Reversible Reduction Research Articles

The Diagnosis and Treatment of Hypertrophic Cardiomyopathy.

Hypertrophic cardiomyopathy (HCM) with or without left ventricular outflow tract (LVOT) obstruction is a common primary myocardial disease, with a prevalence of 1:500. It is characterized by thickening of the myocardium. Its diagnostic evaluation includes history-taking and physical examination, genetic studies, transthoracic echocardiography, and cardiac MRI. When optimally treated, it carries a mortality of less than 1% per year. This review is based on pertinent publications retrieved by a selective literature search, including the current guidelines. In symptomatic patients with high LVOT gradients (≥ 50 mm Hg), the treatment of first choice is pharmacotherapy with non-vasodilating beta-blockers or non-dihydropyridine-type calcium channel antagonists. Common side effects include bradycardia and hypotension, and there is a risk of AV nodal blockade. Both substance classes lower the LVOT gradient. Beta-blockers alleviate dyspnea and improve patients' quality of life. Verapamil can increase physical resilience. A further option is mavacamten, a myosin inhibitor that gained approval in Germany in mid-2023: it, too, lowers the LVOT gradient and improves quality of life. In 7-10% of patients, there is a reversible reduction of the left ventricular ejection fraction to less than 50%. Septal reduction treatments can be considered if drug therapy fails. Attention must also be paid to the management of sequelae such as atrial fibrillation, malignant arrhythmias, and mitral valve insufficiency. Patients with HCM have a near-normal life expectancy if the disease is diagnosed early and treated according to the guidelines. The treatment of HCM and HOCM (hypertrophic obstructive cardiomyopathy) have been studied in no more than a few clinical trials, and randomized studies with clinical endpoints are needed.

Unusually high selectivity (100 %) of photocatalytic C[sbnd]C coupling achieved by instant reverse reduction of byproducts

The photocatalytic CC coupling of benzyl alcohol (BA) into hydrobenzoin (HB), is appealing to obtain high-value chemicals. However, the selectivity of HB is still low due to the inevitable formation of benzaldehyde. Herein, we report In(OH)3-ZnS photocatalyst for CC coupling of BA into HB with very high selectivity (∼100 %). The introduction of In(OH)3 onto ZnS with stable interaction facilitates light harvesting and separation of photo-excited charges. As a result, BA conversion on optimized In(0.1)-ZnS catalyst (73 %) is much higher than ZnS (29 %). Besides, the surface hydroxyl groups derived from In(OH)3 enables the facile desorption of CH(OH)Ph radical. Therefore, the over oxidation of CH(OH)Ph radical into by-product of benzaldehyde can be effectively inhibited. More significantly, in-situ FTIR spectra and reduction of by-product manifest the instant reverse reduction process of benzaldehyde into CH(OH)Ph radical during CC coupling of BA, which is the key to realizing satisfied HB selectivity (100 %). Theoretical simulations reveal that the weak adsorption of CH(OH)Ph radical over catalyst and the high energy barrier of over-oxidation of CH(OH)Ph into benzaldehyde contributes to the formation of highly selective coupling products. This work will inspire new insights to design rational photoredox systems for organic transformations with high selectivity

Electron-Deficient Indenofluorene-Based Systems: Multicolor and Visible-To-Near-Infrared (NIR) Electrochromism and OFF-OFF-ON Electrofluorochromism.

