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Carbon materials with defect-rich structure are highly demanded for various electrochemical scenes, but encountering a conflict with the deteriorative intrinsic conductivity. Herein, we build a highway-mediated nanoarchitecture that consists of the ordered pseudographitic nanodomains among disordered highly nitrogen-doped segments through a supramolecular self-assembly strategy. The "order-in-disorder" nanosheet-like carbon obtained at 800 °C (O/D NSLC-800) achieves a tradeoff with high defect degree (21.9 at% of doped nitrogen) and compensated electrical conductivity simultaneously. As expected, symmetrical O/D NSLC-800 electrodes exhibit superior capacitive deionization (CDI) performance, including brackish water desalination (≈82 mgNaCl g-1 at a cell voltage of 1.6 V in a 1000 mg L-1 NaCl solution) and reusage of actual refining circulating cooling water, outperforming most of the reported state-of-the-art CDI electrodes. The implanted pseudographitic nanodomains lower the resistance and activation energy of charge transfer, which motivates the synergy of hosting sites of multiple nitrogen configurations. Our findings shed light on electrically conductive nanoarchitecture design of defect-rich materials for advanced electrochemical applications based on molecular-level modulation.
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Developing stable, high-performance chloride-ion storage electrodes is essential for energy storage and water purification application. Herein, a P, S co-doped porous hollow nanotube array, with a free ion diffusion pathway and highly active adsorption sites, on carbon felt electrodes (CoNiPS@CF) is reported. Due to the porous hollow nanotube structure and synergistic effect of P, S co-doped, the CoNiPS@CF based capacitive deionization (CDI) system exhibits high desalination capacity (76.1 mgCl- g-1), fast desalination rate (6.33 mgCl- g-1 min-1) and good cycling stability (capacity retention rate of > 90%), which compares favorably to the state-of-the-art electrodes. The porous hollow nanotube structure enables fast ion diffusion kinetics due to the swift ion transport inside the electrode and the presence of a large number of reactive sites. The introduction of S element also reduces the passivation layer on the surface of CoNiP and lowers the adsorption energy for Cl- capture, thereby improving the electrode conductivity and surface electrochemical activity, and further accelerating the adsorption kinetics. Our results offer a powerful strategy to improve the reactivity and stability of transition metal phosphides for chloride capture, and to improve the efficiency of electrochemical dechlorination technologies.
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We have disclosed a novel metal-free tandem cyclization reaction for the synthesis of 3-methyleneisoindolin-1-ones starting from ester-functionalized aziridines. This strategy can be effectively promoted by DBU and carboxylic acids. Mechanistically, it involves sequential ring opening of aziridines with carboxylic acids, lactamization, and elimination of carboxylic acids.
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Despite the promising potential of transition metal oxides (TMOs) as capacitive deionization (CDI) electrodes, the actual capacity of TMOs electrodes for sodium storage is significantly lower than the theoretical capacity, posing a major obstacle. Herein, we prepared the kinetically favorable ZnxNi1 - xO electrode in situ growth on carbon felt (ZnxNi1 - xO@CF) through constraining the rate of OH- generation in the hydrothermal method. ZnxNi1 - xO@CF exhibited a high-density hierarchical nanosheet structure with three-dimensional open pores, benefitting the ion transport/electron transfer. And tuning the moderate amount of redox-inert Zn-doping can enhance surface electroactive sites, actual activity of redox-active Ni species, and lower adsorption energy, promoting the adsorption kinetic and thermodynamic of the Zn0.2Ni0.8O@CF. Benefitting from the kinetic-thermodynamic facilitation mechanism, Zn0.2Ni0.8O@CF achieved ultrahigh desalination capacity (128.9 mgNaCl g-1), ultra-low energy consumption (0.164 kW h kgNaCl-1), high salt removal rate (1.21 mgNaCl g-1 min-1), and good cyclability. The thermodynamic facilitation and Na+ intercalation mechanism of Zn0.2Ni0.8O@CF are identified by the density functional theory calculations and electrochemical quartz crystal microbalance with dissipation monitoring, respectively. This research provides new insights into controlling electrochemically favorable morphology and demonstrates that Zn-doping, which is redox-inert, is essential for enhancing the electrochemical performance of CDI electrodes.
