Exclusive Selectivity Research Articles

The Art of Self-selection or the Intervention of the Voters? The 2023 Election and the Shifting Social Bias of Slovak Parliamentary Elites since 2006

Recent research has shown a trend towards more participatory nomination procedures in new as well as more established parties. However, in Slovakia most politically relevant parties have equally centralised, leadership dominated, and exclusive candidate selection modes. In the first part of the article I draw on the elite literature to investigate cross-party variation in the social bias of parliamentary elites since 2006. Using the 2023 election as a point of departure, I go on to assess how representative MPs are of their own voters, and why social bias varies across parties despite their similar selection modes. The analysis demonstrates that the impact of the selection mode as well as of voter preferences is contingent on the nomination practices of the individual parties. I found strong elements of self-selection in nearly all parties: the members of the presidium nominated themselves, and the composition of the parliamentary elites thus to a considerable extent reflects who the presidium members are. The influence of the voters is limited, because they tend to confirm the priorities of the selectorates; however, in the case of the four smallest parties in 2023, preference voting to some extent mitigated the effect of self-selection. The main drivers of preference voting were the idiosyncratic nomination practice of Ordinary People, and the presence of organised groups and parties on the list (informal alliances).

Regioselective intermolecular carboamination of allylamines via nucleopalladation: empowering three-component synthesis of vicinal diamines.

An intermolecular carboamination reaction of allyl amines under Pd(ii)-catalysis is reported, expediting the synthesis of valuable vicinal diamines embedded in a functionally enriched linear carbon framework with high yields and exclusive Markovnikov selectivity. Central to our approach is the strategic use of a removable picolinamide auxiliary, which directs the regioselectivity during aminopalladation and stabilizes the crucial 5,5-palladacycle intermediate. This stabilization facilitates oxidative addition to carbon electrophiles, enabling the simultaneous incorporation of diverse aryl/styryl groups as well as important amine motifs, such as sulfoximines and anilines, across carbon-carbon double bonds. The protocol features broad substrate compatibility, tolerance to various functional groups, and scalability. The utility of this method is further demonstrated by the site-selective diversification of pharmaceutical agents. Additionally, these products serve as versatile intermediates for synthesizing heterocycles and function as effective ligands in catalytic transfer hydrogenation reactions. Notably, this work represents a rare instance of nucleopalladation-guided intermolecular carboamination of allylamines.

Homogenous Palladium-Catalyzed Dehalogenative Deuteration and Tritiation of Aryl Halides with D2/T2 Gas.

Hydrogen isotopically labeled compounds have extensive utility across diverse domains, especially in drug discovery and development. However, synthesis of the labeled compounds with exclusive site selectivity and/or high isotope incorporation is challenging. One widely employed method is heterogeneous palladium(0)-catalyzed (such as Pd/C) dehalogenative deuteration and tritiation with D2/T2 gas. While commonly used, the method faces two long-standing challenges related to insufficient isotope incorporation and functional group tolerance, particularly with aryl bromides and chlorides. These long-standing issues pose a substantial obstacle in the synthesis of deuterated drug molecules and high-specific-activity tritium tracers. Herein, we present a novel palladium catalytic system using Zn(OAc)2 as an additive, enabling novel homogenous dehalogenative deuteration/tritiation using D2/T2 gas. Under mild reaction conditions, a wide range of drug-like aryl halides and pseudohalides undergo selective deuteration with complete isotope incorporation. The reaction displays excellent compatibility with diverse functional groups, including multiple bonds and O/N-benzyl, and cyano groups, which are frequently problematic in the Pd/C reactions. Furthermore, this method was successfully applied to the tritiation of four halogenated pharmaceutically relevant molecules, resulting in predictable high specific activity per halogen atom (26.5-27.7 Ci/mmol). Notably, the developed system allows gram-scale preparation of a deuterium-containing intermediate, a crucial step in synthesizing a deuterium-labeled drug molecule. A key intermediate, Pd(Ar)OAc, is proposed to activate hydrogen gas during dehalogenative deuteration and tritiation, and Zn(OAc)2 plays an essential role in inhibiting Pd poisoning by halides.

Performance of ChatGPT in medical licensing examinations in countries worldwide: A systematic review and meta-analysis protocol.