Multifunctional electrochromic systems with divergent functions are highly sought after but rare and challenging to develop. Here, we report the synthesis and multi-functional electrochromic behaviour (multi-colour modulation, visible-to-near IR absorption switching, and electrofluorochromism) of electron-deficient indenofluorene-based systems. The compounds (IF1-IF5) have been obtained via Knoevenagel condensation of indenofluorenone (IFK) with various nucleophiles (malononitrile, benzylcyanide, dimethyl malonate, methyl cyanoacetate, benzothiazole-2-acetonitrile). IF1-IF5 possess strong colours and absorb in the visible region (λmax=295-388 nm). These compounds are electroactive and exhibit two reversible reduction waves (-0.35--0.88 V and -0.65--1.30 V vs Ag/AgCl), generating radical anion and dianion systems. For the electrochromic studies, upon applying the one-electron reduction potential (-0.35 V vs Ag/AgCl), the absorption maximum of IF1 redshift from 382 nm to 1240 nm (IF1 -⋅), which subsequently blueshifts to 466 & 745 nm (IF1 2-⋅) upon increasing to two-electron reduction potential (-0.65 V vs Ag/AgCl). The color of the solution was switched from green to dark blue and further to light orange. The electrochromic behaviour is highly reversible and cycling. In addition, unlike the non-fluorescent (IF1 and IF1 -⋅), the two-electron reduced system (IF1 2-⋅) is red-emissive (λem=630 nm) due to the combination of radicals leading to the formation of antiaromatic quinoidal π-conjugated system (IF1 2-).

Personalized Adjunctive Hemoperfusion Therapy for Refractory Septic Shock Caused by Vibrio Cholerae in Thalassemia Patient

This case report describes a patient with Beta-thalassemia/hemoglobin E that developed Vibrio cholerae septicemia, leading to refractory septic shock with a maximum norepinephrine equivalent dose of 1.84 µg/kg/min and multi-organ failure. As the patient remained in refractory shock despite receiving proper antibiotics and organ support for 48 hours, adjunctive therapy including, HA330 hemoperfusion, was initiated. Shock reversal and significant reduction of inflammatory cytokines were achieved after two intervention sessions. The patient was discharged home, despite an initial predicted mortality rate of 85% based on Acute Physiology and Chronic Health Evaluation II (APACHE II).

Impact of Legacy Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) on GABA Receptor-Mediated Currents in Neuron-Like Neuroblastoma Cells: Insights into Neurotoxic Mechanisms and Health Implications.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are persistent environmental pollutants, raising concerns due to their widespread presence and disruptive biological effects. These compounds are highly stable, allowing them to bioaccumulate in the environment and living organisms, potentially impacting critical physiological functions such as hormonal balance, immune response, and increasing cancer risk. Despite regulatory restrictions, their pervasive nature necessitates further research into their potential effects on cellular and neuronal function. This study first evaluated the cytotoxic effects of PFOS and PFOA on S1 neuroblastoma cells; a dose-dependent reduction in cell viability was revealed for PFOS, while PFOA exhibited minimal toxicity until millimolar concentrations. We further investigated their potential to modulate GABAergic neurotransmission using patch-clamp electrophysiology. Both PFOS and PFOA caused a significant but reversible reduction in GABA receptor-mediated currents following one-minute pre-treatment. These findings suggest that PFOS and PFOA can interfere with both cellular viability and GABAergic signaling, providing critical insights into their functional impacts and highlighting the need for further investigation into the long-term consequences of PFAS exposure on nervous system health.

Long-term safety and efficacy of mavacamten in obstructive hypertrophic cardiomyopathy: up to 3.5-year follow-up results of the EXPLORER cohort of MAVA-Long-Term Extension study

