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.

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.

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.

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.

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.

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.

Regularly irregular atrial rhythm after superior vena cava isolation: Another manifestation of sinoatrial node injury?

The present case described an unusual clinical manifestation of the sinoatrial node (or sinoatrial junction) injury during superior vena cava isolation.

Validation of the correlation between angiosome-based target arterial path, mid-term limb-based patency, and the global limb anatomical staging system.

This study aimed to validate the correlation between the Global Limb Anatomical Staging System (GLASS) and limb-based patency (LBP) and angiosome-based target arterial path (TAP) and to detect the predictors of LBP loss. After the publication of the Global Vascular Guidelines in 2019, the evaluation of GLASS and identification of TAP have been recommended. However, there are few reports regarding GLASS. Eighty-three patients with chronic limb-threatening ischemia (CLTI) and tissue loss from 2016 to 2020 were evaluated. The correlation between GLASS and LBP and successful revascularization of angiosome-based TAP was analyzed. We also investigated the predictors of LBP loss. The number of patients in each GLASS stage was as follows: GLASS I, 6 patients; GLASS II, 15 patients; GLASS III, 62 patients. At 6 months, the Kaplan-Meier estimate of LBP was 66.7% in GLASS I, 41.6% in GLASS II, and 16.4% in GLASS III, respectively (p = 0.034). The rate of successful revascularization of angiosome-based TAP was 100% in GLASS I, 86.7% in GLASS II, and 46.8% in GLASS III, respectively (p = 0.002). Multivariate analysis showed that the Wound, Ischemia, and foot Infection (WIfI) stage [hazard ratio (HR) 1.58; 95% confidence interval (CI) 1.07-2.33; p = 0.021] and GLASS infrapopliteal (IP) grade (HR 1.96; 95% CI 1.31-2.95; p = 0.001) were the independent predictors of LBP loss. The GLASS stage was significantly correlated with successful revascularization of angiosome-based TAP and mid-term LBP. The WIfI stage and GLASS IP grade were the independent predictors of loss of LBP.

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.

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.

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.

Phototriggered Spatially Controlled Out-of-Equilibrium Patterns of Peptide Nanofibers in a Self-Sorting Double Network Hydrogel.

Out-of-equilibrium patterns arising from diffusion processes are ubiquitous in nature, although they have not been fully exploited for the design of artificial materials. Here, we describe the formation of phototriggered out-of-equilibrium patterns using photoresponsive peptide-based nanofibers in a self-sorting double network hydrogel. Light irradiation using a photomask followed by thermal incubation induced the spatially controlled condensation of peptide nanofibers. According to confocal images and spectroscopic analyses, metastable nanofibers photodecomposed in the irradiated areas, where thermodynamically stable nanofibers reconstituted and condensed with a supply of monomers from the nonirradiated areas. These supramolecular events were regulated by light and diffusion to facilitate the creation of unique out-of-equilibrium patterns, including two lines from a one-line photomask and a line pattern of a protein immobilized in the hydrogel.

Spatiotemporal Control of Supramolecular Polymerization and Gelation of Metal-Organic Polyhedra.

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA) and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption, and 1H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

What is the attributing electrocardiographic phenomenon underlying a concomitant 2:1 and Wenckebach atrio-ventricular block?

We herein describe the case of a spontaneously observed bidirectional block (both entrance and exit block) at the sino-atrial junction. This bidirectional block at the sino-atrial junction associated with the failure of conduction to the ventricle revealed the Wenckebach periodicity of the atrio-ventricular conduction.

GPR91 antagonist and TGF-ß inhibitor suppressed collagen production of high glucose and succinate induced HSC activation.

Activated hepatic stellate cells (HSCs) play a central role in fibrillary collagen production, the primary cause of liver fibrosis. Although it is known that primary cultured HSCs are activated by plastic culture dish stiffness, HSC activation and quiescent-state-reversion mechanisms are still unclear. In this study, we used cultured normal rat HSCs on 3.2 kPa collagen normal liver stiffness equivalent gel, to determine whether high glucose or high succinate conditions induce HSC activation, and examined whether activated HSCs reverted to a quiescent state when suppressed by GPR91 antagonists or TGF-ß1 receptor inhibitors. We measured the gene expression levels of α-SMA and type I collagen HSC activation markers using real-time PCR. Our data indicated that high glucose conditions induced HSC activation, and showed that under continuous high glucose exposure HSC activation progressed. A GPR91 antagonist, 2 d, and a TGF-ß1 receptor inhibitor, SB525334, suppressed the Col1α mRNA expression level of these activated HSCs. Similarly, under extended high succinate exposure, 2 d and SB525334 reduced Col1α mRNA expression levels of activated HSCs. From the above, we determined that even though HSCs had already been activated by high glucose or succinate conditions which persisted after activation, the GPR91 antagonist and the TGF-ß1 receptor inhibitor were able to reduce the production of type I collagen from activated HSCs.

A 2:1 atrioventricular block presenting paradoxical ventriculophasic response.

Ventriculophasic response (VR) is defined as the shortening of the sinus cycle length in the setting of greater than second-degree atrioventricular (AV) block. Typically, the PP intervals interposing a QRS complex are shorter than those without a QRS complex. Paradoxical VR is a rare clinical entity. We report about an 80-year-old man presenting with a 2:1 AV block, in whom typical and paradoxical VRs were observed.

Endogenous Adenosine May Be Related to Left Ventricular Dysfunction, Dilation, and Wall Thinning in Patients With Heart Disease.

BACKGROUND: The role of endogenous adenosine in cardiac patients is still unclear, so we investigated the relationship between the plasma adenosine concentration and left ventricular (LV) function, LV dilation and LV wall thinning in cardiac patients.Methods and Results:In 97 cardiac patients, with angina pectoris, old myocardial infarction, dilated or hypertrophic cardiomyopathy, and valvular heart disease, plasma adenosine concentrations were measured using the LC-MS/MS system, and the LV function, LV end-diastolic dimension (LVDd), LV posterior wall thickness (LVPWth), and interventricular septum thickness (IVSth) were assessed by echocardiography. The plasma adenosine concentration was significantly higher in patients with a LV ejection fraction (EF), an indicator of the LV systolic function, <47% compared with those with LVEF ≥47% (P=0.027). There was no difference between the plasma adenosine concentration and E/e', an indicator of LV diastolic function. The plasma adenosine concentration was significantly higher in patients with LVDd ≥50 mm than in those with LVDd <50 mm (P=0.030). The plasma adenosine concentration was inversely correlated with IVSth (P=0.003) and LVPWth (P=0.0007). The plasma adenosine concentration was significantly higher in patients with IVSth <8 mm than in those with IVSth ≥8 mm (P=0.015), and was significantly higher in patients with LVPWth <8 mm than in those with LVPWth ≥8 mm (P=0.020). CONCLUSIONS: Endogenous adenosine may be related to LV dysfunction, dilation, and wall thinning in cardiac patients.