In November 2022, the online artificial intelligence (AI) chatbot ChatGPT was released to the public, and swiftly garnered global attention because of its ability to provide detailed answers to complex queries. In medical field, ChatGPT has shown great potential to be used in medical education and has excelled in many English-language medical licensing examinations. However, due to the variability of medical licensing examinations in different countries, and ChatGPT's particular proficiency in English, the previous literatures showed that ChatGPT is unable to pass medical licensing examinations from non-English-speaking countries or those not administered in English. To the best of our knowledge, this is the first study to review whether ChatGPT can demonstrate consistent accuracy across diverse medical licensing examinations and be used in medical education across countries. In this study protocol, we aimed to analyze and review the differences in performance of ChatGPT in medical exams in various language environments and countries, as well as its potential in medical education. A systematic review and meta-analysis was conducted using PubMed, Web of Science, and Scopus to collect papers testing the performance of ChatGPT in medical licensing examinations. We imported all the collected literatures into Rayyan and screened the literatures based on the selection criteria and exclusion criteria. The risk of bias and quality of included studies was assessed by using Mixed Methods Appraisal Tool (MMAT). Data from included studies was extracted into an Excel spreadsheet. All of the above processes were completed by two reviewers independently. A third reviewer was consulted in cases of disagreement. Finally, we provided both quantitative and qualitative analysis of the findings from the included studies. PROSPERO registration number: CRD42024506687.

IMPACTO DOS COMPOSTOS BIOATIVOS DA UVA, COM ÊNFASE NO RESVERATROL, NA REDUÇÃO DA PRESSÃO ARTERIAL: UMA REVISÃO DE LITERATURA

The study aimed to analyze the main studies that address the impacts of grape bioactive compounds, with an emphasis on resveratrol, on reducing blood pressure. This is a literature review, which was carried out based on the definition of the research question, inclusion and exclusion criteria, search strategies, and selection of studies. 40 articles were selected from 230 identified, after assessing their methodological quality. Data analysis focused on the mechanisms of action of resveratrol, the effectiveness of supplementation methods, and its clinical perspectives. The study highlighted the potential of resveratrol, a grape bioactive compound, in reducing blood pressure, acting as an adjuvant in the treatment of hypertension. It promotes vasodilation, reduces oxidative stress, and improves cardiovascular health. Its effectiveness, however, depends on dosage and bioavailability. Despite advances, more clinical studies are needed to standardize its use and investigate interactions with medications. Continued research can consolidate resveratrol in integrative health strategies.

Propensity score matching analysis of early vs. delayed surgery for intertrochanteric fracture in older patients: a retrospective multicenter cohort study of 7414 patients with a mean 4-year follow up

BackgroundThe widespread acceptance of early surgery as a treatment for acute intertrochanteric fracture (ITF) has been accompanied by ongoing controversy due to conflicting conclusions presented in previous studies. This study aims to compare the occurrence of perioperative complications and mortality, as well as functional outcomes in older patients with ITF who underwent either early or delayed surgery.MethodsA retrospective multicenter cohort study involving 7414 patients with ITF between Jan. 2017 and Dec. 2021 was conducted. After predefined participants selection inclusion and exclusion criteria, 2323 surgically treated ITF patients were included and analyzed utilizing propensity score matching (PSM) method. Their demographics, injury-related data, surgery-related data, and perioperative adverse outcomes during hospitalization were collected and compared between the early or delayed surgery groups by PSM with a 1:4 ratio. All participants received a minimum of two-year follow-up and perioperative outcomes, functional outcomes, and survival analyses were conducted and compared.ResultsAfter adjustment for potential confounders, there were no significant difference in surgery duration, intraoperative blood loss, transfusion rate, mortality rates, functional outcomes, and perioperative complications rates including severe complications, cardiac complications, pulmonary complications, and neurological complications regardless of whether the patient was treated with early or delayed surgery (all P > 0.05). Although length of hospital stay (mean, 11.5 versus 14.4 days, P < 0.001), total hospital costs (mean, 39305 versus 42048 yuan, P < 0.001), and minor complications rates including hematological complications (31.7% versus 41.2%, P = 0.007) and nutritional/metabolic complications (59.3% versus 66.4%, P = 0.039) were lower in the early surgery group, our result indicated patients with early surgery were more inclined to receive more blood transfusion (mean, 2.8 versus 2.2 units, P = 0.004).ConclusionsOur findings suggest that a 48-hour delay in surgical intervention for older patients with an ITF does not result in a higher mortality rate, worse functional outcomes, and increased incidence of major perioperative complications when compared to early surgery. While expedited surgery is undoubtedly necessary for suitable patients, a reasonable preoperative delay of 48 h may be justified and safe for those with severe conditions, rather than strictly adhering to the current guidelines.