Abstract Introduction Mavacamten safety and efficacy in patients with obstructive hypertrophic cardiomyopathy (HCM) was demonstrated in the phase 3 EXPLORER-HCM trial. Long-term safety and efficacy of mavacamten in patients with obstructive HCM is being studied in the MAVA-Long-Term Extension (LTE) study (NCT03723655). Purpose To present long-term safety and efficacy data from the EXPLORER cohort of MAVA-LTE up to week 180 (data cutoff: August 31, 2023). Methods Patients who completed EXPLORER-HCM could enroll in MAVA-LTE following washout. All patients received mavacamten 5 mg at baseline; dose titration to 2.5, 10, or 15 mg was based on site-read echocardiographic evaluation of Valsalva left ventricular outflow tract (LVOT) gradient and left ventricular ejection fraction (LVEF). Following titration, patients were assessed at 12-week intervals between weeks 24 to 156; week 180 was the first visit following a 24-week interval. Results At the data cutoff, 211 of 231 patients who enrolled in MAVA-LTE were on treatment; 185 and 99 patients had reached week 156 and 180, respectively (median [interquartile range (IQR)] time on study: 166 [160–189] weeks; total exposure: 739 patient-years). Sustained improvements from baseline to weeks 156 and 180 were observed in mean (standard deviation [SD]) resting LVOT gradient (−40.2 [32.8] mmHg, n=187; and −40.3 [32.7] mmHg, n=94; respectively), Valsalva LVOT gradient (−55.3 [37.3] mmHg, n=184; and −55.3 [33.7] mmHg, n=91) (Figure 1), and median (IQR) N-terminal pro B-type natriuretic peptide levels (−504 [−1160, −143] ng/L, n=179; and −562 [−1162.5, −209] ng/L, n=88). Improvements from baseline to weeks 144 and 180 were sustained in mean (SD) left atrial volume index (−3.5 [10.4] mL/m2, n=193; and −5.5 [9.7] mL/m2, n=62; respectively). At week 156 and 180, 53.5% and 66.3% of patients, respectively, were in New York Heart Association class I. Mean (SD) LVEF decreased from baseline to week 180 (−11.0% [8.9%]; n=93) but the mean (63.9%) remained within normal range. Overall, 33 patients (14.3%) experienced atrial fibrillation, 14 patients (6.1%) experienced cardiac failure episodes, 13 patients (5.6%) permanently discontinued treatment owing to adverse events and 20 patients (8.7%) experienced transient reductions in LVEF < 50% (range: 30–48%), of whom 6 (2.6%) experienced LVEF < 40% (Figure 2). Of these 20 patients (13 from the placebo group in EXPLORER-HCM), all recovered LVEF ≥ 50% following treatment interruption and 14 reinitiated medication. In total, 5 patients died during the study (all deaths unrelated to mavacamten). Conclusions Long-term mavacamten treatment in patients with obstructive HCM resulted in sustained improvements in echocardiographic measures, symptoms, and biomarkers. Treatment was well-tolerated; no new safety signals were observed. Transient and reversible reductions in LVEF were observed in a small proportion of patients during long-term therapy.

Glaser-Hay-Coupled Random Copolymers Containing Boron Difluoride Formazanate Dyes.

𝜋-Conjugated polymers, including those based on acetylenic repeating units, are an exciting class of materials that offer narrow optical band gaps and tunable frontier orbital energies that lead to their use in organic electronics. This work expands the knowledge of structure-property relationships of acetylenic polymers through the synthesis and characterization of a series of Glaser-Hay-coupled model compounds and random copolymers comprised of BF2 formazanate, fluorene, and/or bis(alkoxy)benzene units. The model compounds and copolymers synthesized exhibit redox activity associated with the reversible reduction of the BF2 formazanate units and the irreversible reduction of the fluorene and bis(alkoxy)benzene units. The copolymers exhibit absorption profiles characteristic or intermediate of their respective models and homopolymers, leading to broad absorption of UV-vis light. The alkyne linkages of the model compounds and copolymers are reacted with [Co2(CO)8] to convert the alkyne functional groups into cobalt carbonyl clusters. This transformation leads to blue-shifted absorption profiles due to a decrease in π-conjugation, demonstrating the ability to tune the properties of these materials through post-polymerization functionalization. The redox activity and broad absorption bands of the polymers reported make them excellent candidates for use in photovoltaics and other light-harvesting applications.

