Record High Uranium Photoassisted Capture Performance from Fluorine-Containing Wastewater by Ag/WO with Surface Defect and Heterostructure.

The uranium recovery from high concentration fluorine-containing uranium wastewater is a desired research target in the field of environmental radiochemistry but is very challenging due to the formation of stable uranium fluoride complexes that are quite difficult to extract. By employing surface defect engineering and interfacial heterostructure design, we present here the rational design of an efficient photocatalyst (Ag/WO) for U(VI) uptake from fluorine-containing uranium wastewater without any sacrificial agents. The defect-rich surface of Ag/WO facilitates confined adsorption of uranium, while the introduction of Ag nanoparticles enables both efficient electron-hole separation and a plasmon effect upon light irradiation.

Thorium Cluster Synthesized by a Solvent-Free Flux Approach: The Richest Coordination Diversity and Application Exploration.

The renaissance of research interests in actinide oxo clusters in the past decade arises from both the concerns of radioactive contamination and their potential utility as nanoscale materials. Compared to the uranium cluster, the thorium (Th) cluster shows less coordination variation. Herein, we presented a unique Th cluster () that exhibits the most diverse coordination chemistry found within a single Th cluster via a solvent-free flux synthesis approach.

Clearance of β-amyloid and synapses by the optogenetic depolarization of microglia is complement selective.

Microglia actively monitor the neighboring brain microenvironments and constantly contact synapses with their unique ramified processes. In neurodegenerative diseases, including Alzheimer's disease (AD), microglia undergo morphological and functional alterations. Whether the direct manipulation of microglia can selectively or concurrently modulate synaptic function and the response to disease-associated factors remains elusive.

Assembling a Heterobimetallic Actinide Metal-Organic Framework by a Reaction-Induced Preorganization Strategy.

Periodically arranging coordination-distinct actinides into one crystalline architecture is intriguing but of great synthetic challenge. We report a rare example of a heterobimetallic actinide metal-organic framework (An-MOF) by a unique reaction-induced preorganization strategy. A thorium MOF (SCU-16) with the largest unit cell among all Th-MOFs was prepared as the precursor, then the uranyl was precisely embedded into the MOF precursor under oxidation condition.

Enhanced Xe/Kr separation the pore size confinement effect of a microporous thorium-based metal-organic framework.

A three-dimensional microporous thorium-based metal-organic framework (Th-BPYDC-I) that features a suitable pore size for Xe was prepared. The pore confinement effect enables high Xe uptake (2.15 mmol g) and good Xe/Kr selectivity (7.

Thermodynamics-Kinetics-Balanced Metal-Organic Framework for In-Depth Radon Removal under Ambient Conditions.

Radon (Rn), a ubiquitous radioactive noble gas, is the main source of natural radiation to human and one of the major culprits for lung cancer. Reducing ambient Rn concentration by porous materials is considered as the most feasible and energy-saving option to lower this risk, but the in-depth Rn removal under ambient conditions remains an unresolved challenge, mainly due to the weak van der Waals (vdW) interaction between inert Rn and adsorbents and the extremely low partial pressure (<1.8 × 10 bar, <10 Bq/m) of Rn in air.

Turn-up Luminescent Sensing of Ultraviolet Radiation by Lanthanide Metal-Organic Frameworks.

Here, we report a series of two-dimensional lanthanide metal-organic frameworks Ln-DBTPA (where DBTPA = 2,5-dibromoterephthalic acid and Ln = Tb (), Eu (), or Gd ()) showing a unique turn-up responsiveness toward ultraviolet (UV) radiation. The luminescence enhancement was derived from the accumulated radicals that can promote the intersystem crossing process. The compound shows an ultralow detection limit of 9.

Task-Specific Tailored Cationic Polymeric Network with High Base-Resistance for Unprecedented TcO Cleanup from Alkaline Nuclear Waste.

Direct removal of TcO from alkaline nuclear waste is desirable because of the nuclear waste management and environmental protection relevant to nuclear energy but is yet to be achieved given that combined features of decent base-resistance and high uptake selectivity toward anions with low charge density have not been integrated into a single anion-exchange material. Herein, we proposed a strategy overcoming these challenges by rationally modifying the imidazolium unit of a cationic polymeric network (SCU-CPN-4) with bulky alkyl groups avoiding its ring-opening reaction induced by OH because of the steric hindrance effect. This significantly improves not only the base-resistance but also the affinity toward TcO as a result of enhanced hydrophobicity, compared to other existing anion-exchange materials.

Efficient Sr-90 removal from highly alkaline solution by an ultrastable crystalline zirconium phosphonate.

We report here a distinct case of strontium removal under 1 M NaOH solution by an ultrastable crystalline zirconium phosphonate framework (SZ-7) with high adsorption capacity (183 mg g) and in-depth removal performance (K = 3.9 × 10 mL g), demonstrating the potential application of SZ-7 for Sr removal in highly alkaline nuclear waste.

Development of a Prognostic Five-Gene Signature for Diffuse Lower-Grade Glioma Patients.

Diffuse lower-grade gliomas (LGGs) are infiltrative and heterogeneous neoplasms. Gene signature including multiple protein-coding genes (PCGs) is widely used as a tumor marker. This study aimed to construct a multi-PCG signature to predict survival for LGG patients.

Deuterated Covalent Organic Frameworks with Significantly Enhanced Luminescence.

Luminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation-caused quenching (ACQ) or the molecular thermal motion-based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high-frequency oscillators X-H (X=O, N, C) by heavier isotope deuterium. Combining the "bottom-up" and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19-fold enhancement in quantum yield over that of the non-deuterated counterpart.