Copper‐Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes

P‐stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P‐C bond formation remains both challenging and underdeveloped. We report the first copper‐catalyzed enantioselective hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2‐diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50% conversion, our approach employs a distinct dynamic kinetic asymmetric transformation mechanism, achieving complete conversion of racemic starting materials. This reaction is compatible with a broad range of aromatic and aliphatic terminal alkynes, producing products with high yields (up to 95%), exclusive cis selectivity, and exceptional regio‐ and enantioselectivity (&gt; 20:1 r.r. and up to 96% ee). The resulting products were further transformed into a diverse array of enantioenriched P‐stereogenic scaffolds. Preliminary mechanistic studies were conducted to elucidate the reaction details.

Copper-Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes.

P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed enantioselective hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs a distinct dynamic kinetic asymmetric transformation mechanism, achieving complete conversion of racemic starting materials. This reaction is compatible with a broad range of aromatic and aliphatic terminal alkynes, producing products with high yields (up to 95 %), exclusive cis selectivity, and exceptional regio- and enantioselectivity (>20 : 1 r.r. and up to 96 % ee). The resulting products were further transformed into a diverse array of enantioenriched P-stereogenic scaffolds. Preliminary mechanistic studies were conducted to elucidate the reaction details.

A Metal-Free Direct Decarboxylative Fluoroacylation of Indole Carboxylic Acids with Fluorinated Acids.

A straightforward preparation of diversified fluorinated indol-3-yl ketones was developed by the direct decarboxylative fluoroacylation of indole carboxylic acids. The reaction could be performed on a gram scale under net conditions. Neither a metal catalyst nor an additive was employed. This methodology featured simple reaction conditions, high efficiency, exclusive selectivity, a broad substrate scope, and easy operation, which allowed it to meet the green chemistry requirement of the modern pharmaceutical industry. Control experiments confirmed that a radical process might be involved in the tandem decarboxylative fluoroacylation sequence.

Defect Engineering in a Nanoporous Thulium-Organic Framework in Catalyzing Knoevenagel Condensation and Chemical CO2 Fixation.

Defect engineering is an extremely effective strategy for modifying metal-organic frameworks (MOFs), which can break through the application limitations of traditional MOFs and enhance their functionality. Herein, we report a highly robust nanoporous thulium(III)-organic framework, {[Tm2(BDCP)(H2O)5](NO3)·3DMF·2H2O}n (NUC-105), with [Tm(COO)2(H2O)]n chains and [Tm2(COO)4(H2O)8] dinuclears as metal nodes and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (BDCP) linkers. In NUC-105, each of the four chains of [Tm(COO)2]n and the two rows of [Tm2(COO)4(H2O)8] units is unified by the organic skeleton, resulting in a rectangular nanochannel with dimensions of 15.35 Å × 11.29 Å, which leads to a void volume of 50%. It is worth mentioning that the [Tm2(COO)4(H2O)8] cluster is very rare in terms of its higher level of associated water molecules, implying that the activated host framework can serve as a strong Lewis acid. NUC-105a exhibited great heterogeneous catalytic performance for CO2 cycloaddition with epoxides under the reaction conditions (0.60 mol % NUC-105a, 5.0 mol % n-Bu4NBr, 65 °C, 5 h), ensuring exclusive selectivity and high conversion rates. In addition, NUC-105a's strong catalytic impact on the Knoevenagel condensation of aldehydes and malononitrile can be attributed to the collaboration between the drastically unsaturated Lewis acidic Tm3+ centers and Lewis basic pyridine groups.

Cation Enrichment Promotes High-rate CO Electroreduction to C2+ Liquid Products.