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The treatment of wastewater has become increasingly challenging as a result of its growing complexity. To achieve synergistic removal of coexisting pollutants in wastewater, one promising approach involves the integration of electric fields. We conducted a comprehensive literature review to explore the potential of integrating electric fields and developing efficient electro-intensified simultaneous decontamination systems for wastewater containing coexisting pollutants. The review focused on comprehending the applications and mechanisms of these systems, with a particular emphasis on the deliberate utilization of positive and negative charges. After analyzing the advantages, disadvantages, and application efficacy of these systems, we observed electro-intensified systems exhibit flexible potential through their rational combination, allowing for an expanded range of applications in addressing simultaneous decontamination challenges. Unlike the reviews focusing on single elimination, this work aims to provide guidance in addressing the environmental problems resulting from the coexistence of hazardous contaminants.
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The efficiency of persulfate-assisted advanced oxidation processes (PS-AOPs) in degrading organic pollutants is affected by the electron-donating capability of organic substances present in the water source. In this study, we systematically investigate the electron-donating capacity (EDC) difference between groundwater and surface water and demonstrate the dependence of removal efficiency on the EDC of target water by PS-AOPs with carbon nanotubes (CNTs) as a catalyst. Laboratory analyses and field experiments reveal that the CNT/PS system exhibits higher performance in organic pollutant removal in groundwater with a high concentration of phenols, compared to surface water, which is rich in quinones. We attribute this disparity to the selective electron transfer pathway induced by potential difference between PS-CNT and organic substance-CNT intermediates, which preferentially degrade organic substances with stronger electron-donating capability. This study provides valuable insights into the inherent selective removal mechanism and application scenarios of electron transfer process-dominated PS-AOPs for water treatment based on the electron-donating capacity of organic pollutants.
Assuntos
Poluentes Ambientais , Água Subterrânea , Nanotubos de Carbono , Elétrons , OxirreduçãoRESUMO
An intramolecular formal [3+2] cycloaddition of activated aziridines and epoxides with electron-deficient alkene has been developed for the general and efficient construction of bridged aza- and oxa-[n.2.1] (n = 3 or 4) skeletons. This strategy can be efficiently promoted by lithium iodide. To demonstrate its potential, the intramolecular formal [3+2] cycloaddition was used to access the important intermediate of homoepiboxidine.
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Alcenos , Aziridinas , Catálise , Reação de Cicloadição , Elétrons , Compostos de Epóxi , EsqueletoRESUMO
A pH-triggered transition from micellar aggregation to a host-guest complex was achieved based on the supramolecular interactions between calixpyridinium and pyrroloquinoline quinone disodium salt (PQQ-2Na) accompanied by a color change. Our design has the following three advantages: (1) a regular spherical micellar assembly is fabricated by the supramolecular interactions between calixpyridinium and PQQ-2Na at pH 6 in an aqueous solution, (2) increasing the pH can lead to a transition from micellar aggregation to a host-guest complex due to the deprotonation of calixpyridinium, and at the same time (3) increasing the pH can lead to a color change owing to the deprotonation of calixpyridinium and the complexation of deprotonated calixpyridinium with PQQ-2Na. Benefitting from the low toxicity of calixpyridinium and PQQ-2Na, this pH-induced transition from micellar aggregation to a host-guest complex was further studied as a controllable-release model.
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Micelas , Cofator PQQ , Concentração de Íons de Hidrogênio , Cofator PQQ/química , ÁguaRESUMO
A novel 9,9a-BN anthracene 5 has been synthesized by the Ru-catalyzed electrocyclization of BN-aromatic enynes. The photophysical properties of 5 are different from those of all-carbon anthracene and other reported BN-anthracenes. The reactivity of 5 has been investigated by treating 5 with organolithium compounds, Br2, or N-iodosuccinimide. The resulting halogenated compounds can be easily functionalized via cross-coupling reactions. UV-vis and fluorescence spectroscopy of 5 have been investigated to explore the photophysical properties of these BN-anthracenes.
