Organosulfur and Organoselenium Functionalized Benzimidazo[1,2-a]quinolines: From Experimental and Theoretical Photophysics to All-Solution-Processed OLEDs.

In this study, we present the synthesis of benzimidazo[1,2-a] quinoline-based heterocycles bearing organosulfur and organoselenium moieties through transition-metal-free cascade reactions involving a sequential intermolecular aromatic nucleophilic substitution (SNAr). Both sulfur and selenium derivatives presented absorption maxima located around 355 nm related to spin and symmetry allowing electronic 1π-π* transitions, and fluorescence emission at the violet-blue region (~440 nm) with relatively large Stokes shift. The fluorescence quantum yields were slightly influenced by the chalcogen, with the sulfur derivatives presenting higher values than the selenium analogs. In this sense, the quantum yields for selenium derivatives can probably be affected by the intersystem crossing or even the photoinduced electron transfer process (PET). The compounds were successfully applied in all-solution-processed organic light-emitting diodes (OLEDs), where poly(9-vinylcarbazole) was employed as a dispersive matrix generating single-layer device cells. The obtained electroluminescence spectra are a sum of benzimidazo[1,2-a]quinolines and PVK singlet and/or triplet emissive states, according to their respective energy band gaps. The best diode rendered a luminance of 25.4 cd⋅m-2 with CIE (0.17, 0.14) and current efficiency of 20.2 mcd⋅A-1, a fivefold improvement in comparison to the PVK device that was explained by a 50-fold increase of charge-carriers electrical mobility.

All-Solution Processed Single-Layer WOLEDs Using [Pt(salicylidenes)] as Guests in a PFO Matrix.

Herein, we report the synthesis and characterization of two Pt(II) coordination compounds, the new platinum(II)[N,N'-bis(salicylidene)-3,4-diaminobenzophenone)] ([Pt(sal-3,4-ben)]) and the already well-known platinum(II)[N,N'-bis(salicylidene)-o-phenylenediamine] ([Pt(salophen)]), along with their application as guests in a poly [9,9-dioctylfluorenyl-2,7-diyl] (PFO) conjugated polymer in all-solution processed single-layer white organic light-emitting diodes. Completely different performances were achieved: 2.2% and 15.3% of external quantum efficiencies; 2.8 cd A-1 and 12.1 cd A-1 of current efficiencies; and 3103 cd m-2 and 6224 cd m-2 of luminance for the [Pt(salophen)] and [Pt(sal-3,4-ben)] complexes, respectively. The Commission Internationale de l'Eclairage (CIE 1931) chromaticity color coordinates are (0.33, 0.33) for both 0.1% mol/mol Pt(II):PFO composites at between approximately 3.2 and 8 V. The optoelectronic properties of doped and neat PFO films have been investigated, using steady-state and time-resolved photoluminescence. Theoretical calculations at the level of relativistic density functional theory explained these results, based on the presence of the Pt(II) central ion's phosphorescence emission, considering spin-orbit coupling relationships. The overall results are explained, taking into account the active layer morphological properties, along with the device's electric balance and the emitter's efficiencies, according to deep-trap space-charge models. Considering the very simple structure of the device and the ease of synthesis of such compounds, the developed framework can offer a good trade-off for solution-deposited white organic light-emitting diodes (WOLEDs), with further applications in the field of lighting and signage.

A live attenuated vaccine confers superior mucosal and systemic immunity to SARS-CoV-2 variants

Vaccines are a cornerstone in COVID-19 pandemic management. Here, we compare immune responses to and preclinical efficacy of the mRNA vaccine BNT162b2, an adenovirus-vectored spike vaccine, and the live-attenuated-virus vaccine candidate sCPD9 after single and double vaccination in Syrian hamsters. All regimens containing sCPD9 showed superior efficacy. The robust immunity elicited by sCPD9 was evident in a wide range of immune parameters after challenge with heterologous SARS-CoV-2 including rapid viral clearance, reduced tissue damage, fast differentiation of pre-plasmablasts, strong systemic and mucosal humoral responses, and rapid recall of memory T cells from lung tissue. Our results demonstrate that use of live-attenuated vaccines may offer advantages over available COVID-19 vaccines, specifically when applied as booster, and may provide a solution for containment of the COVID-19 pandemic.

Enhancing the phosphorescence decay pathway of Cu(I) emitters - the role of copper-iodide moiety.

