Mechanically Enhanced Detoxification of Chemical Warfare Agent Simulants by a Two-Dimensional Piezoresponsive Metal-Organic Framework.

Chemical warfare agents (CWAs) refer to toxic chemical substances used in warfare. Recently, CWAs have been a critical threat for public safety due to their high toxicity. Metal-organic frameworks have exhibited great potential in protecting against CWAs due to their high crystallinity, stable structure, large specific surface area, high porosity, and adjustable structure. However, the metal clusters of most reported MOFs might be highly consumed when applied in CWA hydrolysis. Herein, we fabricated a two-dimensional piezoresponsive UiO-66-F4 and subjected it to CWA simulant dimethyl-4-nitrophenyl phosphate (DMNP) detoxification under sonic conditions. The results show that sonication can effectively enhance the removal performance under optimal conditions; the reaction rate constant k was upgraded 45% by sonication. Moreover, the first-principle calculation revealed that the band gap could be further widened with the application of mechanical stress, which was beneficial for the generation of 1O2, thus further upgrading the detoxification performance toward DMNP. This work demonstrated that mechanical vibration could be introduced to CWA protection, but promising applications are rarely reported.

Starfruit-Shaped Zirconium Metal-Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity.

Invited for the cover of this issue is the group of Cheng-an Tao, Jianfang Wang and co-workers at the University of Defense Technology. The image depicts a novel starfruit-shaped metal-organic framework composed of zirconium and tetra(4-carboxyphenyl)porphine linkers and characterized by 2D nanosheet petals grown through edge-sharing that showcases superior catalytic activity. Read the full text of the article at 10.1002/chem.202302835.

Starfruit-Shaped Zirconium Metal-Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity.

We present the fabrication of a novel Starfruit-shaped metal-organic framework (SMOF) composed of zirconium and Tetra(4-carboxyphenyl)porphine linkers. The SMOF exhibits a unique morphology with edge-sharing two-dimensional (2D) nanosheet petals. Our investigation unravels a captivating transformation process, wherein three-dimensional (3D) shuttle-shaped MOFs form initially and subsequently evolve into 2D nanosheet-based SMOF structures. The distinct morphology of SMOF showcases superior catalytic activity in detoxifying G-type nerve agent and blister agent simulants, surpassing that of its 3D counterparts. This discovery of the 3D-to-2D transition growth pathway unlocks exciting opportunities for exploring novel strategies in advanced MOF nanostructure development, not only for catalysis but also for various other applications.

Humidity Enhances the Solid-Phase Catalytic Ability of a Bulk MOF-808 Metal-Organic Gel toward a Chemical Warfare Agent Simulant.

Zirconium-based metal-organic frameworks have emerged as promising materials for detoxifying chemical warfare agents (CWAs) due to their remarkable stability and porosity. However, their practical application is hindered by issues with their powder form and poor catalytic performance in solid-phase degradation. To address these challenges, herein, a granular MOF-808 metal-organic gel (G808) is prepared under optimized conditions for catalytic degradation of the simulant 2-chloroethyl ethyl sulfide (2-CEES), a sulfide blister agent, in a neat state under different humidity conditions. The detoxification performance of G808 toward 2-CEES is significantly enhanced as the content of water present increases. The half-life of 2-CEES decontaminated by G808 can be shortened to 816 s, surpassing those of many other benchmark materials. To confirm the mechanism of catalytic degradation, we used gas chromatography, gas chromatography-mass spectrometry, and theoretical calculations. The findings revealed that hydrolysis was the predominant route. Additionally, granular G808 was reusable and adaptable to high-moisture environments, making it an excellent protective material with practical potential.

Metal-Organic Framework Gels for Adsorption and Catalytic Detoxification of Chemical Warfare Agents: A Review.

Chemical warfare agents (CWAs) have brought great threats to human life and social stability, and it is critical to investigate protective materials. MOF (metal-organic framework) gels are a class with an extended MOF architecture that are mainly formed using metal-ligand coordination as an effective force to drive gelation, and these gels combine the unique characteristics of MOFs and organic gel materials. They have the advantages of a hierarchically porous structure, a large specific surface area, machinable block structures and rich metal active sites, which inherently meet the requirements for adsorption and catalytic detoxification of CWAs. A series of advances have been made in the adsorption and catalytic detoxification of MOF gels as chemical warfare agents; however, overall, they are still in their infancy. This review briefly introduces the latest advances in MOF gels, including pure MOF gels and MOF composite gels, and discusses the application of MOF gels in the adsorption and catalytic detoxification of CWAs. Meanwhile, the influence of microstructures (pore structures, metal active site, etc.) on the detoxification performance of protective materials is also discussed, which is of great significance in the exploration of high-efficiency protective materials. Finally, the review looks ahead to next priorities. Hopefully, this review can inspire more and more researchers to enrich the performance of MOF gels for applications in chemical protection and other purification and detoxification processes.

