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.

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.

Radiation-Induced De Novo Defects in Metal-Organic Frameworks Boost CO2 Sorption.

Defects in metal-organic frameworks (MOFs) can significantly change their local microstructures, thus notably leading to an alteration-induced performance in sorption or catalysis. However, achieving de novo defect engineering in MOFs under ambient conditions without the scarification of their crystallinity remains a challenge. Herein, we successfully synthesize defective ZIF-7 through 60Co gamma ray radiation under ambient conditions. The obtained ZIF-7 is defect-rich but also has excellent crystallinity, enhanced BET surface area, and hierarchical pore structure. Moreover, the amount and structure of these defects within ZIF-7 were determined from the two-dimensional (2D) 13C-1H frequency-switched Lee-Goldburg heteronuclear correlation (FSLG-HETCOR) spectra, continuous rotation electron diffraction (cRED), and high-resolution transmission electron microscopy (HRTEM). Interestingly, the defects in ZIF-7 all strongly bind to CO2, leading to a remarkable enhancement of the CO2 sorption capability compared with that synthesized by the solvothermal method.

Metal-Organic Framework@Metal Oxide Heterostructures Induced by Electron-Beam Radiation.

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high-energy (1.5 MeV) electron beam radiation from a commercially available electron-accelerator. Using ZIF-8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF-8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF-8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes.

Biocontrol activity and action mechanism of Paenibacillus polymyxa strain Nl4 against pear Valsa canker caused by Valsa pyri.

Pear Valsa canker caused by Valsa pyri is among the most destructive diseases of pear, which causes significant economic loss. The present study was developed to explore the biocontrol efficiency and underlying antagonistic mechanism of Paenibacillus polymyxa strain Nl4 against V. pyri. P. polymyxa strain Nl4, one of the 120 different endophytic bacterial strains from pear branches, exhibited strong inhibitory effects against the mycelial growth of V. pyri and caused hyphal malformation. Culture filtrate derived from strain Nl4 was able to effectively suppress mycelial growth of V. pyri, and was found to exhibit strong protease, cellulase and ß-1, 3-glucanase activity. Through re-isolation assay, strain Nl4 was confirmed to be capable of colonizing and surviving in pear branch. Treatment with strain NI4 effectively protected against pear Valsa canker symptoms on detached pear twigs inoculated with V. pyri. Moreover, strain Nl4 promoted enhanced plant growth probably through the solubilization of phosphorus. Comparative transcriptomic analyses revealed that strain NI4 was able to suppress V. pyri growth in large part through the regulation of the expression of membrane- and energy metabolism-related genes in this pathogen. Further transcriptomic analyses of pear trees indicated that strain NI4 inoculation was associated with changes in the expression of genes associated with secondary metabolite biosynthesis, signal transduction, and cutin, suberine, and wax biosynthesis. Together, these data highlighted P. polymyxa strain Nl4 as a promising biocontrol agent against pear Valsa canker and investigated the possible mechanisms of strain Nl4 on control of this devastating disease.

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.

Efficient Xe/Kr Separation Based on a Lanthanide-Organic Framework with One-Dimensional Local Positively Charged Rhomboid Channels.

Efficient xenon/krypton (Xe/Kr) separation has played an important role in industry due to the wide application of high-purity Xe and with regard to the safe disposal of radioactive noble gases (85Kr and 133Xe). A less energy-demanding separation technology, adsorptive separation using porous solid materials, has been proposed to replace the traditional cryogenic distillation with intensive energy consumption. As a cutting-edge class of porous materials, metal-organic frameworks (MOFs) featuring permanent porosity, designable chemical functionalities, and tunable pore sizes hold great promise for Xe/Kr separation. Here, we report a two-dimensional (2D) lanthanide-organic framework (termed LPC-MOF, [Eu(Ccbp)(NO3)(HCOO)]·DMF0.3(H2O)2.5) with one-dimensional (1D) local positively charged rhomboid channels whose size matches well with the kinetic diameter of Xe, leading to its superior Xe/Kr separation performance. Column breakthrough experiments demonstrate that LPC-MOF exhibits a high Xe/Kr selectivity of 12.4 and an Xe adsorption amount of 3.39 mmol kg-1 under simulated conditions for real used nuclear fuel (UNF)-reprocessing plants. Furthermore, density functional theory (DFT) calculations elucidate not only the intrinsic mechanisms of Xe/Kr separation at the molecular level but also the detailed influence of the local positive charge (N+) on the performance of Xe/Kr separation in the MOF system.

Biocontrol activity of Bacillus halotolerans strain Pl7 against Botryosphaeria dothidea causing apple postharvest decay and potential mechanisms.