Electrochemical reduction of CO into valuable multicarbon (C2+) liquids is crucial for reducing CO2 emissions and advancing clean energy, yet mastering efficiency and selectivity in this process remains a tough challenge. Herein, we employ a surface-modification strategy using electrochemically active polymeric 1,4,5,8-naphthalenete-tracarboxylic dianhydride (PNTCDA)-modified copper nanosheets (PM-Cu) to rearrange reactive species in the electric double layer, where the PNTCDA triggers a distinctive enolization that anchor potassium ions (K+) onto the cathode surface under reduction condition. Electrochemical analysis and computational simulations revealed that this approach fine-tunes K+ distribution in the double layer, making the dehydration of hydrated K+ more efficient and reducing active water molecules at the interface, thus inhibiting the hydrogen evolution reaction while concurrently promoting CO reduction via enhanced C‒C coupling. For the first time, the PM-Cu catalyst demonstrates ampere-scale current densities with the exclusive selectivity of a C2+ liquid product yield exceeding 90%. Thus, by tailoring the local microenvironment with electrochemically active organics, it is possible to modulate CO reduction, improve sustainable energy storage, and increase industrial carbon utilization.

From Methane to Methanol: Pd-iC-CeO2 Catalysts Engineered for High Selectivity via Mechanochemical Synthesis.

In the pursuit of selective conversion of methane directly to methanol in the liquid-phase, a common challenge is the concurrent formation of undesirable liquid oxygenates or combustion byproducts. However, we demonstrate that monometallic Pd-CeO2 catalysts, modified by carbon, created by a simple mechanochemical synthesis method exhibit 100% selectivity toward methanol at 75 °C, using hydrogen peroxide as oxidizing agent. The solvent free synthesis yields a distinctive Pd-iC-CeO2 interface, where interfacial carbon (iC) modulates metal-oxide interactions and facilitates tandem methane activation and peroxide decomposition, thus resulting in an exclusive methanol selectivity of 100% with a yield of 117 μmol/gcat at 75 °C. Notably, solvent interactions of H2O2 (aq) were found to be critical for methanol selectivity through a density functional theory (DFT)-simulated Eley-Rideal-like mechanism. This mechanism uniquely enables the direct conversion of methane into methanol via a solid-liquid-gas process.

Identification of K+-determined reaction pathway for facilitated kinetics of CO2 electroreduction

Cations such as K+ play a key part in the CO2 electroreduction reaction, but their role in the reaction mechanism is still in debate. Here, we use a highly symmetric Ni-N4 structure to selectively probe the mechanistic influence of K+ and identify its interaction with chemisorbed CO2−. Our electrochemical kinetics study finds a shift in the rate-determining step in the presence of K+. Spectral evidence of chemisorbed CO2− from in-situ X-ray absorption spectroscopy and in-situ Raman spectroscopy pinpoints the origin of this rate-determining step shift. Grand canonical potential kinetics simulations - consistent with experimental results - further complement these findings. We thereby identify a long proposed non-covalent interaction between K+ and chemisorbed CO2−. This interaction stabilizes chemisorbed CO2− and thus switches the rate-determining step from concerted proton electron transfer to independent proton transfer. Consequently, this rate-determining step shift lowers the reaction barrier by eliminating the contribution of the electron transfer step. This K+-determined reaction pathway enables a lower energy barrier for CO2 electroreduction reaction than the competing hydrogen evolution reaction, leading to an exclusive selectivity for CO2 electroreduction reaction.

Photoinduced synthesis of polymer-coated covalent organic framework microspheres for highly efficient lithium recovery

The increasing demand for lithium-ion batteries has led to a surge in global lithium consumption, calling for efficient extraction and recovery methods. Adsorption-based lithium recovery has gained attention for its simplicity, selectivity, and low energy requirements. However, conventional adsorption materials for lithium-ion (Li+) suffer from low surface area and covered active sites, resulting in slow recovery and inefficient uptake. Herein, we present a facile photoinduced synthesis of crown ether (CE)-based polymer grafted covalent organic framework (COF) microspheres, termed COF-CE, as an efficient lithium adsorbent. The COF-CE hybrid material possesses abundant nanochannels and highly porous surfaces, enabling rapid ion diffusion and enhancing ion accessibility to functional groups with the exclusive selectivity imparted by the grafted CE polymer towards Li+ over other monovalent cations. Notably, COF-CE exhibits exceptional absorption capacity (7.4 mg/g), rapid adsorption rates (k2 = 0.137 g mg−1 min−1) and high selectivity towards Li+, outperforming existing adsorbents. Moreover, COF-CE demonstrates remarkable Li+ regeneration and recycling capabilities, achieving near-unity recovery of lithium during the desorption phase and retaining 97 % of its adsorption capacity after five cycles. These results highlight the potential of COF-CE as an advanced adsorbent for lithium recovery in various applications, including industrial wastewater treatment and environmental remediation efforts.