An Angle-Independent Multi-Color Display Electro-Responsive Hydrogel Film.

In nature, some organisms have the ability to camouflage to adapt to environmental changes; they blend with the environment by changing their skin colors. Such a phenomenon is of great significance for the research of adaptive camouflage materials. In this study, we propose a novel design scheme for the study of angle-independent photonic materials and successfully prepare an electrically tunable multi-color display angle-independent inverse opal photonic gel (IOPG). After photopolymerization of hydroxyethyl methacrylate with ionizable monomer acrylic acid (AA) in a long-range disordered opal template and etching, the angle-independent inverse opal photonic gel is obtained, presenting a single structural color. The electrically responsive color changes can be achieved at different angles. The color of the disordered AA-IOPG changes from green to blue-green when applying +4 V bias voltage and from green to orange when applying -4 V bias voltage. The electrochromism of the disordered AA-IOPG is mainly due to the local pH change caused by water electrolysis under bias voltage, which leads to a change of the swelling ratio. The disordered AA-IOPG shows high color tunability and durability through repeated opposite bias voltage tests, indicating that it is a promising conductive photonic material.

A portable acetylcholinesterase-based electrochemical sensor for field detection of organophosphorus.

A portable acetylcholinesterase (AChE)-based electrochemical sensor based on a screen-printed carbon electrode (SPCE) and a miniature potentiostat was constructed for the rapid field detection of organophosphorus pesticides (OPs). Graphene (GR) and gold nanoparticles (AuNPs) were successively introduced onto SPCE for surface modification. Due to the synergistic effect of the two nanomaterials, the signal of the sensor has a significant enhancement. Take isocarbophos (ICP) as a model for chemical warfare agents (CAWs) and Ops; the SPCE/GR/AuNPs/AChE/Nafion sensor shows a wider linear range (0.1-2000 µg L-1), and a lower limit of detection (0.012 µg L-1) than SPCE/AChE/Nafion and SPCE/GR/AChE/Nafion sensors. Tests in actual fruit and tap water samples also yielded satisfactory results. Therefore, the proposed method can be used as a simple and cost-effective strategy for construction of portable electrochemical sensors for OP field detection.

Porphyrin-Moiety-Functionalized Metal-Organic Layers Exhibiting Catalytic Capabilities for Detoxifying Nerve Agent and Blister Agent Simulants.

The development of very efficient bifunctional catalysts for the simultaneous detoxification of two kinds of the deadliest chemical warfare agents (CWAs), nerve agent and blister agent, is highly desirable. In this study, two porphyrin-based ligands [tetrakis(4-carboxyphenyl) porphyrin (TCPP) and protoporphyrin IX (PPIX)] are introduced into 2D Zr-1,3,5-tris(4-carboxyphenyl)benzene (BTB) metal-organic layers (MOLs), composed of six-connected Zr6 nodes and the tritopic carboxylate ligand BTB, by a solvent-assisted ligand incorporation method. The loads of TCPP and PPIX are 6.4 and 10.9 wt %, respectively. The detoxification of simulants of the nerve agent and the blister agent was conducted to investigate the catalytic activity of porphyrin-moiety-functionalized MOLs. The reaction half-life of optimal TCPP-functionalized MOL catalyzing the hydrolysis of a nerve agent simulant is only 2.8 min, meanwhile, the half-life of the selective catalytic oxidation of a blister agent simulant is only 1.2 min under LED illumination. More importantly, such a degradation half-life is only about 4 min under natural sunlight (∼60 mW/cm2). To our knowledge, TCPP-functionalized MOL is by far the most efficient catalyst for blister agent simulant degradation under solar light. Therefore, 2D ultrathin MOLs on demand appear to be a promising and efficient material platform for the development of bifunctional catalysts for CWA protection.

Ultrafast Degradation and High Adsorption Capability of a Sulfur Mustard Simulant under Ambient Conditions Using Granular UiO-66-NH2 Metal-Organic Gels.

