Correction: Metal-organic-framework derived Co-Pd bond is preferred over Fe-Pd for reductive upgrading of furfural to tetrahydrofurfuryl alcohol.

Correction for 'Metal-organic-framework derived Co-Pd bond is preferred over Fe-Pd for reductive upgrading of furfural to tetrahydrofurfuryl alcohol' by Saikiran Pendem et al., Dalton Trans., 2019, 48, 8791-8802, https://doi.org/10.1039/C9DT01190K.

Conjugated microporous polymer membranes for light-gated ion transport.

Inspired by the light-gated ion channels in cell membranes that play important roles in many biological activities, herein, we developed an artificial light-gated ion channel membrane out of conjugated microporous polymers. Through bottom-up design of the monomer molecular structure and by the electropolymerization method, the membrane pore size and thickness were precisely controlled on the molecular level. The obtained membrane exhibited uniform pore size and highly sensitive light-switchable response. The photoisomerization of the polymer chain resulted in a reversible "on and off" light control over the pore size and subsequently led to light-gated ion transport across the membrane for a series of ions including hydrogen, potassium, sodium, lithium, calcium, magnesium, and aluminum ions.

Giant Osmotic Energy Conversion through Vertical-Aligned Ion-Permselective Nanochannels in Covalent Organic Framework Membranes.

Nanofluidic membranes have been demonstrated as promising candidates for osmotic energy harvesting. However, it remains a long-standing challenge to fabricate high-efficiency ion-permselective membranes with well-defined channel architectures. Here, we demonstrate high-performance osmotic energy conversion membranes based on oriented two-dimensional covalent organic frameworks (COFs) with ultrashort vertically aligned nanofluidic channels that enabled efficient and selective ion transport. Experiments combined with molecular dynamics simulations revealed that exquisite control over channel orientation, charge polarity, and charge density contributed to high ion selectivity and permeability. When applied to osmotic energy conversion, a pair of 100 nm thick oppositely charged COF membranes achieved an ultrahigh output power density of 43.2 W m-2 at a 50-fold salinity gradient and up to 228.9 W m-2 for the Dead Sea and river water system. The achieved power density outperforms the state-of-the-art nanofluidic membranes, suggesting the great potential of oriented COF membranes in the fields of advanced membrane technology and energy conversion.

Foldable Solid-State Batteries Enabled by Electrolyte Mediation in Covalent Organic Frameworks.

Solid-state electrolytes with high Li+ conductivity, flexibility, durability, and stability offer an attractive solution to enhance safety and energy density. However, meeting these stringent requirements poses challenges to the existing solid polymeric or ceramic electrolytes. Here, an electrolyte-mediated single-Li+ -conductive covalent organic framework (COF) is presented, which represents a new category of quality solid-state Li+ conductors. In situ solidification of a tailored liquid electrolyte boosts the charge-carrier concentration in the COF channels, decouples Li+ cations from both COF walls and molecular chains, and eliminates defects by crystal soldering. Such an altered microenvironment activates the motion of Li+ ions in a directional manner, which leads to an increase in Li+ conductivity by 100 times with a transference number of 0.85 achieved at room temperature. Moreover, the electrolyte conversion cements the ultrathin COF membrane with fortified mechanical toughness. With the COF membrane, foldable solid-state pouch cells are demonstrated.

Oriented Two-Dimensional Covalent Organic Framework Membranes with High Ion Flux and Smart Gating Nanofluidic Transport.

Nanofluidic ion transport holds high promise in bio-sensing and energy conversion applications. However, smart nanofluidic devices with high ion flux and modulable ion transport capabilities remain to be realised. Herein, we demonstrate smart nanofluidic devices based on oriented two-dimensional covalent organic framework (2D COF) membranes with vertically aligned nanochannel arrays that achieved a 2-3 orders of magnitude higher ion flux compared with that of conventional single-channel nanofluidic devices. The surface-charge-governed ion conductance is dominant for electrolyte concentration up to 0.01 M. Moreover, owing to the customisable pH-responsivity of imine and phenol hydroxyl groups, the COF-DT membranes attained an actively modulable ion transport with a high pH-gating on/off ratio of ≈100. The customisable structure and rich chemistry of COF materials will offer a promising platform for manufacturing nanofluidic devices with modifiable ion/molecular transport features.

