Quasi-Homogeneous Photocatalysis in Ultrastiff Microporous Polymer Aerogels.

The development of efficient and low-cost catalysts is essential for photocatalysis; however, the intrinsically low photocatalytic efficiency as well as the difficulty in using and recycling photocatalysts in powder morphology greatly limit their practical performance. Herein, we describe quasi-homogeneous photocatalysis to overcome these two limitations by constructing ultrastiff, hierarchically porous, and photoactive aerogels of conjugated microporous polymers (CMPs). The CMP aerogels exhibit low density but high stiffness beyond 105 m2 s-2, outperforming most low-density materials. Extraordinary stiffness ensures their use as robust scaffolds for scaled photocatalysis and recycling without damage at the macroscopic level. A challenging but desirable reaction for direct deaminative borylation is demonstrated using CMP aerogel-based quasi-homogeneous photocatalysis with gram-scale productivity and record-high efficiency under ambient conditions. Combined terahertz and transient absorption spectroscopic studies unveil the generation of high-mobility free carriers and long-lived excitonic species in the CMP aerogels, underlying the observed superior catalytic performance.

Message From an Automated External Defibrillator.

This case report describes a man in his 80s who received shock from an automated external defibrillator that registered 3 types of tachycardia.

Validation of the Usefulness of the Diameter Reduction, Spiral Shape, Flow Impairment, or Adverse Morphology Classification System in Real-World Clinical Practice.

AIM: The accuracy of the DISFORM (diameter reduction, spiral shape, flow impairment, or adverse morphology) classification system has not been validated. METHODS: This retrospective multicenter observational study enrolled 288 consecutive patients with lower extremity artery disease who underwent endovascular therapy with drug-coated balloons for femoropopliteal lesions between January 2018 and December 2021. Patients were classified into DISFORM I-IV groups. Primary patency (PP) and freedom from clinically driven target lesion revascularization (CD-TLR) at 12 months, and recurrence predictors at 12 months were investigated. RESULTS: In total, 183, 66, 11, and 28 patients were classified into DISFORM I, II, III, and IV groups, respectively. In the DISFORM I, II, III, and IV groups, the PP rates were 75.3%, 91.1%, 87.5%, and 50.0%, respectively, and freedom from CD-TLR rates were 86.0%, 91.6%, 88.9%, and 76.7%, respectively, at 12 months. In the DISFORM I-III and IV groups, the PP rates were 79.4% and 50.0%, respectively, and freedom from CD-TLR rates were 87.5% and 76.7%, respectively, at 12 months. Multivariate analysis showed that chronic limb-threatening ischemia, DISFORM IV, and Lutonix™ use were independent predictors of PP loss at 12 months. CONCLUSION: DISFORM IV had a lower PP rate than DISFORM I-III in midterm phase.

Demonstration of differential ventricular overdrive pacing during long RP' supraventricular tachycardia.

We described the differential ventricular overdrive pacing during long RP' supraventricular tachycardia and discussed about its response leading to the dianosis.

Complete atrioventricular block following internal electrical cardioversion during atrial fibrillation ablation.

BACKGROUND: Complete atrioventricular block (C-AVB) following internal electrical cardioversion (IEC) during atrial fibrillation (AF) ablation has not been fully investigated. We aimed to determine the prevalence and predictors of C-AVB following IEC during AF ablation. METHODS: C-AVB (non-conducted sinus impulse after IEC) and ventricular pause (VP) (the interval between IEC and the QRS complex) following the first attempt of IEC, and baseline electrocardiographic parameters were investigated in patients who underwent first-time AF ablation. RESULTS: We investigated the first attempt of IEC in 124 patients (mean age:70 ± 11 years, 81 men, 99 non-paroxysmal AF). AF was terminated in 109/124 (88%) patients, with a VP of 1590 [1014-2208] (maximum, 8780) ms. Transient C-AVB following IEC occurred in 14/109 (13%) patients. The VP was longer in patients with transient C-AVB than in those without transient C-AVB (2418 [1693-4425] vs. 1530 [876-2083] ms, p = 0.002). In multivariate analysis, the left atrial diameter (Odds ratio [OR]:1.21; 95% confidence interval (95%CI):1.06-1.39; p = 0.005) and preexisting intraventricular conduction abnormality (OR:9.22; 95%CI:1.60-53.3; p = 0.013) were predictors of transient C-AVB following IEC. CONCLUSION: Left atrial diameter and preexisting intraventricular conduction abnormalities were predictors of transient C-AVB following IEC during AF ablation.

Porous supramolecular gels produced by reversible self-gelation of ruthenium-based metal-organic polyhedra.