Zirconium-based metal-organic frameworks (Zr-MOFs) have been considered as prospective materials for the degradation of nerve chemical warfare agents (CWAs) but show poor catalytic performance toward blister agents. Moreover, the powder issues and the poor adsorption capability also remain as the major challenges for the application of Zr-MOFs in practical CWA detoxification. Herein, a series of defected granular UiO-66-NH2 metal-organic gels are synthesized via adjusting the amount of added concentrated hydrochloric acid for the decontamination of 2-chloroethyl ethyl sulfide (2-CEES), a sulfur mustard simulant. The half-life of 2-CEES decontaminated by defected granular UiO-66-NH2 metal-organic gels can be shortened to 7.6 min, which is the highest reported value for MOFs under ambient conditions. The mechanism of decontamination is that the amino group on the linkers in UiO-66-NH2 MOGs undergoes a substitution reaction with 2-CEES to yield 2-(2-(ethylthio)ethylamino)terephthalic acid, which is less toxic and fixed in the frameworks. The recycling test corroborates that the granular UiO-66-NH2 xerogels possess good stability and reusability. Static adsorption and desorption tests show that UiO-66-NH2 xerogels possess a high 2-CEES vapor adsorption capacity of 802 mg/g after exposure for 1 d and only 28 wt % desorption capacity after air exposure for 7 d. The dual function of ultrafast degradation and high adsorption capability provide a firm foundation for using UiO-66-NH2 xerogels as a future protection media.

Aptamer-binding zirconium-based metal-organic framework composites prepared by two conjunction approaches with enhanced bio-sensing for detecting isocarbophos.

A novel label-free and enzyme-free detection strategy has been developed for the electrochemical biosensor detection of isocarbophos (ICP) using UiO-66-NH2 and aptamer as the signal transducers. In this work, the ICP aptamers were attached to UiO-66-NH2 through physical mixing and chemical combination methods. In the presence of ICP, the aptamers could undergo conformational change and bind to them, which prevent the electron transfer to the surface of electrode. By comparing the two conjunction approaches of aptasensors, these proposed strategies could selectively and sensitively detect ICP with a detection limit of 6 ng mL-1 (20.74 nM) and 0.9 ng mL-1 (3.11 nM). Furthermore, we have also demonstrated the capability of this strategy in the detection of ICP in real samples from vegetable and fruit extract, indicating the potential application of this strategy in food safety issues.

Facile Synthesis of Metal-Organic Layers with High Catalytic Performance toward Detoxification of a Chemical Warfare Agent Simulant.

Two-dimensional (2D) metal-organic layer (MOL) materials are highly desired against chemical warfare agents (CWAs). However, the rapid synthesis of 2DMOLs with open metal sites in a single step is very challenging. Herein, a facile bottom-up method for synthesizing MOLs with microwave assistance is applied to produce Zr/Hf-BTB MOLs, composed of six-connected M6O4(OH)412+ and the tritopic carboxylate ligand 1,3,5-tris(4-carboxyphenyl)benzene (BTB). The synthesis and ligand exchange steps can be combined into a single step to yield MOLs with active open sites directly. The as-synthesized MOLs demonstrate excellent catalytic performance toward the degradation of a CWA simulant. The theoretical calculations confirm that the high catalytic activity is due to the formate groups coordinated to the metal nodes being replaced by hydroxyl groups. The present work not only develops a method for the fast synthesis of 2D MOLs with active open metal sites in a single step but also provides a first demonstration for the application of 2D metal coordination materials in CWA protection.

Synthesis of macroscopic monolithic metal-organic gels for ultra-fast destruction of chemical warfare agents.

The potential threat that has originated from chemical warfare agents (CWAs) has promoted the development of advanced materials to enhance the protection of civilian and military personnel. Zr-based metal-organic frameworks (Zr-MOFs) have recently been demonstrated as excellent catalysts for decomposing CWAs, but challenges of integrating the microcrystalline powders of Zr-MOFs into monoliths still remain. Herein, we report hierarchically porous monolithic UiO-66-X xerogels for the destruction of CWAs. We found that the UiO-66-NH2 xerogel with a larger pore size and a higher surface area than the UiO-66-NH2 powder possessed better degradability of 2-chloroethyl ethyl sulfide (2-CEES), which is a sulfur mustard simulant. These UiO-66-X xerogels exhibit outstanding performance for decomposing CWAs. The half-lives of vesicant agent sulfur mustard (HD) and nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) are as short as 14.4 min and 1.5 min, respectively. This work is, to the best of our knowledge, the first report on macroscopic monolithic UiO-66-X xerogels for ultrafast decomposition of CWAs.