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Capacitive deionization (CDI) is considered as a promising desalination technology due to its low energy consumption and no two-second pollution. But the development of traditional CDI is limited by its two drawbacks, which are low deionization capacity and unavoidable parasitic reactions. Hybrid capacitive deionization (HCDI), which is composed of a faradic electrode and an electrical-double-layer electrode, effectively solves the above problem. Herein, we report a typical NASICON material Na3(VO)2(PO4)2F and modify it with rGO, then apply it in HCDI firstly and receive a superior desalination performance. Five samples are prepared by adding different contents GO solution and we choose the best one (NVOPF-4) with the lowest resistance for the desalination tests according to electrochemical performance. The result of desalination shows a high desalination capacity of 175.94 mg·g-1, low energy consumption of 0.35 kWh·kg-NaCl-1, and the energy recovery is 20% at a current density of 25 mg·g-1. NVOPF@rGO displays a promising ability for desalination in capacitive deionization, further confirming NASICON be a suitable material type for HCDI electrode materials.
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In this work, an irregular calixpyridinium-suramin sodium supramolecular assembly was constructed by the strong host-guest electrostatic interactions. More interestingly, a novel regular spherical supramolecular assembly was also fabricated by the hydrogen bonding interactions between suramin sodium and the UV accelerated addition product of deprotonated calixpyridinium in water. The same principle was also applied to construct a UV accelerated regular spherical self-assembly by the addition product of deprotonated calixpyridinium in water. Compared with the complicated and irreversible covalent connection of the light-responsive groups to the building block, which is one of the common means of obtaining light-responsive supramolecular systems, this finding not only provides a smart, facile, and universally applicable method to construct deprotonated calixpyridinium-based light-responsive host-guest systems but also provides a new idea for the development of other novel light-responsive building blocks.
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A series of novel bis-BN-naphthalene-fused oxepin derivatives were synthesized via a Pd-catalyzed tandem reaction from brominated 2,1-borazaronaphthalenes and cis-bis(boryl)alkenes. X-ray crystallographic analysis revealed that bis-BN-naphthalene-fused oxepins feature a planar framework. The electronic and photophysical properties of the novel BN-naphthalene-fused oxepins were investigated by UV-vis and fluorescence spectroscopies and density functional theory (DFT) calculations, which disclosed the distinct electronic and photophysical properties of the analogous hydrocarbon system. Interestingly, dual-fluorescent emissions were observed upon dissolving N-substituted derivatives 10-14 in dimethyl sulfoxide. Tunable emission colors especially for white-light emissions can be achieved by controlling the ratio of solvents, concentration, or temperature using only a single-molecule compound.
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A new calixpyridinium-based light-responsive host-guest recognition motif was found in this work. This host-guest recognition motif was further discovered to be applied as a selective turn-on fluorescent sensor for lysine over other natural amino acids.
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Corantes Fluorescentes/química , Lisina/química , Compostos Macrocíclicos/química , Fotólise , Compostos de Piridínio/química , Técnicas Biossensoriais/métodos , Interações Hidrofóbicas e Hidrofílicas , Conformação Molecular , Espectrometria de Fluorescência , ÁguaRESUMO
In this work, cationic macrocyclic calixpyridinium was employed as a new strategy to condense DNA. Moreover, the degradation of DNA by DNase I could lead to the calixpyridinium-DNA supramolecular aggregates being dissipated. Therefore, the present system is potentially applicable as the targeted drug delivery model at DNase I-overexpressed sites.
