Effective detoxification of chemical warfare agents is a global necessity. As a powerful photosensitizer, a halogenated BODIPY ligand is postsynthetically appended to the Zr6 nodes of the ...metal–organic framework (MOF), NU-1000, to enhance singlet oxygen generation from the MOF. The BODIPY/MOF material is then used as a heterogeneous photocatalyst to produce singlet oxygen under green LED irradiation. The singlet oxygen selectively detoxifies the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), to the less toxic sulfoxide derivative (2-chloroethyl ethyl sulfoxide, CEESO) with a half-life of approximately 2 min.
Metal–organic frameworks (MOFs) are promising candidates for the catalytic hydrolysis of nerve agents and their simulants. Though highly efficient, bulk water and volatile bases are often required ...for hydrolysis with these MOF catalysts, preventing real-world implementation. Herein we report a generalizable and scalable approach for integrating MOFs and non-volatile polymeric bases onto textile fibers for nerve agent hydrolysis. Notably, the composite material showed similar reactivity under ambient conditions compared to the powder material in aqueous alkaline solution. This represents a critical step toward a unified strategy for nerve agent hydrolysis in practical settings, which can significantly reduce the dimensions of filters and increase the efficiency of protective suits.
Amino‐functionalized zirconium‐based metal‐organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non‐functionalized analogues for hydrolysis of organophosphonate‐based ...toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO‐66‐NH2, where the amino groups reside near the node, compared to UiO‐67‐m‐NH2, where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate‐based nerve agents. The generality of the observed amine‐proximity‐dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr6‐node active site and therefore increase the overall catalytic rates.
Proximity De‐pendant: The role of amino groups on the hydrolysis of a nerve agent simulant, DMNP, has been explored. Experiments and theoretical calculations reveal that not only the presence but also the proximity of the amino group is important for effective chemical detoxification of DMNP. NU‐1002‐o‐NH2, a Zr‐based mesoporous metal–organic framework (MOF) with pendant amines demonstratest1/2 of 1.2 min with only 3 mol % catalyst loading.
Engendering electrical conductivity in high-porosity metal-organic frameworks (MOFs) promises to unlock the full potential of MOFs for electrical energy storage, electrocatalysis, or integration of ...MOFs with conventional electronic materials. Here we report that a porous zirconium-node-containing MOF, NU-901, can be rendered electronically conductive by physically encapsulating C
, an excellent electron acceptor, within a fraction (
60%) of the diamond-shaped cavities of the MOF. The cavities are defined by node-connected tetra-phenyl-carboxylated pyrene linkers,
species that are excellent electron donors. The bulk electrical conductivity of the MOF is shown to increase from immeasurably low to 10
S cm
, following fullerene incorporation. The observed conductivity originates from electron donor-acceptor interactions,
charge-transfer interactions - a conclusion that is supported by density functional theory calculations and by the observation of a charge-transfer-derived band in the electronic absorption spectrum of the hybrid material. Notably, the conductive version of the MOF retains substantial nanoscale porosity and continues to display a sizable internal surface area, suggesting potential future applications that capitalize on the ability of the material to sorb molecular species.
Zirconium-based metal–organic frameworks (Zr-MOFs) based on edge-transitive nets such as fcu, spn, she, csq, and ftw with diverse potential applications have been widely reported. Zr-MOFs based on ...the highly connected 6,12-connected alb net, however, remain absent on account of synthetic challenges. Herein we report the ligand-directed reticular syntheses and isoreticular expansion of a series of Zr-MOFs with the edge-transitive alb net from 12-connected hexagonal-prismatic Zr6 nodes and 6-connected trigonal-prismatic linkers, i.e., microporous NU-1600, mesoporous NU-1601, and mesoporous NU-1602. These Zr-MOFs exhibit remarkable activities toward the destruction of a nerve agent (soman) and a nerve agent simulant (DMNP).
Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well‐defined spin structures. Confinement of the ...tetracationic cyclophane (ExBox4+) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g−1 in ExBox•PSS. Efficient intersystem crossing is achieved by combining the spin‐orbit coupling associated to Br heavy atoms in 1,3,5,8‐tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP⊂ExBox4+ supramolecular dyad. The TBP⊂ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed‐electronic states. The lowest triplet state (T1, 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP⊂ExBox4+, for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4, confirming the importance of the newly formed excited‐state manifold in TBP⊂ExBox4+ for the population of the low‐lying T1 state. The high stability, facile preparation, and high performance of the TBP⊂ExBox•PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host–guest chemistry.