Rational construction of positively charged polyamide nanofiltration membranes for precision cation separations

Nanofiltration has gained extensive attention in various energetically efficient separations towards a sustainable water–energy nexus. However, state-of-the-art polyamide nanofiltration membranes are constrained by the inherent trade-off between water permeance and solute selectivity, and a remarkable improvement in membrane permselectivity remains a big challenge. Here we conceived a density functional theory (DFT) assisted surface modification approach using triaminoguanidine hydrochloride (TGH) as the functional modifier to fabricate polyamide membranes with extremely high surface electropositivity and well-defined nanopores to overcome this challenge. Experimental data and DFT simulation results show that TGH surface modification can significantly manipulate surface charges and polarity to facilitate water permeation and enhance Donnan exclusion selectivity. Compared with the pristine benchmark membrane, the TGH-modified membrane exhibited a 4-fold increase in water permeance and a 6-fold increase in salt rejection, which successfully breaks the trade-off, excellent monovalent/divalent cation selectivity, and superior operational stability over a wide range of testing pressure, feed pH, and operation time, outperforming state-of-the-art membranes with similar chemistry. Taken together, this study demonstrates a feasible and reliable method combining DFT and experiments to rationally tailor the membrane characteristics at the molecular level, enabling the successful fabrication of effective polyamide nanofiltration membranes with precisely regulated structural and surface properties for water purification and precision ion separations.

Accessing a Diverse Set of Functional Red-Light Photoswitches by Selective Copper-Catalyzed Indigo N-Arylation.

The ability to correlate the structure of a molecule with its properties is the key to the rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of the metastable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The lack of synthetic techniques to derivatize the abundant parent dye and a thorough understanding of the impact of structural factors on the photochemical and thermal properties hinder broad applications of this emerging photoswitch class. Herein, we report an efficient copper-catalyzed indigo N-arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for monoarylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N-aryl-N'-alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N-aryl substituents, while the N'-alkyl groups enable the independent attachment of functional moieties without affecting the photochromic properties. A strong correlation between the structure of the N-aryl moiety and the thermal stability of the photogenerated Z-isomers was achieved by multivariate linear regression models obtained through a data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules.

Robust heterometallic {In2CdO}-Organic framework for efficiently catalyzing CO2 cycloaddition and Knoevenagel condensation

The catalytic performance of MOFs mainly comes from the coordination defects of their metal ions. However, developing promising MOF catalysts with a large number of small coordination molecules on metal ions remains a huge challenge. Herein, we report a highly robust heterometallic {In2CdO}-organic framework of {[In2Cd(CPPDP)(µ3 − OH)(H2O)5](NO3)2⋅2DMF⋅3H2O}n (NUC-103) with scarcely reported [In2Cd(OH)(O2CR)5(H2O)5] clusters (abbreviated as {In2CdO}) as secondary building units (SBUs), each of which contains five associated water molecules, implying that activated host framework can serve as strong Lewis acid. In NUC-103, three rows of {In2CdO} are shaped into hierarchical triangle-nanochannels of 17.42 × 17.98 Å2 and triangle-microchannels of 10.15 × 11.00 Å2 along c axis. On account of the following unique characteristics such as three kinds of active sites (Lewis acid sites of In3+ and Cd2+, Lewis base sites of free Npyridine atoms and electrophilic H-bond donors (HBD) of µ3 − OH moieties), large solvent-free channels, high thermal stability, and resistance to various solvents, NUC-103a is a promising catalytic platform. Catalytic experiments prove that NUC-103a is a significant heterogeneous catalyst for the cycloaddition of CO2 with epoxides with exclusive selectivity and high conversion. In addition, NUC-103a as a bifunctional catalyst displays the high catalytic performance on the Knoevenagel condensation reactions of aldehydes and malononitrile. Therefore, this work not only provides an indium(III) + cadmium(II)-based heterometallic cluster of {In2CdO}, but also provides a valuable insight into designing metal–organic catalytic materials with high defect coordination.