Precise Sub-Angstrom Ion Separation Using Conjugated Microporous Polymer Membranes.

Polymer membranes typically possess a broad pore-size distribution that leads to much lower selectivity in ion separation when compared to membranes made of crystalline porous materials; however, they are highly desirable because of their easy processability and low cost. Herein, we demonstrate the fabrication of ion-sieving membranes based on a polycarbazole-type conjugated microporous polymer using an easy to scale-up electropolymerization strategy. The membranes exhibited high uniform sub-nanometer pores and a precisely tunable membrane thickness, yielding a high ion-sieving performance with a sub-1 Å size precision. Both experimental results and molecular simulations suggested that the impressive ion-sieving performance of the CMP membranes originates from their uniform and narrow pore-size distribution.

A Robust, Safe, and Scalable Magnetic Nanoparticle Workflow for RNA Extraction of Pathogens from Clinical and Wastewater Samples.

Molecular diagnosis and surveillance of pathogens such as SARS-CoV-2 depend on nucleic acid isolation. Pandemics at the scale of COVID-19 can cause a global shortage of proprietary commercial reagents and BSL-2 laboratories to safely perform testing. Therefore, alternative solutions are urgently needed to address these challenges. An open-source method, magnetic-nanoparticle-aided viral RNA isolation from contagious samples (MAVRICS), built upon readily available reagents, and easily assembled in any basically equipped laboratory, is thus developed. The performance of MAVRICS is evaluated using validated pathogen detection assays and real-world and contrived samples. Unlike conventional methods, MAVRICS works directly in samples inactivated in phenol-chloroform (e.g., TRIzol), thus allowing infectious samples to be handled safely without biocontainment facilities. MAVRICS allows wastewater biomass immobilized on membranes to be directly inactivated and lysed in TRIzol followed by RNA extraction by magnetic nanoparticles, thereby greatly reducing biohazard risk and simplifying processing procedures. Using 39 COVID-19 patient samples and two wastewater samples, it is shown that MAVRICS rivals commercial kits in detection of SARS-CoV-2, influenza viruses, and respiratory syncytial virus. Therefore, MAVRICS is safe, fast, and scalable. It is field-deployable with minimal equipment requirements and could become an enabling technology for widespread testing and wastewater monitoring of diverse pathogens.

Modulation of destructive quantum interference by bridge groups in truxene-based single-molecule junctions.

Electron transport properties of polycyclic truxene derivatives have been investigated by the single molecule conductance measurement technique and theoretical study. Molecules with nitrogen and carbonyl substituents at the bridge sites exhibit higher single-molecule conductances by almost one order of magnitude compared with non-substituted analogues. It can be ascribed that the anti-resonance feature produced by destructive quantum interference (DQI) is alleviated and pushed away from the Fermi energy. These findings provide an effective chemical strategy for manipulating the DQI behavior in single molecular devices.

Covalent Organic Framework Embedded with Magnetic Nanoparticles for MRI and Chemo-Thermotherapy.