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Calixarenos/química , DNA/química , Desoxirribonuclease I/química , Animais , SalmãoRESUMO
In this work, the host-guest interaction between calixpyridinium and anionic anticancer drug Alimta was studied in aqueous media. Spherical supramolecular amphiphilic assembly rather than simple complex was accidentally fabricated by the complexation of calixpyridinium with Alimta. It is the third kind of anionic guest to be discovered to form the higher-order assembly by the complexation of calixpyridinium besides polyanionic guest and anionic gemini surfactant guest. The finding of this assembly approach supplies a new idea to construct various self-assembly architectures in water via the complexation of calixpyridinium with anionic drugs. The resulting calixpyridinium-drug assemblies may also have the potential to adjust the effects of drugs.
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Antineoplásicos/química , Pemetrexede/química , Piridinas/química , Tensoativos/química , Substâncias Macromoleculares/química , Estrutura Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
An In(OTf)3-catalyzed domino reaction involving sequential oxidative ring opening of aziridines by using the solvent dimethyl sulfoxide and intramolecular Michael addition has been developed for the modular synthesis of 2-aminoindanone compounds by the formation of one new CâO bond and one new C-C bond. The notable feature of this strategy includes broad substrate scope, excellent trans-diastereoselectivities, highly functionalized products, and mild conditions. The catalyst In(OTf)3 plays an important role in the formation of the indanone ring.
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A dramatic N-substituent controlled tandem annulation of 2-(2-(2-bromoethyl)phenyl)-1-sulfonylaziridines with 1,3-dicarbonyl compounds has been developed. When the N-substituent was a 4-methylbenzenesulfonyl group (Ts), sequential ring opening of aziridines, nucleophilic substitution, and lactamization took place to provide a series of hexahydrobenz[ e]isoindole compounds in good yields with good diastereoselectivities. By contrast, 3-benzazepine compounds were afforded in good yields via ring opening of aziridines and nucleophilic substitution when the N-substituent was the 4-nitrobenzenesulfonyl group (Ns).
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The information in the literature concerned with lowering the critical aggregation concentration of anionic surfactants by macrocyclic compounds is scarce. This research develops an effective route for lowering the critical aggregation concentration of anionic gemini surfactants by the complexation of calixpyridinium. Furthermore, the size of complex self-assembled nanostructures can be well controlled by the different mixing ratio of the host and the guest.
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Compostos de Piridínio/química , Tensoativos/síntese química , Nanopartículas/química , Tensoativos/químicaRESUMO
A facile and practical [Cp*RhCl2]2-catalyzed three-component reaction between indolyl aldehydes, amines and alkynes involving C-H activation and cyclization has been developed. A series of ß-carbolinium salts and γ-carbolinium salts are successfully afforded in good to quantitative yields under mild conditions. This efficient and convergent strategy provides a good choice for constructing the libraries of ß-carbolinium salts and γ-carbolinium salts.
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In this work, a comparative study on the supramolecular assemblies formed by calixpyridinium and two alginates with different viscosities was performed. We found that sodium alginate (SA) with medium viscosity (SA-M) had a better capability to induce aggregation of calixpyridinium in comparison with SA with low viscosity (SA-L) because of the stronger electrostatic interactions between calixpyridinium and SA-M. Therefore, the morphology of calixpyridinium-SA-M supramolecular aggregates was a compact spherical structure, while that of calixpyridinium-SA-L supramolecular aggregates was an incompact lamellar structure. As a result, adding much more amount of 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt to calixpyridinium-SA-M solution was required to achieve the balance of the competitive binding, and in comparison with calixpyridinium-SA-L supramolecular aggregates, calixpyridinium-SA-M supramolecular aggregates were more sensitive to alkali. However, for the same reason, in comparison with calixpyridinium-SA-M supramolecular aggregates, calixpyridinium-SA-L supramolecular aggregates were much more stable in water not only at room temperature but also at a higher temperature, and even in salt solution. Therefore, in comparison with calixpyridinium-SA-L supramolecular aggregates, calixpyridinium-SA-M supramolecular aggregates exhibited a completely opposite response to acid because of the generation of salt. Because SA is an important biomaterial with excellent biocompatibility, it is anticipated that this comparative study is extremely important in constructing functional supramolecular biomaterials.