Hydrogen Isotope Effect Endows a Breakthrough in Photoluminescent Covalent Organic Frameworks.

Luminescent covalent organic frameworks (LCOFs) have emerged as indispensable candidates in various applications due to their greater tunable emitting properties and structural robustness compared to small molecule emitters. An unsolved issue in this area is developing highly luminescent LCOFs of which the nonradiative quenching pathways were suppressed as much as possible. Here, a robust aminal-linked COF (DD-COF) possessing perdeuterated light-emitting monomers was designed and synthesized. The solid-state photoluminescence quantum yield of the DD-COF reaches 81%, significantly outcompeting all state-of-the-art LCOFs reported so far. The exceptional luminescent efficiency is attributed to the inhibition of different pathways of nonradiative decay, especially from bond vibrations where only substitution by a heavier isotope with a lower zero-point vibration frequency works. Furthermore, the prepared deuterated COF not only boosts higher photostability under UV irradiation but also enables superior fluorescence sensing performance for iodine detection compared to nondeuterated COF.

Isotope Effect-Enabled Crystal Enlargement in Metal-Organic Frameworks.

Synthesizing large metal-organic framework (MOF) single crystals has garnered significant research interest, although it is hindered by the fast nucleation kinetics that gives rise to numerous small nuclei. Given the different chemical origins inherent in various types of MOFs, the development of a general approach to enhancing their crystal sizes presents a formidable challenge. Here, we propose a simple isotopic substitution strategy to promote size growth in MOFs by inhibiting nucleation, resulting in a substantial increase in the crystal volume ranging from 1.7- to 165-fold. Impressively, the crystals prepared under optimized conditions by normal approaches can be further enlarged by the isotope effect, yielding the largest MOF single crystal (2.9 cm × 0.48 cm × 0.23 cm) among the one-pot synthesis method. Detailed in situ characterizations reveal that the isotope effect can retard crystallization kinetics, establish a higher nucleation energy barrier, and consequently generate fewer nuclei that eventually grow larger. Compared with the smaller crystals, the isotope effect-enlarged crystal shows 33% improvement in the X-ray dose rate detection limit. This work enriches the understanding of the isotope effect on regulating the crystallization process and provides inspiration for exploring potential applications of large MOF single crystals.

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. Single crystal of the resulting thorium-uranium MOF (SCU-16-U) shows that a uranyl-specific site was in situ induced by the formate-to-carbonate oxidation reaction. The heterobimetallic SCU-16-U exhibits multifunction catalysis properties derived from two distinct actinides. The strategy proposed here offers a new avenue to create mixed-actinide functional material with unique architecture and versatile functionality.

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 × 10-14 bar, <106 Bq/m3) of Rn in air. Adsorbents having either favorable adsorption thermodynamics or feasible diffusion kinetics perform poorly in in-depth Rn removal. Herein, we report the discovery of a metal-organic framework (ZIF-7-Im) for efficient Rn capture guided by computational screening and modeling. The size-matched pores in ZIF-7-Im abide by the thermodynamically favorable principle and the exquisitely engineered quasi-open apertures allow for feasible kinetics with little sacrifice of sorption thermodynamics. The as-prepared material can reduce the Rn concentration from hazardous levels to that below the detection limit of the Rn detector under ambient conditions, with an improvement of at least two orders of amplitude on the removal depth compared to the currently best-performing and only commercialized material activated charcoal.

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 (1), Eu (2), or Gd (3)) 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 1 shows an ultralow detection limit of 9.1 × 10-9 J toward UV radiation, representing a new type of luminescent UV detectors.

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. These results are interpreted by theoretical calculations as the consequence of slower C/N-D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs.

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. With the slow host-guest exchange and switchable shape change of the cavity, quantitative release and capture of bipyridinium guests is achieved with the maximum release of 68 %. This work underscores the importance of slow host-guest exchange on realizing accurate release of organic cations in a stepwise manner under light irradiation. The light-responsive system established here could advance further design of novel photoresponsive molecular switches and mechanically interlocked molecules.

Clearance of ß-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. Here, we employ optogenetic methods to stimulate microglia in vitro and in vivo. Membrane depolarization rapidly changes microglia morphology and leads to enhanced phagocytosis. We found that the optogenetic stimulation of microglia can efficiently promote ß-amyloid (Aß) clearance in the brain parenchyma, but it can also enhance synapse elimination. Importantly, the inhibition of C1q selectively prevents synapse loss induced by microglia depolarization but does not affect Aß clearance. Our data reveal independent microglia-mediated phagocytosis pathways toward Aß and synapses. Our results also shed light on a synergistic strategy of depolarizing microglia and inhibiting complement functions for the clearance of Aß while sparing synapses.

Enhanced Xe/Kr separation via 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-1) and good Xe/Kr selectivity (7.49). This work highlights the critical role of the size-matching rule in noble gas separation and provides an alternative option for Xe/Kr separation.

