Enhancing Electrical Conductivity of Semiconducting MOFs via Defect Healing

Electrically conductive metal-organic frameworks (EC-MOFs) have attracted growing interest with their potential uses in various applications such as electrochemical sensing, energy storage, and electrocatalysis. However, their electrical properties are often underestimated due to poor synthetic control, including unavoidable defects that hinder efficient charge transport. Herein, we demonstrate the defect healing on EC-MOFs, utilizing ligands as healing precursors. The results showed enhanced conductivity values up to 700 times higher when Cu3(HAB)2 was treated with hexaaminobenzene (HAB) ligands than the untreated counterpart. Our finding highlights that facile postsynthetic treatment can further improve conductivity of existing EC-MOFs

Tandem Rh(III)-Catalyzed Oxidative Acylation of Secondary Benzamides with Aldehydes and Intramolecular Cyclization: The Direct Synthesis of 3-Hydroxyisoindolin-1-ones

The rhodium-catalyzed oxidative acylation between secondary benzamides and aryl aldehydes via sp² C–H bond activation followed by an intramolecular cyclization is described. This method results in the direct and efficient synthesis of 3-hydroxyisoindolin-1-one building blocks

Structure-Assisted Functional Anchor Implantation in Robust Metal–Organic Frameworks with Ultralarge Pores

A facile functionalization assisted by the structural attributes of PCN-333 has been studied while maintaining the integrity of the parent MOF including ultralarge pores, chemical robustness, and crystallinity. Herein we thoroughly analyzed ligand exchange phenomena in PCN-333 and demonstrate that the extent of exchange can be tailored by varying the exchange conditions as potential applications may require. Through this method a variety of functional groups are incorporated into PCN-333. To further show the capabilities of this system introduction of a BODIPY fluorophore as a secondary functionality was performed to the functionalized framework via a click reaction. We anticipate the PCN-333 with functional anchor can serve as a stable platform for further chemistry to be explored in future applications

Data_Sheet_1_Correlation between temporal muscle thickness and grip strength in hemiplegic patients with acute stroke.PDF

Recently, temporal muscle thickness (TMT) has been investigated as a novel surrogate marker for muscle mass and function in neurologic patients. This study aimed to assess the correlation of TMT with grip strength to establish a new parameter for predicting pre-stroke sarcopenia. A total of 358 patients who were newly diagnosed with acute ischemic stroke at our institution between November 2021 and August 2022 were enrolled. Eighty-four patients met the eligibility criteria. The mean TMT was measured within initial brain MRI using previously described methods. Pearson's correlation analyses assessed the relationship between grip strength and TMT. Multiple logistic regression analyses were performed to identify associations between TMT and other associated factors including grip strength, sarcopenia risk, body mass index, age, Charlson Comorbidity Index and Geriatric nutrition risk index. Mean TMT values indicated a strong correlation with the grip strength of the non-hemiplegic hand in both male and female patients. Multiple logistic regression analyses showed that TMT was associated with grip strength and sarcopenia risk in hemiplegic patients. Measuring TMT using cranial MR images during the initial stages of stroke could help predict a patient's pre-stroke muscle strength status. Further studies are required to apply TMT in pre-stroke sarcopenia diagnosis.</p

Dual Exchange in PCN-333: A Facile Strategy to Chemically Robust Mesoporous Chromium Metal–Organic Framework with Functional Groups

A facile preparation of a mesoporous Cr-MOF, PCN-333­(Cr) with functional group, has been demonstrated through a dual exchange strategy, involving a sequential ligand exchange and metal metathesis process. After optimization of the exchange system, the functionalized PCN-333­(Cr), N₃–PCN-333­(Cr) shows well maintained crystallinity, porosity, as well as much improved chemical stability. Because of the exceptionally large pores (∼5.5 nm) in PCN-333­(Cr), a secondary functional moiety, Zn-TEPP with a size of 18 Å × 18 Å, has been successfully clicked into the framework. In this article, we have also analyzed kinetics and thermodynamics during dual exchange process, showing our attempts to interpret the exchange event in the PCN-333. Our findings not only provide a highly stable mesoporous Cr-MOF platform for expanding MOF-based applications, but also suggest a route to functionalized Cr-MOF which may have not been achievable through conventional approaches