Amplified Analysis of DNA or Proteins by TdT-generated DNAzyme.

Sensitive and specific detection of nucleic acids or proteins, which act as biomarkers, is of great importance in disease diagnosis. By combing the concept and operation of an endonuclease-assisted target-responsive amplification method and peroxidase-mimic DNAzyme generated by terminal deoxynucleotidyl transferase (TdT), a novel and facile colorimetric biosensor was developed for DNA and protein. Target DNA and thrombin were chosen as representative biomolecules. The production of cleavage fragments can only be triggered by specific target binding and the following nicking process, which do not occur spontaneously. In the signal collection part, numerous guanine-rich DNA were produced through the prolongation of cleavage fragments by TdT and formed highly effective DNAzyme with hemin. In this novel amplification method, we succeeded in realizing sensitive and specific detection of target DNA and thrombin. Under optimal conditions, target DNA can be detected as low as 1 pM, and thrombin with a detection limit of 100 pM. The method also proves the potential versatility and feasibility of TdT-generated DNAzyme in various bio-analyses.

Layer-by-Layer Fabrication of Core-Shell Fe3O4@UiO-66-NH2 with High Catalytic Reactivity toward the Hydrolysis of Chemical Warfare Agent Simulants.

Detoxifying materials against chemical warfare agents (CWAs) and their simulants are highly desired for proper handling of contamination by and destruction of CWAs. Herein, we report a facile layer-by-layer fabrication of core-shell Fe3O4@UiO-66-NH2 and its application in fast degradation of CWA simulants. The Fe3O4@UiO-66-NH2 composite was prepared through a layer-by-layer epitaxial growth strategy, by alternately immersing Fe3O4 nanoparticles in ethanol solutions of a metal node [Zr6O4(OH)4]12+ precursor and organic linkers [NH2-BDC, 2-aminoterephthalic acid], respectively, and separating using a magnet. As confirmed by characterization results, the Fe3O4@UiO-66-NH2 composites with 24.4 µmol/g Zr6 node content showed a well-defined core-shell structure as well as good thermal and chemical stability. These core-shell magnetic metal-organic frameworks (MOFs) were further tested in the catalytic hydrolysis of dimethyl-4-nitrophenyl phosphate (a nerve agent simulant) and demonstrated 36 times higher catalytic activity than the UiO-66-NH2 powder due to their highly defective surface, high percentage of MOFs on the surface, and their rich mesoporous structure. Since magnetism was retained after the coating of MOFs, Fe3O4@UiO-66-NH2 could be easily recovered and reused after catalysis.

Catalytic MOF-loaded cellulose sponge for rapid degradation of chemical warfare agents simulant.

Various metal-organic frameworks (MOF) are highly effective catalysts for detoxifying chemical warfare agents (CWAs). In this study, we reported a MOF-loaded cellulose sponge for fast degradation of CWAs simulant. In situ growth of UiO-66-NH2 onto γ-Glycidoxypropyltrimethoxysilane (GPTMS) modified cellulose sponge was achieved. This sponge featured high porosity (88%), high specific surface area (310.5 g/m2) and low density (36 mg/cm3). The UiO-66-NH2 functionalized cellulose sponge showed excellent catalytic activity for detoxifying 4-Nitrophenyl Phosphate (DMNP) and the half-life was as short as 9 min.

Construction of a Biosensor Based on a Combination of Cytochrome c, Graphene, and Gold Nanoparticles.

A biosensor based on a combination of cytochrome c (Cyt c), electrochemical reduced graphene oxides (ERGO), and gold nanoparticles (AuNPs) on a glassy carbon electrode (GCE) was fabricated. The proposed biosensor electrode was denoted as GCE/ERGO-Nafion/AuNPs/Cyt c/Nafion, where ERGO-Nafion was deposited by dropping graphene oxides-Nafion mixed droplet first and following electrochemical reduction, AuNPs were directly deposited on the surface of the ERGO-Nafion modified electrode by electrochemical reduction, and other components were deposited by the dropping-dry method. The effect of the deposition amount of AuNPs on direct electrochemistry of Cyt c in the proposed electrode was investigated. The hydrogen peroxide was taken to evaluate the performance of the proposed biosensor. The results showed that the biosensor has great analytical performance, including a high sensitivity, a wide linear range, a low detection limit, and good stability, reproducibility, and reliability.