Differential diagnosis of optic neuritis and anterior ischemic optic neuropathy

Background. Acute anterior ischemic neuropathy and optic neuritis are among the most common diseases that are the most frequent cause of both reversible and persistent visual acuity reduction. There is a sudden loss of vision, the clinical picture is often similar, and the restoration of visual functions and the prevention of complications in the form of optic nerve atrophy and disease relapses depend on a correct diagnosis and timely prescribed therapy. A significant level of medico-social and economic losses for society in all regions of the world is related to complications, namely the occurrence of optic nerve atrophy due to both optic nerve inflammation (neuritis) and ischemic optic neuropathy. The purpose was to determine the differential signs of optic neuritis and anterior ischemic optic neuropathy. Materials and methods. Eighty-five patients were examined, 52 (61.2 %) women and 33 (38.8 %) men. Seventy-one (83.5 %) participants were employed. The patients were divided into two groups: the first one — 38 patients with optic neuritis (papillitis); the second one — 47 people with ischemic optic neuropathy. General ophthalmological examinations were carried out. Results. Computed perimetry showed the presence of scotoma and quadrantanopia, both in anterior optic neuropathy (typical altitudinal scotomas) and optic neuritis (peripheral and central scotomas). The difference in the indicators of the electrical activity of the visual analyzer according to phosphene between the groups was 15.8 % (p < 0.05), which indicates a more significant increase in the functional activity of the visual analyzer in the group with anterior optic vascular neuropathy. Thinning of the peripapillar nerve fiber layer and partial atrophy of the optic nerve were noted 2 times less often in patients with anterior vascular ischemic neuropathy — 7 (16.3 %) vs. 14 (33.3 %) in those with partial atrophy of the optic nerve (Pearson’s χ2 = 22.59, p = 0.00001). Conclusions. The issue of early differential diagnosis of anterior optic ischemic neuropathy and optic neuritis is relevant, which determines the prognosis of the disease, allows increasing the effectiveness of treatment and preventing irreversible consequences. The therapeutic effect of treating the consequences of damage to the optic nerve is not stable and is weak, and success is not always achieved. First of all, the treatment of the underlying disease is indicated. Computed perimetry showed the presence of scotoma and quadrantanopia in both anterior optic neuropathy (typical altitudinal scotomas) and optic neuritis (peripheral and central scotomas).

Soft X-ray spectromicroscopic proof of a reversible oxidation/reduction of microbial biofilm structures using a novel microfluidic in situ electrochemical device

In situ electrochemistry on micron and submicron-sized individual particles and thin layers is a valuable, emerging tool for process understanding and optimization in a variety of scientific and technological fields such as material science, process technology, analytical chemistry, and environmental sciences. Electrochemical characterization and manipulation coupled with soft X-ray spectromicroscopy helps identify, quantify, and optimize processes in complex systems such as those with high heterogeneity in the spatial and/or temporal domain. Here we present a novel platform optimized for in situ electrochemistry with variable liquid electrolyte flow in soft X-ray scanning transmission X-ray microscopes (STXM). With four channels for fluid control and a modular design, it is suited for a wealth of experimental conditions. We demonstrate its capabilities by proving the reversible oxidation and reduction of individual microbial biofilm structures formed by microaerophilic Fe(II)-oxidizing bacteria, also known as twisted stalks. We show spectromicroscopically the heterogeneity of the redox activity on the submicron scale. Examples are also provided of electrochemical modification of liquid electrolyte species (Fe(II) and Fe(III) cyanides), and in situ studies of electrodeposited copper nanoparticles as CO2 reduction electrocatalysts under reaction conditions.

Synthesis, Structure, and Redox Properties of Nonsymmetric 6-Oxoverdazyls.

Nonsymmetric 6π-electron ("oxidized") 6-oxoverdazyls have been synthesized for the first time. After formal incorporation of a hydrogen atom, the corresponding 7π-electron neutral verdazyl radical is generated. The 7π radical can undergo a further electrochemically reversible reduction to an 8π anion. Both redox processes occur at more moderate potentials than the parent verdazyl, tuning the accessible potential windows of 6π, 7π, and 8π verdazyl species.