Supramolecular gels based on metal-organic polyhedra (MOPs) represent a versatile platform to access processable soft materials with controlled porosity. Herein, we report a self-gelation approach that allows the reversible assembly of a novel Ru-based MOP in the form of colloidal gels. The presence of cationic mixed-valence [Ru2(COO)4]+ paddlewheel units allows for modification of the MOP charge via acid/base treatment, and therefore, its solubility. This feature enables control over supramolecular interactions, making it possible to reversibly force MOP aggregation to form nanoparticles, which further assemble to form a colloidal gel network. The gelation process was thoroughly investigated by time-resolved ζ-potential, pH, and dynamic light scattering measurements. This strategy leads to the evolution of hierarchically porous aerogel from individual MOP molecules without using any additional component. Furthermore, we demonstrate that the simplicity of this method can be exploited for the obtention of MOP-based gels through a one-pot synthetic approach starting from MOP precursors.

Predictors of recurrence based on intravascular ultrasound findings after Eluvia placement in symptomatic peripheral arterial disease: A retrospective study.

Background and Aims: Polymer-coated drug-eluting stents (Eluvia) have shown favorable clinical outcomes in real-world registries. There are no reports on recurrent predictors after Eluvia placement based on intravascular ultrasound (IVUS) findings. Methods: We analyzed clinical data from the ASIGARU PAD registry, a retrospective, multicenter, observational study that enrolled patients who underwent endovascular therapy for superficial femoral and proximal popliteal arteries lesions using Eluvia or drug-coated balloon. The primary outcome was the identification of recurrent predictors, including IVUS parameters at 12 months. The rate of target lesion recurrence was also assessed. Results: IVUS images were obtained in 54 of 65 cases. Seven recurrent cases (13.0%) were observed within 12 months. The random survival forest method presented eight predictive variables of recurrence: Clinical Frailty Scale (CFS), distal stent edge area, distal plaque burden, age, sex, distal external elastic membrane (EEM) area, minimum stent area (MSA), and distal lumen area. Furthermore, the partial dependence plot showed that frailty (CFS ≥ 6), smaller distal stent edge area, higher and lower distal plaque burden, older and younger age, female sex, smaller distal EEM area, smaller MSA, and smaller and larger distal lumen area predicted recurrence after Eluvia placement within 12 months. Conclusion: CFS, distal stent edge area, distal plaque burden, age, sex, distal EEM area, MSA, and distal lumen area were significant recurrent predictors after Eluvia placement.

Pore-Networked Gels: Permanently Porous Ionic Liquid Gels with Linked Metal-Organic Polyhedra Networks.

Porous liquids (PLs) are attractive materials because of their capability to combine the intrinsic porosity of microporous solids and the processability of liquids. Most of the studies focus on the synthesis of PLs with not only high porosity but also low viscosity by considering their transportation in industrial plants. However, a gap exists between PLs and solid adsorbents for some practical cases, where the liquid characteristics and mechanical stability without leakage are simultaneously required. Here, we fill in this gap by demonstrating a new concept of pore-networked gels, in which the solvent phase is trapped by molecular networks with accessible porosity. To achieve this, we fabricate a linked metal-organic polyhedra (MOPs) gel, followed by exchanging the solvent phase with a bulky liquid such as ionic liquids (ILs); the dimethylformamide solvent trapped inside the as-synthesized gel is replaced by the target IL, 1-butyl-3-methylimidazolium tetrafluoroborate, which in turn cannot enter MOP pores due to their larger molecular size. The remaining volatile solvents in the MOP cavities can then be removed by thermal activation, endowing the obtained IL gel (Gel_IL) with accessible microporosity. The CO2 capacities of the gels are greatly enhanced compared to the neat IL. The exchange with the IL also exerts a positive influence on the final gel performances such as mechanical properties and low volatility. Besides ILs, various functional liquids are shown to be amenable to this strategy to fabricate pore-networked gels with accessible porosity, demonstrating their potential use in the field of gas adsorption or separation.

Four distinct network patterns of supramolecular/polymer composite hydrogels controlled by formation kinetics and interfiber interactions.

Synthetic composite hydrogels comprising supramolecular fibers and covalent polymers have attracted considerable attention because their properties are similar to biological connective tissues. However, an in-depth analysis of the network structures has not been performed. In this study, we discovered the composite network can be categorized into four distinct patterns regarding morphology and colocalization of the components using in situ, real-time confocal imaging. Time-lapse imaging of the network formation process reveals that the patterns are governed by two factors, the order of the network formation and the interactions between the two different fibers. Additionally, the imaging studies revealed a unique composite hydrogel undergoing dynamic network remodeling on the scale of a hundred micrometers to more than one millimeter. Such dynamic properties allow for fracture-induced artificial patterning of a network three dimensionally. This study introduces a valuable guideline to the design of hierarchical composite soft materials.