Nanoscale imine-linked covalent organic frameworks (nCOFs) were first loaded with the anticancer drug Doxorubicin (Dox), coated with magnetic iron oxide nanoparticles (γ-Fe2O3 NPs), and stabilized with a shell of poly(l-lysine) cationic polymer (PLL) for simultaneous synergistic thermo-chemotherapy treatment and MRI imaging. The pH responsivity of the resulting nanoagents (γ-SD/PLL) allowed the release of the drug selectively within the acidic microenvironment of late endosomes and lysosomes of cancer cells (pH 5.4) and not in physiological conditions (pH 7.4). γ-SD/PLL could efficiently generate high heat (48 °C) upon exposure to an alternating magnetic field due to the nCOF porous structure that facilitates the heat conduction, making γ-SD/PLL excellent heat mediators in an aqueous solution. The drug-loaded magnetic nCOF composites were cytotoxic due to the synergistic toxicity of Dox and the effects of hyperthermia in vitro on glioblastoma U251-MG cells and in vivo on zebrafish embryos, but they were not significantly toxic to noncancerous cells (HEK293). To the best of our knowledge, this is the first report of multimodal MRI probe and chemo-thermotherapeutic magnetic nCOF composites.

Electropolymerization of robust conjugated microporous polymer membranes for rapid solvent transport and narrow molecular sieving.

Pore size uniformity is one of the most critical parameters in determining membrane separation performance. Recently, a novel type of conjugated microporous polymers (CMPs) has shown uniform pore size and high porosity. However, their brittle nature has prevented them from preparing robust membranes. Inspired by the skin-core architecture of spider silk that offers both high strength and high ductility, herein we report an electropolymerization process to prepare a CMP membrane from a rigid carbazole monomer, 2,2',7,7'-tetra(carbazol-9-yl)-9,9'-spirobifluorene, inside a robust carbon nanotube scaffold. The obtained membranes showed superior mechanical strength and ductility, high surface area, and uniform pore size of approximately 1 nm. The superfast solvent transport and excellent molecular sieving well surpass the performance of most reported polymer membranes. Our method makes it possible to use rigid CMPs membranes in pressure-driven membrane processes, providing potential applications for this important category of polymer materials.

Tuning the Surface Structure of Polyamide Membranes Using Porous Carbon Nitride Nanoparticles for High-Performance Seawater Desalination.

Enhancing the water flux while maintaining the high salt rejection of existing reverse osmosis membranes remains a considerable challenge. Herein, we report the use of a porous carbon nitride (C3N4) nanoparticle to potentially improve both the water flux and salt rejection of the state-of-the-art polyamide (PA) thin film composite (TFC) membranes. The organic-organic covalent bonds endowed C3N4 with great compatibility with the PA layer, which positively influenced the customization of interfacial polymerization (IP). Benefitting from the positive effects of C3N4, a more hydrophilic, more crumpled thin film nanocomposite (TFN) membrane with a larger surface area, and an increased cross-linking degree of PA layer was achieved. Moreover, the uniform porous structure of the C3N4 embedded in the "ridge" sections of the PA layer potentially provided additional water channels. All these factors combined provided unprecedented performance for seawater desalination among all the PA-TFC membranes reported thus far. The water permeance of the optimized TFN membrane is 2.1-folds higher than that of the pristine PA-TFC membrane, while the NaCl rejection increased to 99.5% from 98.0%. Our method provided a promising way to improve the performance of the state-of-art PA-TFC membranes in seawater desalination.

Pore engineering of ultrathin covalent organic framework membranes for organic solvent nanofiltration and molecular sieving.

The advantages of two dimensional covalent organic framework membranes to achieve high flux have been demonstrated, but the capability of easy structural modification to manipulate the pore size has not been fully explored yet. Here we report the use of the Langmuir-Blodgett method to synthesize two ultrathin covalent organic framework membranes (TFP-DPF and TFP-DNF) that have a similar framework structure to our previously reported covalent organic framework membrane (TFP-DHF) but different lengths of carbon chains aiming to rationally control the pore size. The membrane permeation results in the applications of organic solvent nanofiltration and molecular sieving of organic dyes showed a systematic shift of the membrane flux and molecular weight cut-off correlated to the pore size change. These results enhanced our fundamental understanding of transport through uniform channels at nanometer scales. Pore engineering of the covalent organic framework membranes was demonstrated for the first time.