Acetazolamide Therapy and Kidney Function in Persons with Nonalbuminuric Diabetes Mellitus Type 1.

Background: Sodium-glucose cotransporter-2 inhibitors (SGLT2i) lower the risk of kidney failure in persons with type 2 diabetes. The presumed mechanism of action is through greater delivery of sodium to the distal tubule, activation of tubuloglomerular feedback which lowers glomerular filtration rate (GFR) and intra-glomerular pressure. SGLT2is are not approved for use in persons with type 1 diabetes due to the risk of diabetic ketoacidosis. Acetazolamide, a proximal tubule diuretic, delivers more sodium to the distal nephron, and may activate tubuloglomerular feedback in a similar way to SGLT2is without a higher risk of diabetic ketoacidosis. The kidney effects and safety of acetazolamide in persons with type 1 diabetes have not been well studied. Methods: We conducted a dose-escalation trial to determine the effects of 3 dosages of oral acetazolamide (62.5mg, 125mg, and 250mg, all twice-daily) in 12 persons with type 1 diabetes. Participants were treated for 2 weeks followed by a 2-week washout before exposure to the next dosage level. Blood and urine chemistries, as well as iohexol measured GFR, were assessed before and after each treatment interval. We aimed to identify a dose that maximized measured GFR reductions while minimizing adverse effects. Results: The mean age was 46±17 years, 100% were White, and 75% were female. The mean measured GFR was 89±18ml/min/1.73m2 at baseline. Acetazolamide reduced measured GFR by 15% (95% CI 9, 21), 14% (95% CI 7, 21), and 15% (95% CI 10, 21) after 2 weeks at the 62.5mg, 125mg, and 250mg twice-daily dosage levels respectively. The measured GFR reduction was fully reversed after each 2-week washout. Serum bicarbonate was reduced by 2.3, 4.2 and 4.4 mEq/L with escalating doses, and no episodes of hypokalemia (< 3.5 mEq/L) were observed. Conclusions: Among persons with type 1 diabetes and preserved kidney function, acetazolamide caused an acute, reversible reduction in measured GFR without effects on glucose metabolism.

Reversible Redox Ligand-Centered Reactivity in 2,6-Bisiminopyridine Aluminum Systems.

We report the synthesis of cationic 2,6-bisiminopyridine organoaluminum complexes, [(BIP)AlR2]+, as stable BArF4- or PF6- salts, and their reversible single-electron reduction into well-defined paramagnetic species, [(BIP·)AlR2]. Four redox couples, [(BIP)AlR2]+/0, have been fully characterized through structural, spectroscopic, electrochemical and computational techniques.

Atomic Insights into the Competitive Edge of Nanosheets Splitting Water.

The oxygen evolution reaction (OER) provides the protons for many electrocatalytic power-to-X processes, such as the production of green hydrogen from water or methanol from CO2. Iridium oxohydroxides (IOHs) are outstanding catalysts for this reaction because they strike a unique balance between activity and stability in acidic electrolytes. Within IOHs, this balance varies with the atomic structure. While amorphous IOHs perform best, they are least stable. The opposite is true for their crystalline counterparts. These rules-of-thumb are used to reduce the loading of scarce IOH catalysts and retain the performance. However, it is not fully understood how activity and stability are related at the atomic level, hampering rational design. Herein, we provide simple design rules (Figure 12) derived from the literature and various IOHs within this study. We chose crystalline IrOOH nanosheets as our lead material because they provide excellent catalyst utilization and a predictable structure. We found that IrOOH signals the chemical stability of crystalline IOHs while surpassing the activity of amorphous IOHs. Their dense bonding network of pyramidal trivalent oxygens (μ3Δ-O) provides structural integrity, while allowing reversible reduction to an electronically gapped state that diminishes the destructive effect of reductive potentials. The reactivity originates from coordinative unsaturated edge sites with radical character, i.e., μ1-O oxyls. By comparing to other IOHs and literature, we generalized our findings and synthesized a set of simple rules that allow prediction of stability and reactivity of IOHs from atomistic models. We hope that these rules will inspire atomic design strategies for future OER catalysts.

