bosch process. However, it is currently restricted by low effective overpotential due to the concentration polarization, which arises from accumulated products, ammonium, at the reaction interface. Here, a novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle this challenge. The whole network exhibits strong positive charge and effectively repels the positively charged ammonium, enabling an ultra-low interfacial product concentration, and successfully driving the reaction equilibrium to the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a continuous high-level reaction rate. As expected, when this tailored microenvironment is coupled with a transition metal-based catalyst, a 24-fold improvement is generated in the Faradaic efficiency (73.74 %) as compared with the bare one. The proposed strategy underscores the importance of optimizing dynamic processes as a means of improving overall performance in electrochemical syntheses.

Hollow NiCo2O4-ZnO-Co3O4-/N-C Micro-Cage for Synergistic Bisphenol A Degradation by Activating Persulfate.

The NiCo2O4-ZnO-Co3O4-/N-C micro-cage was successfully synthesized by calcination of the precursor obtained from a hollow ZIF-8/ZIF-67 with nickel nitrate. The preparation process concerning ion exchange and leaching was illustrated by the investigation of the composition and structure of the composites. As a catalyst for the activation of persulfate (PDS) to degrade bisphenol A (BPA), it was discovered that the BPA degradation in the presence of NiCo2O4-Co3O4-ZnO/N-C was more efficient than the solids obtained by ZIF-67 with nickel nitrate, indicated by the sevenfold increase of the apparent reaction rate. The further electrochemical analysis evidenced that the electron transfer was more easily accomplished in the system of BPA-PDS-NiCo2O4-Co3O4-ZnO/N-C. This enhanced activity of NiCo2O4-Co3O4-ZnO/N-C was mainly due to the hollow structure, the synergistic effect of NiCo2O4, as well as the smaller size of the active species, which facilitated the transportation of molecules and ions as well as the activation of PDS.

Improving the catalytic ability of a peptide-based artificial glycosidase through a tyrosine strategy.

Recently, peptide-based artificial enzymes have attracted growing interest due to the similar composition of peptide assemblies to natural enzymes. However, low catalytic activity and stability are still the main challenges for these enzyme-like catalysts. In this study, a tyrosine strategy was developed to construct a peptide-based artificial glycosidase through engaging the Tyr residue into the peptide sequence. We found that the appropriate substitution of Tyr produced an enhanced catalytic ability, because the proximal Tyr residue around catalytic sites acts as a nucleophile, playing an important role in the substrate orientation and proton transfer. Moreover, inspired by the biological function of dityrosine bonds in structural proteins, a photo-crosslinking reaction between the phenolic side chains of Tyr was also employed to form intermolecular covalent bonds in peptide assemblies, which further improved the activity and stability of the artificial glycosidase. This work provides a simple avenue for the designing and construction of efficient glycosidase-like catalysts based on a peptide-based material platform.

Bleeding the Excited State Energy to the Utmost: Single-Molecule Iridium Complexes for In Vivo Dual Photodynamic and Photothermal Therapy by an Infrared Low-Power Laser.

A series of cyclometalated Ir(III) complexes with morpholine and piperazine groups are designed as dual photosensitizers and photothermal agents for more efficient antitumor phototherapy via infrared low-power laser. Their ground and excited state properties, as well as the structural effect on their photophysical and biological properties, are investigated by spectroscopic, electrochemical, and quantum chemical theoretical calculations. They target mitochondria in human melanoma tumor cells and trigger apoptosis related to mitochondrial dysfunction upon irradiation. The Ir(III) complexes, particularly Ir6, demonstrate high phototherapy indexes to melanoma tumor cells and a manifest photothermal effect. Ir6, with minimal hepato-/nephrotoxicity in vitro, significantly inhibits the growth of melanoma tumors in vivo under 808 nm laser irradiation by dual photodynamic therapy and photothermal therapy and can be efficiently eliminated from the body. These results may contribute to the development of highly efficient phototherapeutic drugs for large, deeply buried solid tumors.

Facilitating Reconstruction of the Heterointerface Electronic Structure by the Enriched Oxygen Vacancy for the Oxygen Evolution Reaction.

Exploring high-performance non-precious metal-based electrocatalysts for the sluggish oxygen evolution reaction (OER) process is fundamentally significant for the development of multifarious renewable energy conversion and storage systems. Oxygen vacancy (Vo) engineering is an effective leverage to boost the intrinsic activity of OER, but the underlying catalytic mechanism remains anfractuous. Herein, we realize the construction of oxygen vacancy-enriched porous NiO/ln2O3 nanofibers (designated as Vo-NiO/ln2O3@NFs hereafter) via a facile fabrication strategy for efficient oxygen evolution electrocatalysis. Theoretical calculations and experimental results uncover that, compared with the no-plasma engraving component, the presence of abundant oxygen vacancies in the Vo-NiO/ln2O3@NFs is conducive to modulating the electronic configuration of the catalyst, altering the adsorption of intermediates to reduce the OER overpotential and promote O* formation, upshifting the d band center of metal centers near the Fermi level (Ef), and also increasing the electrical conductivity and enhancing the OER reaction kinetics simultaneously. In situ Raman spectra proclaim that the oxygen vacancy can render the NiO/ln2O3 more easily reconstructible on the surface during the OER course. Therefore, the as-obtained Vo-NiO/ln2O3@NFs demonstrated distinguished OER activity, with an overpotential of only 230 mV at 10 mA cm-2 and excellent stability in alkaline medium, surmounting the majority of the previously reported representative non-noble metal-based candidates. The fundamental insights gained from this work can pave a new path for the electronic structure modulation of efficient, inexpensive OER catalysts via Vo engineering.