Metal-organic-framework derived Co-Pd bond is preferred over Fe-Pd for reductive upgrading of furfural to tetrahydrofurfuryl alcohol.

Combined noble-transition metal catalysts have been used to produce a wide range of important non-petroleum-based chemicals from biomass-derived furfural (as a platform molecule) and have garnered colossal research interest due to the urgent demand for sustainable and clean fuels. Herein, we report the palladium-modified metal-organic-framework (MOF) assisted preparation of PdCo3O4 and PdFe3O4 nanoparticles encapsulated in a graphitic N-doped carbon (NC) matrix via facile in situ thermolysis. This provides a change in selectivity with superior catalytic activity for the reductive upgrading of biomass-derived furfural (FA). Under the optimized reaction conditions, the newly designed PdCo3O4@NC catalyst exhibited highly efficient catalytic performance in the hydrogenation of furfural, providing 100% furfural conversion with 95% yield of tetrahydrofurfuryl alcohol (THFAL). In contrast, the as-synthesized Pd-Fe3O4@NC afforded a THFAL yield of 70% after an 8 h reaction with four consecutive recycling tests. Based on different characterization data (XPS, H2-TPR) for nanohybrids, we can conclude that the presence of PdCo-Nx active sites, and the multiple synergistic effects between Co3O4 and Pd(ii), Co3O4 and Pd0, as well as the presence of N in the carbonaceous matrix, are responsible for the superior catalytic activity and improved catalyst stability. Our strategy provides a facile design and synthesis process for a noble-transition metal alloy as a superior biomass refining, robust catalyst via noble metal modified MOFs as precursors.

Crystalline 2D Covalent Organic Framework Membranes for High-Flux Organic Solvent Nanofiltration.

Two-dimensional (2D) covalent organic framework (COF) materials have the most suitable microstructure for membrane applications in order to achieve both high flux and high selectivity. Here, we report the synthesis of a crystalline TFP-DHF 2D COF membrane constructed from two precursors of 1,3,5-triformylphloroglucinol (TFP) and 9,9-dihexylfluorene-2,7-diamine (DHF) through the Langmuir-Blodgett (LB) method, for the first timed. A single COF layer is precisely four unit cells thick and can be transferred to different support surfaces layer by layer. The TFP-DHF 2D COF membrane supported on an anodic aluminum oxide (AAO) porous support displayed remarkable permeabilities for both polar and nonpolar organic solvents, which were approximately 100 times higher than that of the amorphous membranes prepared by the same procedure and similar to that for the best of the reported polymer membranes. The transport mechanism through the TFP-DHF 2D COF membrane was found to be a viscous flow coupled with a strong slip boundary enhancement, which was also different from those of the amorphous polymer membranes. The membrane exhibited a steep molecular sieving with a molecular weight retention onset (MWRO) of approximately 600 Da and a molecular weight cutoff (MWCO) of approximately 900 Da. The substantial performance enhancement was attributed to the structural change from an amorphous structure to a well-defined ordered porous structure, which clearly demonstrated the high potential for the application of 2D COFs as the next generation of membrane materials.

Self-templated chemically stable hollow spherical covalent organic framework.

Covalent organic frameworks are a family of crystalline porous materials with promising applications. Although active research on the design and synthesis of covalent organic frameworks has been ongoing for almost a decade, the mechanisms of formation of covalent organic frameworks crystallites remain poorly understood. Here we report the synthesis of a hollow spherical covalent organic framework with mesoporous walls in a single-step template-free method. A detailed time-dependent study of hollow sphere formation reveals that an inside-out Ostwald ripening process is responsible for the hollow sphere formation. The synthesized covalent organic framework hollow spheres are highly porous (surface area ∼1,500 m(2 )g(-1)), crystalline and chemically stable, due to the presence of strong intramolecular hydrogen bonding. These mesoporous hollow sphere covalent organic frameworks are used for a trypsin immobilization study, which shows an uptake of 15.5 µmol g(-1) of trypsin.