Negative and Positive Energetic Elasticity of Polydimethylsiloxane Gels.

We investigated the thermoelasticity of polydimethylsiloxane (PDMS) gels containing six types of solvents with different solubilities. The contribution of energetic elasticity to the total stress (σE/σ) ranges from +0.20 to -0.20 depending on the solvent species. The σE/σ values are positive for the solvents with low molecular mass. By contrast, it is negative for oligodimethylsiloxane (ODMS) or PDMS solvents acting as athermal solvents, each of which has the same chemical structure as the network strands. The investigation using a PDMS rubber without a solvent and the PDMS gels with various ODMS contents reveal a crossover of the σE/σ value from positive to negative with increasing ODMS content. The pronounced dependence of σE/σ on the solvent species and the negative energetic elasticity specific to the high contents of ODMS and PDMS unveil previously unknown aspects of thermoelasticity of polymer gels. The orientation coupling between the segments of the free polymeric chains and network strands is one of the possible scenarios to explain the negative energetic elasticity specific to the ODMS and PDMS solvents, because it stabilizes the aligned state, reducing the elastic energy.

Revisiting exit block after entrance block: Investigation of ablation index-guided pulmonary vein isolation.

INTRODUCTION: Unidirectional block, left atrium to pulmonary vein (LA-PV) entrance block without PV-LA exit block, has not been fully investigated in the setting of ablation index (AI)-guided pulmonary vein (PV) isolation (PVI). The aim of this study was to investigate unidirectional blocks during AI-guided PVI. METHODS: After achieving entrance block, exit block was evaluated by pacing from the catheter placed in the PV. Local PV musculature capture without conduction to the LA was necessary to prove exit block. RESULTS: In total, 441 PVs (including nine left common PVs) from 113 consecutive patients (mean age: 71 ± 12 years, 77 men, 61 paroxysmal atrial fibrillation cases) who underwent initial AI-guided PVI for atrial fibrillation were studied. Entrance block was achieved in all PVs. of the 247/441 (56%) PVs showing local PV musculature capture, 5/247 (2.0%) showed unidirectional blocks. Three of the five PVs (left superior and inferior PVs in one patient; right superior PV in another patient) showed LA-PV reconnection, requiring additional ablation to achieve bidirectional block during the procedure. Two of the five PVs (left superior and inferior PVs in one patient) showed LA-PV reconnection, and thereafter, LA-PV conduction became blocked again spontaneously, leading to bidirectional block without further ablation during the procedure. CONCLUSION: AI-guided PVI presented a low prevalence of unidirectional block (2%), using entrance block alone as the endpoint of PVI could therefore be justified.

Atrial activation sequence changes during ventricular overdrive pacing: What is the mechanism?

We describe atrial activation sequence changes during ventricular overdrive pacing in a patient with a concealed left-sided accessory pathway and discuss its potential mechanism.

True Brugada syndrome ECG or Brugada phenocopy ECG? Can the ECG itself tell us the diagnosis?

We described a type 1 Brugada electrocardiogram and discussed about the potential diagnostic electrocardiographic indicators to differentiate true Brugada syndrome and Brugada phenocopy.

Time-strain inseparability in multiaxial stress relaxation of supramolecular gels formed via host-guest interactions.

Supramolecular hydrogels utilizing host-guest interactions (HG gels) exhibit large deformability and pronounced viscoelasticity. The inclusion complexes between ß-cyclodextrin (host) and adamantane (guest) units on the water-soluble polymers form transient bonds. The HG gels show significant stress relaxation with finite equilibrium stress following the step strain. The stress relaxation process reflects the detachment dynamics of the transient bonds which sustain the initial stress, while the finite equilibrium stress is preserved by the permanent topological cross-links with a rotaxane structure. Nonlinear stress relaxation experiments in biaxial stretching with various combinations of two orthogonal strains unambiguously reveal that time and strain effects on stress are not separable. The relaxation is accelerated for a short time frame (<102 s) with an increase in the magnitude of strain, whereas it is retarded for a longer time window with an increase in the anisotropy of the imposed biaxial strain. The time-strain inseparability in the HG gels is in contrast to the simple nonlinear viscoelasticity of a dual cross-link gel with covalent and transient cross-links in which the separability was previously validated by the same assessment. We currently interpret that the significant susceptibility of the detachment dynamics to the deformation type results from the structural characteristics of the HG gels, i.e., the host and guest moieties covalently connected to the network chains, the considerably low concentrations (<0.1 M) of these moieties, and the slidability of the permanent rotaxane cross-links.

Marked Sensitivity of Ultimate Elongation to Loading Axiality in Polyrotaxane Gels with Largely Slidable Cross Links.