Anionic Ring-Opening Polymerization of a Functional Epoxide Monomer with an Oxazoline Protecting Group for the Synthesis of Polyethers with Carboxylic Acid Pendants

Polymers with carboxylic acid functionalities are widely used in adhesives, absorbents, dispersants, drug delivery systems, and hydrogels. Unlike common radical polymerization, it is difficult to synthesize polymers with carboxylic acid groups via anionic ring-opening polymerization because of the harsh reaction conditions. Although a carboxylic acid-functionalized polyether, poly­(glycidoxy acetic acid), was previously prepared by using monomer-activated ring-opening polymerization, this approach often suffers from a low initiation efficiency and is limited to homopolymerization. Herein, we present a novel functional epoxide monomer bearing oxazoline as a protecting group, 4,4-dimethyl-2-oxazoline glycidyl ether, for a controlled synthesis of poly­(4,4-dimethyl-2-oxazoline glycidyl ether) by overcoming the aforementioned limitations. The stepwise syntheses of the monomer and polymers were carefully analyzed via 1H NMR, GPC, FT-IR spectroscopy, and MALDI-ToF analysis. Furthermore, copolymerization with another monomer and a macroinitiator yielded well-defined polymers. We anticipate that this study will provide a new platform for the synthesis of polyethers with carboxylic acid functional groups

3D Long-Range Triplet Migration in a Water-Stable Metal–Organic Framework for Upconversion-Based Ultralow-Power <i>in Vivo</i> Imaging

Triplet–triplet annihilation upconversion (TTA-UC) has gained increasing attention because it allows for harvesting of low-energy photons in the solar spectrum with high efficiency in relevant applications including solar cells and bioimaging. However, the utilization of conventional TTA-UC systems for low-power bioapplications is significantly hampered by their general incompatibility and low efficiency in aqueous media. Herein we report a metal–organic framework (MOF) as a biocompatible nanoplatform for TTA-UC to realize low-power <i>in vivo</i> imaging. Our MOF consists of a porphyrinic sensitizer in an anthracene-based Zr-MOF as a TTA-UC platform. In particular, closely aligned chromophores in the MOF facilitate a long-range 3D triplet diffusion of 1.6 μm allowing efficient energy migration in water. The tunable ratio between sensitizer and annihilator by our synthetic method also allows an optimization of the system for maximized TTA-UC efficiency in water at a very low excitation power density. Consequently, the low-power imaging of lymph node in a live mouse was successfully demonstrated with an excellent signal-to-noise ratio (SNR > 30 at 5 mW cm^–2)

Logistic regression analysis for IBD flare-up related to international air travel in inflammatory bowel disease patients.

Logistic regression analysis for IBD flare-up related to international air travel in inflammatory bowel disease patients.</p

Threading Subunits for Polymers to Predict the Equilibrium Ensemble of Solid Polymer Electrolytes

We present a computational method for polymer growth called “threading subunits for polymers (TSP)” that can efficiently sample solid polymer electrolyte structures with extended conformations. The TSP method involves equilibrating subunit (e.g., monomer) conformations that form favorable solvation ion shells, followed by consecutively connecting the subunits and minimizing the structures. The TSP method can sample polymers with good solvent-like conformations and from near-equilibrium structures in which ions are well-dispersed, avoiding unusual ion clustering under ambient conditions. Using the TSP method, the equilibration time can be reduced significantly by effectively sampling the polymer conformations near equilibrium. We anticipate that the TSP method can be applied to simulate various polymer electrolytes

Patient characteristics (N = 94).

Patient characteristics (N = 94).</p