A 1,4-benzoquinone with counteracting inductive donor and acceptor substituents

Investigation of a published route to produce 3,5-di- tert-butylphenol, starting from commercial 3,5-di- tert-butylbenzoic acid via 3,5-di- tert-butylanlinium hydrogen sulfate, unexpectedly yielded 2,6-dintitro-3,5-di- tert-butylphenol. Attempts to increase the yield of the latter resulted, instead, in the previously unreported 2,6-dinitro-3,5-di- tert-butylcyclohexa-2,5-dien-1,4-dione. Single-crystal X-ray diffraction structures are reported for the anilinium salt, the nitrated phenol, and the quinone. Voltammetry of the quinone shows two chemically reversible reductions in anhydrous solution and the radical anion produced from the first reduction step has been characterized by electron paramagnetic resonance spectroscopy. This compound fits well to the middle range of electron-poor quinones, indicating that the inductive effects of the tert-butyl and nitro groups counteract each other. This conclusion is also supported by the infrared spectroscopic data where the ν(C=O) and ν(C=C) bands are of very similar energy to those of 2,3,5,6-tetrachloro-1,4-benzoquinone.

Photo- and Electrocatalytic Hydrogen Evolution by Heteroleptic Dirhodium(II,II) Complexes: Role of the Bridging and Diimine Ligands.

A series of heteroleptic Rh2(II,II) complexes, cis-[Rh2(μ-DPhF)2(μ-bncn)2]2+ (1; bncn = benzo[c]cinnoline), cis-[Rh2(μ-DPhF)(μ-OAc)(μ-bncn)2]2+ (2), and cis-[Rh2(μ-OAc)2(μ-bncn)2]2+ (3), is presented, and the excited state and redox properties of each complex was characterized for the photo- and electrocatalytic production of H2. The oxidation potentials shift anodically from 1 to 3, consistent with a highest occupied molecular orbital (HOMO) with significant metal-ligand mixing, Rh2(δ*)/DPhF(π/nb). In contrast, modest differences in the first two bncn-localized reversible reduction potentials were observed in 1 - 3. The lowest energy metal/ligand-to-ligand charge transfer (1ML-LCT) transition, Rh2(δ*)/DPhF(π/nb) → bncn(π*), shifts from 633 nm in 1 to 553 nm in 2, and the metal-to-ligand charge transfer (1MLCT) Rh2(π*) → bncn(π*) absorption in 3 appears at 462 nm in CH3CN. Although the 3ML-LCT excited state of 2 is shorter lived than that of 1, 2.7 ns as compared to 19 ns, respectively, photocatalytic hydrogen generation is observed for the former upon 595 nm irradiation in the presence of 0.1 M TsOH (p-tolylsulfonic acid) and 0.1 M BNAH (1-benzyl-1,4-dihydronicotinamide). The temperature dependence of the 3ML-LCT lifetimes of 1 and 2 shows the presence of a thermally accessible deactivating state. In addition, the singly reduced intermediate, [2]-, is photoactive and able to generate hydrogen in the presence of TsOH. Importantly, the electrocatalytic currents generated by equimolar concentrations of 1 - 3 in CH3CN are nearly identical, consistent with a mechanism of catalysis that is localized on the bncn ligand and does not require a Rh-H hydride intermediate. This finding can be used to develop earth-abundant first-row transition metal complexes for photo- and electrocatalytic H2 production.

Long-term effect of mavacamten in obstructive hypertrophic cardiomyopathy.