Polyrotaxane (PR) gels with low ring densities have figure-of-eight cross links that can slide along network strands. The slidable cross links have a unique ability to increase the network strand length between adjacent cross links in the loading direction via chain supply from the stress-free direction, thereby enhancing the ultimate elongation (λm) of the gels. We reveal that this enhancement of λm due to the slidable cross links is pronounced specifically in uniaxial stretching, while it is considerably modest in biaxial stretching. The sensitivity of λm to loading axiality becomes larger as the ring densities decrease. The corresponding difference in λm is markedly larger for the PR gels with low ring densities than that for the networks with fixed cross links. The exceptional sensitivity of λm to loading axiality unveils a previously unidentified aspect of the chain-supply mechanism based on slidable cross links.

Control of Extrinsic Porosities in Linked Metal-Organic Polyhedra Gels by Imparting Coordination-Driven Self-Assembly with Electrostatic Repulsion.

The linkage of metal-organic polyhedra (MOPs) to synthesize porous soft materials is one of the promising strategies to combine processability with permanent porosity. Compared to the defined internal cavity of MOPs, it is still difficult to control the extrinsic porosities generated between crosslinked MOPs because of their random arrangements in the networks. Herein, we report a method to form linked MOP gels with controllable extrinsic porosities by introducing negative charges on the surface of MOPs that facilitates electrostatic repulsion between them. A hydrophilic rhodium-based cuboctahedral MOP (OHRhMOP) with 24 hydroxyl groups on its outer periphery can be controllably deprotonated to impart the MOP with tunable electrostatic repulsion in solution. This electrostatic repulsion between MOPs stabilizes the kinetically trapped state, in which an MOP is coordinated with various bisimidazole linkers in a monodentate fashion at a controllable linker/MOP ratio. Heating of the kinetically trapped molecules leads to the formation of gels with similar colloidal networks but different extrinsic porosities. This strategy allows us to design the molecular-level networks and the resulting porosities even in the amorphous state.

Hypercrosslinked Polymer Gels as a Synthetic Hybridization Platform for Designing Versatile Molecular Separators.

Hypercrosslinked polymers (HCPs), amorphous microporous three-dimensional networks based on covalent linkage of organic building blocks, are a promising class of materials due to their high surface area and easy functionalization; however, this type of material lacks processability due to its network rigidity based on covalent crosslinking. Indeed, the development of strategies to improve its solution processability for broader applications remains challenging. Although HCPs have similar three-dimensionally crosslinked networks to polymer gels, HCPs usually do not form gels but insoluble powders. Herein, we report the synthesis of HCP gels from a thermally induced polymerization of a tetrahedral monomer, which undergoes consecutive solubilization, covalent bond formation, colloidal formation, followed by their aggregation and percolation to yield a hierarchically porous network. The resulting gels feature concentration-dependent hierarchical porosities and mechanical stiffness. Furthermore, these HCP gels can be used as a platform to achieve molecular-level hybridization with a two-dimensional polymer during the HCP gel formation. This method provides functional gels and corresponding aerogels with the enhancement of porosities and mechanical stiffness. Used in column- and membrane-based molecular separation systems, the hybrid gels exhibited a separation of water contaminants with the efficiency of 97.9 and 98.6% for methylene blue and KMnO4, respectively. This result demonstrated the potentials of the HCP gels and their hybrid derivatives in separation systems requiring macroscopic scaffolds with hierarchical porosity.

Electrocardiographic features of paradoxical ventriculophasic response.

BACKGROUND: Paradoxical ventriculophasic response (P-VR), a rare entity, has not been fully investigated. This study sought to compare the electrocardiographic features of P-VR and typical ventriculophasic response (T-VR). METHODS: The 12­lead electrocardiogram (ECG) data recorded before implantation of a cardiac implantable electronic device were analyzed in patients with greater than second-degree atrioventricular block (AVB). P-VR or T-VR was defined as present if the PP interval interposing a QRS complex was prolonged or shortened, respectively, by >3% compared with the preceding PP interval without a QRS complex when a QRS complex occurred within a span of 60% of the preceding PP interval. RESULTS: Of 95 patients (age 80 ± 9 years; 49 men) with heart block, 1868 instances (an instance was defined as a set of PP intervals without a QRS complex and the subsequent PP interval interposing a QRS complex) from 214 ECGs were analyzed: 894 instances from 122 ECGs in 64 patients with complete AVB (cAVB) and 974 instances from 92 ECGs in 43 patients with 2:1 AVB (12 showed both cAVB and 2:1 AVB). P-VR was observed in 48 patients (51%). The position of the interposed QRS complex relative to the preceding PP interval was earlier in P-VR than in T-VR. The PP interval was shorter in P-VR than in T-VR. CONCLUSION: P-VR was present in >50% of patients and was affected by the position of the interposed QRS complex and the PP interval.