Apple ring rot, one of the most common apple postharvest diseases during storage, is caused by Botryosphaeria dothidea. Fungicide application is the most widely used method to control this disease, but the increasing environmental and food safety concerns greatly limit their use. The present study aimed to examine the biocontrol activity and underlying action mechanism of Bacillus halotolerans strain Pl7 against B. dothidea. The results revealed that B. halotolerans strain Pl7 exhibited strong inhibitory activity against B. dothidea by 69% in vitro. The culture filtrate of strain Pl7 possessed cellulase, ß-1, 3-glucanase, protease activity and mediated the antifungal activity against B. dothidea. Further analysis demonstrated that culture filtrate of strain Pl7 could cause cell membrane permeabilization of B. dothidea. Apple fruit suffering from ring rot induced by a carbendazim (CBZ)-sensitive or -resistant B. dothidea isolate was much suppressed after being treated with strain Pl7, maintaining postharvest quality. The ability of strain Pl7 to swiftly colonize and thrive in apple fruit wounds was demonstrated by a re-isolation assay. Additional transcriptome studies of untreated and treated apple fruit with strain Pl7 revealed that strain Pl7 mostly changed the expression of genes functioning in plant secondary metabolite biosynthesis and plant-pathogen interaction. In light of these outcomes, the underlying antagonistic mechanism was investigated, and B. halotolerans strain Pl7 was identified as a promsing microbial biocontrol agent against apple postharvest decay.

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.

Electron Beam Irradiation-Induced Formation of Defect-Rich Zeolites under Ambient Condition within Minutes.

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites.

Pyrene-Based Nonwoven Fabric with Tunable Fluorescence Properties by Employing the Aggregation-Caused Quenching Effect.

Conventional aromatic compounds tend to exhibit the formation of sandwich-shaped excimers and exciplexes between their excited and ground states at high concentrations or in their aggregated states, causing their fluorescence to weaken or disappear due to the aggregation-caused quenching (ACQ) effect. This limits their applications in concentrated solutions or solid materials. Herein, for the first time, ACQ-based pyrene (Py) units are covalently connected to the surface of polyethylene/polypropylene nonwoven fabric (PE/PP NWF) via electron beam preradiation-induced graft polymerization followed by chemical modification. The matrix can be considered a solid solvent and Py units as a solid solute, such that the amount of Py units can be controlled by varying the reaction time. The obtained fluorescent fabric not only exhibits remarkable fluorescence properties with high fluorescence intensity, high quantum yield (>90%), and excellent fluorescence stability after laundering or in harsh chemical environments, but the fluorescence color and intensity, quantum yield, and lifetime can also be regulated by employing the ACQ effect. Additionally, the as-prepared fluorescent fabric can effectively distinguish common monocyclic aromatic hydrocarbons via a simple fluorescence response test.

Radiation-Induced In Situ-Printed Nonconjugated Fluorescent Nonwoven Fabric with Superior Fluorescent Properties.

A new technique is proposed for the in situ printing of fluorescent fabrics with superior fluorescent properties that have the potential for continuous roll-to-roll production in the industry. Nonconjugated chemical moieties were covalently connected to polyethylene/polypropylene nonwoven fabric (PE/PP NWF) to successfully prepare fluorescent PE/PP NWF, which emits a bright blue light and has a high quantum yield (∼83.35%) that can be attributed to a unique aggregation-induced emission effect. The fluorescent PE/PP NWF exhibits excellent fluorescent stability under high shear forces during accelerated laundering and in harsh chemical environments. The fluorescent PE/PP NWF can also be tailored into diverse shapes and printed in situ with high resolution. The versatility of the method was also demonstrated by fabricating fluorescent materials with different polymer matrices such as Nylon 66 fiber and PE terephthalate membrane.

Electron Beam Irradiation as a General Approach for the Rapid Synthesis of Covalent Organic Frameworks under Ambient Conditions.

Crystalline porous materials such as covalent organic frameworks (COFs) are advanced materials to tackle challenges of catalysis and separation in industrial processes. Their synthetic routes often require elevated temperatures, closed systems with high pressure, and long reaction times, hampering their industrial applications. Here we use a traditionally unperceived strategy to assemble highly crystalline COFs by electron beam irradiation with controlled received dosage, contrasting sharply with the previous observation that radiation damages the crystallinity of solids. Such synthesis by electron beam irradiation can be achieved under ambient conditions within minutes, and the process is amendable for large-scale production. The intense and targeted energy input to the reactants leads to new reaction pathways that favor COF formation in nearly quantitative yield. This strategy is applicable not only to known COFs but also to new series of flexible COFs that are difficult to obtain using traditional methods.

Full-Range Ratiometric Detection of D2O in H2O by a Heterobimetallic Uranyl/Lanthanide Framework with 4f/5f Bimodal Emission.

A uranyl-europium heterobimetallic compound, (TEA)3[(UO2)6Eu(H2O)4(PPA)6] (H3PPA = phosphonoacetic acid, TEA = tetraethylammonium cation), was synthesized under mild hydrothermal conditions. The emission spectrum contains characteristic electronic transition features of both Eu3+ and UO22+, while the peak intensity of Eu3+ is notably higher than that of UO22+. This is primarily attributed to the energy transfer from uranyl to europium in the structure. Significantly, a positive correlation between the Eu3+ peak intensity at 621 nm and the D2O content can be established in the aqueous system, while the uranyl peak intensity is almost unchanged, allowing for the full-range ratiometric detection of D2O in H2O.