Multivalent cooperativity induced by self-assembly for f-element separation.

Preorganization is an effective strategy for f-element separation, but the complexity of extractant synthesis hinders large-scale application. Here the authors discuss an alternative strategy induced by in situ self-assembly that borrows principles of multivalent cooperativity from Nature to separate f-elements.

Highly efficient actinide(III)/lanthanide(III) separation by novel pillar[5]arene-based picolinamide ligands: A study on synthesis, solvent extraction and complexation.

Selective extraction of highly radiotoxic actinides(III) is an important and challenging task in nuclear wastewater treatment. Many proposed ligands containing S or P atoms have drawbacks including high reagent consumption and possible secondary pollution after incineration. The present work reports five novel pillar[5]arene-based extractants that are anchored with picolinamide substituents of different electronic nature by varying spacer.

Controlling the selective synthesis of [2]- and [3]rotaxanes by intermolecular steric hindrance between the macrocyclic hosts.

Two hydrogen-bonded azo-macrocycles with little disparity of the side chains in steric hindrance exhibited a substantial difference in complexation (slow/fast exchange) towards bipyridinium. Inspired by this finding, these macrocycles were applied to efficiently and selectively construct [2]- and [3]rotaxanes through one-pot synthesis. The origin of the selectivity in this novel approach was elucidated by comparing single crystal structures, DFT calculations and stepwise synthesis.

Removal of the environmental pollutant carbamazepine using molecular imprinted adsorbents: Molecular simulation, adsorption properties, and mechanisms.

Carbamazepine (CBZ) is a typical pharmaceutical residue commonly found in aqueous environments, but its removal through activated carbon or advanced oxidation processes is often disrupted by co-existing organic matter. An imprinting system which consisted of the target pollutant CBZ (template molecule) and 10 different kinds of functional monomers was constructed via molecular simulation to screen for appropriate monomers, thereby addressing CBZ removal disruptions. An annealing method simulation was used to search for stable, low-energy conformations of the template-monomer interaction system to calculate the binding energy of these different monomers with CBZ.

A Dynamic Hydrogen-Bonded Azo-Macrocycle for Precisely Photo-Controlled Molecular Encapsulation and Release.

A light-responsive system constructed from hydrogen-bonded azo-macrocycles demonstrates precisely controlled propensity in molecular encapsulation and release process. A significant decrease in the size of the cavity is observed in the course of the E→Z photoisomerization based on the results from DFT calculations and traveling wave ion mobility mass spectrometry. These macrocyclic hosts exhibit a rare 2:1 host-guest stoichiometry and guest-dependent slow or fast exchange on the NMR timescale.

Pillararenes as macrocyclic hosts: a rising star in metal ion separation.

Pillararenes are macrocyclic oligomers of alkoxybenzene akin to calixarenes but tethered at the 2,5-positions via methylene bridges. Benefiting from their unique pillar-shaped architecture favorable for diverse functionalization and versatile host-guest properties, pillararenes decorated with chelating groups worked excellently as supporting platforms to construct extractants or adsorbents for metal ion separation. This feature article provides a detailed summary of pillararenes in Ln/An separation by liquid-liquid extraction and heavy metal separation by solid-liquid extraction.

Convergent Ditopic Receptors Enhance Anion Binding upon Alkali Metal Complexation for Catalyzing the Ritter Reaction.

A supramolecular approach to catalyzing the Ritter reaction by utilizing enhanced anion-binding affinity in the presence of alkali metal cations was developed with ditopic hydrogen-bonded amide macrocycles. With prebound cations in the macrocycle, particularly Li ion, their metal complexes exhibit greatly enhanced catalytic activities. The catalysis is switchable by removal or addition of the bound cation.

Macrocyclic shape-persistency of cyclo[6]aramide results in enhanced multipoint recognition for the highly efficient template-directed synthesis of rotaxanes.

Examples of using two-dimensional shape-persistent macrocycles, those having noncollapsible and geometrically well-defined skeletons, for constructing mechanically interlocked molecules are scarce, which contrasts the many applications of these macrocycles in molecular recognition and functional self-assembly. Herein, we report the crucial role played by macrocyclic shape-persistency in enhancing multipoint recognition for the highly efficient template-directed synthesis of rotaxanes. Cyclo[6]aramides, with a near-planar conformation, are found to act as powerful hosts that bind bipyridinium salts with high affinities.

Reversibly Tunable Lower Critical Solution Temperature Behavior Induced by H-Bonded Aromatic Amide Macrocycle and Imidazolium Host-Guest Complexation.

A new supramolecular host-guest motif comprising an H-bonded aromatic amide macrocycle and imidazolium cation based ionic liquids was developed, which allows tunable binding affinity via altering N-substitution or counterions. This host-guest system exhibits lower critical solution temperature behavior that can be precisely controlled by adjusting concentration, competitive guest, and acid/base. The demonstrated separation of two organic dyes with the supramolecular complex holds promising applications in separation science.

Highly efficient extraction of actinides with pillar[5]arene-derived diglycolamides in ionic liquids via a unique mechanism involving competitive host-guest interactions.

Actinide partitioning is considered as one of the most challenging issues in nuclear waste remediation. Herein, we unravel a novel extraction mode pertinent to the competitive host-guest interactions for highly efficient actinide extraction. The host-guest recognition event involves binding of a room temperature ionic liquid (RTIL), 1-n-octyl-3 methylimidazolium bis(trifluoromethane)sulfonamide (CmimNTf), as both the guest and the solvent by the hosts pillar[5]arene-based diglycolamides (P5DGAs) and the subsequent displacement of the guest by a metal ion.