Palladium(II)-Catalyzed Norbornene-Mediated Selective meta-C-H Silylation for the Synthesis of Arylsilanes from Primary Benzamides.

A palladium(II)-catalyzed norbornene-mediated remote selective meta-C-H silylation of primary benzamides was developed for the synthesis of arylsilanes. Such a conversion provides access to a range of arylsilanes with exclusive selectivity using norbornene (NBE) as the meta-C-H activator. The amide directing group can be detached simultaneously through C-C bond cleavage or undergo a dehydration reaction pathway to form nitriles.

Interfacial Super‐Assembly of Vacancy Engineered Ultrathin‐Nanosheets Toward Nanochannels for Smart Ion Transport and Salinity Gradient Power Conversion

AbstractIon‐selective nanochannel membranes assembled from two‐dimensional (2D) nanosheets hold immense promise for power conversion using salinity gradient. However, they face challenges stemming from insufficient surface charge density, which impairs both permselectivity and durability. Herein, we present a novel vacancy‐engineered, oxygen‐deficient NiCo layered double hydroxide (NiCoLDH)/cellulose nanofibers‐wrapped carbon nanotubes (VOLDH/CNF‐CNT) composite membrane. This membrane, featuring abundant angstrom‐scale, cation‐selective nanochannels, is designed and fabricated through a synergistic combination of vacancy engineering and interfacial super‐assembly. The composite membrane shows interlayer free‐spacing of ~3.62 Å, which validates the membrane size exclusion selectivity. This strategy, validated by DFT calculations and experimental data, improves hydrophilicity and surface charge density, leading to the strong interaction with K+ ions to benefit the low ion transport resistance and exceptional charge selectivity. When employed in an artificial river water|seawater salinity gradient power generator, it delivers a high‐power density of 5.35 W/m2 with long‐term durability (20,000s), which is almost 400 % higher than that of the pristine NiCoLDH membrane. Furthermore, it displays both pH‐ and temperature‐sensitive ion transport behavior, offering additional opportunities for optimization. This work establishes a basis for high‐performance salinity gradient power conversion and underscores the potential of vacancy engineering and super‐assembly in customizing 2D nanomaterials for diverse advanced nanofluidic energy devices.

Interfacial Super-Assembly of Vacancy Engineered Ultrathin-Nanosheets Toward Nanochannels for Smart Ion Transport and Salinity Gradient Power Conversion.

Ion-selective nanochannel membranes assembled from two-dimensional (2D) nanosheets hold immense promise for power conversion using salinity gradient. However, they face challenges stemming from insufficient surface charge density, which impairs both permselectivity and durability. Herein, we present a novel vacancy-engineered, oxygen-deficient NiCo layered double hydroxide (NiCoLDH)/cellulose nanofibers-wrapped carbon nanotubes (VOLDH/CNF-CNT) composite membrane. This membrane, featuring abundant angstrom-scale, cation-selective nanochannels, is designed and fabricated through a synergistic combination of vacancy engineering and interfacial super-assembly. The composite membrane shows interlayer free-spacing of ~3.62 Å, which validates the membrane size exclusion selectivity. This strategy, validated by DFT calculations and experimental data, improves hydrophilicity and surface charge density, leading to the strong interaction with K+ ions to benefit the low ion transport resistance and exceptional charge selectivity. When employed in an artificial river water|seawater salinity gradient power generator, it delivers a high-power density of 5.35 W/m2 with long-term durability (20,000s), which is almost 400 % higher than that of the pristine NiCoLDH membrane. Furthermore, it displays both pH- and temperature-sensitive ion transport behavior, offering additional opportunities for optimization. This work establishes a basis for high-performance salinity gradient power conversion and underscores the potential of vacancy engineering and super-assembly in customizing 2D nanomaterials for diverse advanced nanofluidic energy devices.