A supramolecular photosensitizer with efficient intersystem crossing is achieved by combining the spin‐orbit coupling associated with heavy atoms and the photoinduced electron transfer in a donor–acceptor host–guest dyad. Incorporation of these supramolecular cationic photosensitizers with anionic polymer matrices generates porous nanocomposites with remarkable photocatalytic performances against sulfur mustard simulant.
A ligand incorporating a dithioethenyl moiety is cleaved into fragments which have a lower metal‐ion affinity upon irradiation with low‐energy red/near‐IR light. The cleavage is a result of singlet ...oxygen generation which occurs on excitation of the photosensitizer modules. The method has many tunable factors that could make it a satisfactory caging strategy for metal ions.
Metal ions on demand: Near‐IR irradiation of a designer ligand results in singlet‐oxygen‐mediated fragmentation with the consequent release of metal ions. The modular nature of the “cage” may herald a new class of agents that could supply chemical effectors on demand.
Photodynamic therapy (PDT), especially with the recent advances in photosensitizer (PS) design, has already been established as a noninvasive technique for cancer treatment. Recently, near-IR-based ...absorbing PSs that have a rising potency to implement light-triggered tumor ablation have attracted much attention since near-IR light in the 650–850 nm range penetrates more deeply in tissues. Up to now, numerous nanomaterials tailored to suitable sizes have been studied for effective delivery of PSs. In this study, four different types of Bodipy-based PSs were covalently attached to magnetic resonance imaging (MRI) active, biocompatible, and nontoxic nanocarriers and generation of singlet oxygen capabilities were evaluated. It was demonstrated that these core-shell nanoparticles are promising delivery vehicles of PSs for use in diagnosis and therapy.
Aim:This study aimed to investigate the role of the quick sequential organ failure assessment (qSOFA) score in determining the prognosis of patients with acute pulmonary embolism (PE).Materials and ...Methods:This study included patients aged >18 years who were admitted to the emergency department for complaints of shortness of breath and/or chest pain for 3 years and who were found to have acute PE on computed tomography pulmonary angiography. The qSOFA, pulmonary embolism severity index (PESI), and simplified PESI scores were calculated in patients with acute PE. During follow-up, the in-hospital mortality and requirement of intensive care continuation were determined.Results:In total, 166 patients with acute PE, of which 88 (53%) were female, were included. The mean age of the patients was 67.4±17.3 years, and 26 (15.7%) patients were admitted to the intensive care unit (ICU). The mortality rate was 9% (n=15). The predictive value of qSOFA in predicting in-hospital mortality area under the curve (AUC) 0.907, 95% confidence interval (CI) 0.852-0.946 was similar to that of PESI (AUC: 0.846, 95% CI: 0.782-0.897) and sPESI (AUC: 0.796, 95% CI: 0.726–0.854) (p=0.23 and p=0.16, respectively). While it was superior to PESI (AUC: 0.794, 95% CI: 0.724-0.852) and sPESI (AUC: 0.721, 95% CI: 0.646-0.787) in determining the admission of patients in the ICU (AUC: 0.882, 95% CI: 0.823-0.927) (p=0.04 and p=0.01, respectively). A positive correlation was found between qSOFA and PESI (r=0.49, p=0.001) and sPESI (r=036, p=0.001).Conclusion:In this study, we found that the qSOFA score performed well in predicting in-hospital mortality and ICU admission in patients with acute PE admitted to the emergency department.
While polymers of intrinsic microporosity (PIMs) possess appealing features such as high surface area, good solubility, and tailorable functional groups on the polymer backbone, their ability to ...decompose toxic chemicals has not been explored. Here, an archetypal PIM, PIM-1, has been modified with various nucleophiles and investigated as a reactive, porous, and processable polymer for degradation of a chemical warfare agent (CWA) simulant, dimethyl 4-nitrophenylphosphonate (DMNP). By quantitatively comparing the reactivity of multiple small-molecule nucleophile scaffolds as organophosphate scavengers, we identified potential nucleophiles to incorporate into PIMs. Among the nucleophiles carboxylic acid, amidoxime, and amide, the amidoxime-functionalized PIMs exhibited the most promising performance in detoxifying DMNP. Modified PIMs showed permanent porosity, which is crucial for accessing the reactive groups residing in the pores. With this study, we provide new insight into PIMs as a reactive material for the decontamination of CWAs with their potential use in protective gear such as suits and masks.
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