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

Background: 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. Methods: LGG data including PCG expression profiles and clinical information were downloaded from The Cancer Genome Atlas (TCGA) and the Chinese Glioma Genome Atlas (CGGA). Survival analysis, receiver operating characteristic (ROC) analysis, and random survival forest algorithm (RSFVH) were used to identify the prognostic PCG signature. Results: From the training (n = 524) and test (n = 431) datasets, a five-PCG signature which can classify LGG patients into low- or high-risk group with a significantly different overall survival (log rank P < 0.001) was screened out and validated. In terms of prognosis predictive performance, the five-PCG signature is stronger than other clinical variables and IDH mutation status. Moreover, the five-PCG signature could further divide radiotherapy patients into two different risk groups. GO and KEGG analysis found that PCGs in the prognostic five-PCG signature were mainly enriched in cell cycle, apoptosis, DNA replication pathways. Conclusions: The new five-PCG signature is a reliable prognostic marker for LGG patients and has a good prospect in clinical application.

Task-Specific Tailored Cationic Polymeric Network with High Base-Resistance for Unprecedented 99TcO4 - Cleanup from Alkaline Nuclear Waste.

Direct removal of 99TcO4 - 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 TcO4 - as a result of enhanced hydrophobicity, compared to other existing anion-exchange materials. More importantly, SCU-CPN-4 exhibits record high uptake selectivity, fast sorption kinetics, sufficient robustness, and promising reusability for removing 99TcO4 - from the simulated high-level waste stream at the U.S. Savannah River Site, a typical alkaline nuclear waste, in both batch experiment and dynamic column separation test for the first time.

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-1) and in-depth removal performance (Kd = 3.9 × 105 mL g-1), demonstrating the potential application of SZ-7 for 90Sr removal in highly alkaline nuclear waste.

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. These ligands reveal highly efficient separation of actinides(III) over lanthanides(III). Specifically, almost all of these ligands could extract Am(III) over Eu(III) selectively at around pH 3.0 (SFAm/Eu>11) with fast extraction kinetics. Variation of the pyridine nitrogen basicity via changing para-substitution leads to an increase in the distribution ratios by a factor of over 300 times for Am(III) with an electron-withdrawing group compared to those with an electron donating group. Investigation of complexation mechanism by slope analysis, NMR, IR, EXAFS, and DFT techniques indicates that each ligand binds two metal ions by pyridine nitrogen and amide oxygen. Finally, these ligands do not show obvious decrease in both extraction and separation ability after being exposed to 250 kGy absorbed gamma radiation. These results demonstrate the potential application of pillar[5]arene-picolinamides for actinide(III) separation.

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. The order of binding affinity calculated was: 4-vinylbenzoic acid > itaconic acid > methacrylic acid, which was consistent with the experimental observations. The adsorption capacity of the molecular imprinted polymer (MIP) prepared using 4-vinylbenzoic acid reached 28.40 mg/g, and the imprinting factor reached 2.72. The simulation and measurement of the ultraviolet spectrum of the imprinting system showed that a new interaction system was formed between the template and monomers, and that multiple binding conformations between them took place when specific recognition occurred. Energy calculation and hydrogen bond analysis revealed that the van der Waals force, including the π-π conjugate and electrostatic forces including hydrogen bonding, played an important role during selective adsorption, which was confirmed by infrared spectroscopy analysis.

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.

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. The preorganization effect of the rigid pillararene framework has a profound impact on the extraction of metal ions, and a unique extraction mechanism is observed when employing ionic liquids as solvents. The rich host-guest chemistry of pillararenes enables construction of a wide variety of supramolecular materials as metal ion adsorbents. We also discuss the differences between pillararenes and several well-known macrocycles, with a focus on the metal-ligand coordination and its influencing factors. We hope this review will provide useful information and unleash new opportunities in this field.

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. The method described in this work may be generalized for use in other anion-triggered organic reactions involving heteroditopic receptors capable of ion pairing.

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.

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, i.e. 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. This unique recognition module, composed of two macrocyclic molecules with one bipyridinium ion thread through the cavity, is observed both in the solid state and in solution, with unusually high binding constants ranging from ∼1013 M-2 to ∼1015 M-2 in acetone. The high efficacy of this recognition motif is embodied by the formation of compact [3]rotaxanes in excellent yields based on either a "click-capping" (91%) or "facile one-pot" (85%) approach, underscoring the great advantage of using H-bonded aromatic amide macrocycles for the highly efficient template-directed synthesis of mechanically interlocked structures. Furthermore, three cyclo[6]aramides bearing different peripheral chains 1-3 demonstrate high specificity in the synthesis of a [3]rotaxane from 1 and 2, and a [2]rotaxane from 3via a "facile one-pot" approach, in each case as the only isolated product. Analysis of the crystal structure of the [3]rotaxane reveals a highly compact binding mode that would be difficult to access using other macrocycles with a flexible backbone. Leveraging this unique recognition motif, resulting from the shape-persistency of these oligoamide macrocycles, in the template-directed synthesis of compact rotaxanes may open up new opportunities for the development of higher order interlocked molecules and artificial molecular machines.