Ultrafast Synthesis of Ni-MOF in One Minute by Ball Milling.

A mechanical ball milling method for ultrafast synthesis of a nickel-based metal organic framework (Ni-MOF) has been proposed. The Ni-MOF was successfully synthesized in merely one minute without any solvent, additives, or preliminary preparation. The effect of milling time, mechano-frequency, type of assistant liquid, and amount of assistant water were systematically explored. It was found that the product can be obtained even only at a mechano-frequency of 10 Hz within one minute without any external solvent-assist, which indicated that the crystal water present in the nickel precursor was sufficient to promote MOF formation. Increasing the milling time, raising the mechano-frequency, and the addition of assistant solvent could promote the reaction and increase the yield. The method is rapid, highly efficient, eco-friendly, and has great scalability. The product generated within merely one minute even exhibited high capacitance.

Dopamine Assisted One-Step Pyrolysis of Glucose for the Preparation of Porous Carbon with A High Surface Area.

Herein, a facile dopamine assisted one-pot synthesis approach is proposed for the preparation of porous carbon with a specific surface area (SSA) up to 2593 m²/g through the direct pyrolysis of a mixture of glucose, NH4Cl, and dopamine hydrochloride (DAH). The glucose is adopted as the carbon source and foaming agent, NH4Cl is used as the blowing agent, and DAH is served as collaborative carbon precursor as well as the nitrogen source for the first time. The effect of dopamine on the component, structure, and SSA of the as-prepared porous carbon materials are systematically studied. The moderate addition of dopamine, which influences the condensation and polymerization of glucose, matches better with ammonium salt decomposition. The SSA of porous carbon increases first and then decreases with the increasing amount of dopamine. In our case, the porous carbon produced with 5 wt% dopamine (PC-5) achieves the maximum SSA of up to 2593 m²/g. Accordingly, it also shows the greatest electrochemical performance. The PC-5 shows a capacitance of 96.7 F/g calculated from the discharge curve at 1 A/g. It also has a good capacitive rate capacity, the specific capacitance can still maintain 80%, even at a high current density of 10 A/g. Moreover, PC-5 exhibits a good cycling stability of 98.1% capacitive retention after 1000 cycles. The proposed method may show promising prospects for preparing porous carbon materials as advanced energy storage materials, storage, and catalyst supports.

Comparison of Fabrication Methods of Metal-Organic Framework Optical Thin Films.

Homogeneous metal-organic frameworks (MOFs)-based optical thin films have attracted increasing attention, since they can potentially be used as active components in optical/opt-electrical devices, and how to fabricate MOF thin films with high quality is the premise of practically using them. Herein, five fabrication methods of MOF films are systematically investigated and compared from the aspects of appearance, reflectivity, micro-morphology, surface roughness, and optical properties of the films. The famous robust Zr-based MOF, UiO-66 (UiO = University of Oslo) is chosen as a model, and the five methods are spin-coating, dip-coating, self-assembly, direct growth, and the stepwise layer by layer growth method. This study provides fundamental support for the application of MOFs in the optical field.

Preparation of Graphene Oxide-Based Ink for Inkjet Printing.

Fabrication of graphene-based conductive circuits via inkjet printing processes would be very significant, but preparation of graphene inks which can be used in ordinary household inkjet printer is still a challenge. Graphene oxide (GO) is an important graphene derivative with good dispersion properties in water, because it has a lot of oxygen-containing functional groups. In this paper, the relationship between the concentration of GO and the viscosity and surface tension of its dispersion were studied first, GO were prepared by modified Hummers' method. Moreover, the influence of two surfactants-sodium dodecyl sulfate (SDS) and Triton-X100 (TX-100) on viscosity and surface tension of inks were also investigated. It was found that the concentration of GO was 3.9 mg/mL, and the amount of the addition of SDS and TX-100 were 1 mg/mL and 2.5 mg/mL respectively, which can form stable GO-based inks. Finally, the resultant GO-based inks can be printed by home inkjet printer HP-1010 on normal printing paper, flexible polyimide film and thin aluminum foil. It is expected that the development of inkjet printable GO-based inks will decrease the cost of the preparation of graphene electrode/circuits and open up new ways for the application of GO-based thin film and patterns.