Long-term safety and efficacy of mavacamten in patients with obstructive hypertrophic cardiomyopathy (HCM) are unknown. MAVA-LTE (NCT03723655) is an ongoing, 5-year, open-label extension study designed to evaluate the long-term effects of mavacamten. Participants from EXPLORER-HCM (NCT03470545) could enrol in MAVA-LTE upon study completion. At the latest data cut-off, 211 (91.3%) of 231 patients originally enrolled in MAVA-LTE still received mavacamten. Median (range) time on study was 166.1 (6.0-228.1) weeks; 185 (80.1%) and 99 (42.9%) patients had completed the week 156 and 180 visits, respectively. Sustained reductions from baseline to week 180 occurred in left ventricular outflow tract gradients (mean [standard deviation]: resting, -40.3 [32.7] mmHg; Valsalva, -55.3 [33.7] mmHg), NT-proBNP (median [interquartile range]: -562 [-1162.5, -209] ng/L), and EQ-5D-5L score (mean [standard deviation]: 0.09 [0.17]). Mean left ventricular ejection fraction (LVEF) decreased from 73.9% (baseline) to 66.6% (week 24) and 63.9% (week 180). At week 180, 74 (77.9%) of 95 patients improved by at least one New York Heart Association class from baseline. Over 739 patient-years exposure, 20 patients (8.7%; exposure-adjusted incidence: 2.77/100 patient-years) experienced 22 transient reductions in LVEF to <50% resulting in temporary treatment interruption (all recovered LVEF of ≥50%). Five (2.2%) patients died (all considered unrelated to mavacamten). Long-term mavacamten treatment resulted in sustained improvements in cardiac function and symptoms in patients with obstructive HCM, with no new safety concerns identified. Transient, reversible reductions in LVEF were observed in a small proportion of patients during long-term follow-up.

The indenyl effect on d0 organotransition metal complex LMCT luminescence: Synthesis, structural characterization, cyclic voltammetry, spectroscopic studies, and TD-DFT computations on (η5-permethylindenyl)tetrachlorotantalum(V), and comparison to (η5-pentamethylcyclopentadienyl)tetrachlorotantalum(V)

The new organotantalum(V) chloride (η5-permethylindenyl)tetrachlorotantalum, Ind*TaCl4, was prepared by addition of previously-unreported Ind*SnBu3 to TaCl5 in toluene at 70° in 53 % isolated yield. The solid-state four-legged piano-stool structure, consistent with solution multinuclear NMR spectroscopies, demonstrated that tantalum is bonded to all carbons of the five-membered ring of the permethylindenyl ligand, with little deviation in the Ta-C distances. The permethylindenyl ring torsional angles for the three independent molecules in the unit cell vary from 2.46(17)° to 5.10(17)°. The cyclic voltammogram of Ind*TaCl4 in tetrahydrofuran showed one reversible reduction feature at −1.24 V [Ta(V)/Ta(IV)] and one quasi-reversible reduction feature at −1.65 V [Ta(IV)/Ta(III)] vs. Fc/Fc+. The UV/vis LMCT absorption λmax at 593 nm (ε = 2000 M−1 cm−1) in toluene is remarkably red-shifted from that of the known η5-pentamethylcyclopentadienyl analog, luminescent-yellow Cp*TaCl4. TD-DFT calculations were used to explain the comparative UV/vis absorption spectra.

Localized nitride strategy to construct interfacial and electronic modulated WO3/WN nanoparticles for superior lithium-ion storage

The interfacial effect is important for the tungsten trioxide (WO3)-based anode to achieve superior lithium-ion storage performance. Herein, the interfacial effect was constructed by in-situ surface direct nitridation reaction at 600 ℃ for 30 min of the as-synthesis WO3 nanoparticles (WO3/WN). X-ray photoelectron spectroscopy (XPS) analysis confirms evident chemical interaction between WO3 and WN via the interfacial covalent bond (WON). This WO3/WN anode shows a distinct interfacial effect for an efficient interatomic electron migration. Electrochemical kinetic analysis shows enhanced pseudocapacitance contribution. The galvanostatic intermittent titration technique (GITT) result demonstrates improved charge transfer kinetics. Ex-situ X-ray diffraction (XRD) analysis reveals the reversible oxidation and reduction reaction of the WO3/WN anode. The density functional theory (DFT) result shows that the evident interfacial bonding effect can enhance the electrochemical reaction kinetics of the WO3/WN anode. The discharge capacity can reach up to 546.9 mA h g−1 at 0.1 A g−1 after 200 cycles. After 2000 cycles, the capacity retention is approximately 85.97 % at 1.0 A g−1. In addition, the WO3/WN full cell (LiFePO4/C//WO3/WN) demonstrates excellent rate capability and capacity retention ratio. This in-situ surface nitridation strategy is an effective solution for designing an oxide-based anode with good electrochemical performance and beyond.

CB-839 induces reversible dormancy in lung tumor-cells

Glutaminase inhibitors are currently being explored as potential treatments for cancer. This study aimed to elucidate the molecular mechanisms underlying the effects of CB-839 on lung tumor cell lines compared to non-tumor cell lines. Viability assays based on NADPH-dependent dehydrogenases activity, ATP energy production, or mitochondrial reductase activity were used to determine that CB-839 caused significant tumor cell specific inhibition of cellular functions. Clonogenic survival assay revealed a dose dependent reduction in clonogenic survival of various lung tumor cells presenting estimated IC50 values between 10 and 90 nM, while no effect on non-tumor cells was observed. CB-839 led to a 20% reduction in glutaminase (GLS1, a mitochondrial enzyme that catalyzes the conversion of glutamine to glutamate) activity, and a dose-dependent reduced glutamine consumption in tumor cells and had no effect on non-tumor cells. Cell cycle analysis showed the CB-839 did not lead to cell cycle arrest. Apoptosis and necrosis assays revealed an only slight increase in apoptosis in tumor cells. Furthermore, a trypan blue exclusion assay revealed about 40% growth reduction in tumor cells at 0.1–1 μM CB-839 treatment. Surprisingly, treated cells resumed normal growth when re-plated in a drug-free medium, demonstrating reversibility. In hypoxic conditions, CB-839's effect on clonogenic survival was amplified in a dose dependent manner consistent with increased role of GLS1 for energy production under hypoxic conditions. In conclusion, these results suggest CB-839 efficacy is linked to temporary and reversible reduction in glutamine utilization suggesting induction of dormancy.

Combining Solid FePc Immobilized on Py-Functionalized Carbon Matrix with Soluble Redox Mediator FePc As an Efficient Cathode Catalyst for Non-Aqueous Li-O2 Batteries

It is important to develop bifunctional catalysts with high activity and stability for reversible oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) in lithium-oxygen (Li-O2) batteries. Recently, the iron phthalocyanine (FePc) complex has been considered a promising candidate for bifunctional (ORR/OER) O2 catalysts due to its low cost, high catalytic properties, and ease of preparation. In this work, two different structural types of FePc-based solution-phase catalysts as soluble redox mediators (SRMs) and solid FePc immobilized on pyridine-functional carbon supports (multi-walled carbon nanotube, MWCNT and graphene, GR) are investigated to evaluate the influence of FePc structural design on their catalytic activity and kinetics.Our work demonstrated that FePc(solid)/Py/MWCNT exhibited better bifunctional catalytic activity than FePc(solid)/Py/GR in the same electrolyte because of the stronger axial bonding between FePc(solid) and Py/MWCNT. The combination of FePc(solid)/Py/MWCNT and FePc(sol) displays the best cyclability, which can be attributed to the highly efficient solid-liquid interface. Moreover, FePc(solid)/Py/MWCNT without FePc(sol) shows the lowest overpotential owing to the surface-grown thin film Li2O2 is structurally less order than the solution-grown toroidal Li2O2.