Speeding up the phosphorescence channel in luminescent copper(I) complexes has been extremely challenging due to the copper atoms relatively low spin-orbit coupling constant compared to heavier metals such as iridium. Here, we report the synthesis and characterization of three mononuclear copper(I) complexes with diimines, triphenylphosphine, and iodide ligands to evaluate the effect of the copper-iodide (Cu-I) moiety into the phosphorescence decay pathway. Temperature-dependent photophysical studies revealed combined thermally activated delayed fluorescence and phosphorescence emission, with a phosphorescence decay rate of the order of 104 s-1. Density functional theory calculations indicate very high spin-orbit coupling matrix elements between the low-lying states of these complexes. Compared to the classical [Cu(phen)(POP)]+, our results demonstrate that Cu-I is a versatile moiety to speed up the phosphorescence decay pathway in about one order of magnitude, and it can be prepared by a simplified synthetic route with few synthetic steps. Furthermore, the SOC matrix elements and the phosphorescence decay rates of these complexes are comparable to those of extensively applied coordination complexes based on heavier metals, making them a promising alternative as active layers of organic light-emitting diodes.

Insights into standards of care: dexamethasone and antibodies against COVID-19 in hamster models

RationaleIn face of the ongoing SARS-CoV-2 pandemic, effective and well-understood treatment options are still scarce. While vaccines have proven instrumental in fighting SARS-CoV-2, their efficacy is challenged by vaccine hesitancy, novel variants and short-lasting immunity. Therefore, understanding and optimization of therapeutic options remains essential. ObjectivesWe aimed at generating a deeper understanding on how currently used drugs, specifically dexamethasone and anti-SARS-CoV-2 antibodies, affect SARS-CoV-2 infection and host responses. Possible synergistic effects of both substances are investigated to evaluate combinatorial treatments. MethodsBy using two COVID-19 hamster models, pulmonary immune responses were analyzed to characterize effects of treatment with either dexamethasone, anti-SARS-CoV-2 spike monoclonal antibody or a combination of both. scRNA sequencing was employed to reveal transcriptional response to treatment on a single cell level. Measurements and main resultsDexamethasone treatment resulted in similar or increased viral loads compared to controls. Anti-SARS-CoV-2 antibody treatment alone or combined with dexamethasone successfully reduced pulmonary viral burden. Dexamethasone exhibited strong anti-inflammatory effects and prevented fulminant disease in a severe COVID-19-like disease model. Combination therapy showed additive benefits with both anti-viral and anti-inflammatory potency. Bulk and single-cell transcriptomic analyses confirmed dampened inflammatory cell recruitment into lungs upon dexamethasone treatment and identified a candidate subpopulation of neutrophils specifically responsive to dexamethasone. ConclusionsOur analyses i) confirm the anti-inflammatory properties and indicate possible modes of action for dexamethasone, ii) validate anti-viral effects of anti-SARS-CoV-2 antibody treatment, and iii) reveal synergistic effects of a combination therapy and can thus inform more effective COVID-19 therapies.

De Novo Whole Genome Assembly of the Roborovski Dwarf Hamster (Phodopus roborovskii) Genome, an Animal Model for Severe/Critical COVID-19

The Roborovski dwarf hamster Phodopus roborovskii belongs to the Phodopus genus, one of seven within Cricetinae subfamily. Like other rodents such as mice, rats or ferrets, hamsters can be important animal models for a range of diseases. Whereas the Syrian hamster from the genus Mesocricetus is now widely used as a model for mild to moderate COVID-19, Roborovski dwarf hamster show a severe to lethal course of disease upon infection with the novel human coronavirus SARS-CoV-2.

Evaluation of the acidic strengths on electronic ground and excited states of proton transfer dye using Excitation-Emission fluorescence matrix (EEM) and Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS).

Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) was for the first time successfully used to evaluate an intricate photophysical behavior, where deprotonation on the electronic ground state (S0), intra and intermolecular proton transfer processes (ESPT and ESIPT) on the electronic excited state (S1) can simultaneously be presented. In this sense, the organic dye 2-(2'-hydroxyphenyl)benzothiazole (HBT) was used as a proof-of-concept model, where MCR-ALS showed to be a powerful tool for discriminate chemical reactions that occur concomitantly on different potential energy surfaces, which include photochemical reactions. As a result, the chemometric method showed to be a straightforward approach for the determination of the acidic strengths of those equilibria were estimated as 8.61 and 1.11 to hydroxyl deprotonation on electronic ground and excited states, respectively.

A new interpretation of the mechanism of wormlike micelle formation involving a cationic surfactant and salicylate.

HYPOTHESIS: When tetradecyltrimethylammonium bromide, TTAB, is added to aqueous solution of sodium salicylate, NaSal, the threading of the aromatic anion into the micellar palisade leads to the formation of wormlike micelles. Based on the calorimetric titration of NaSal with TTAB, and on the lifetime of fluorescence of salicylate, we propose that the aggregation of the two components directly leads to the formation of wormlike micelles, without any pre-aggregation. EXPERIMENTS: By using an isothermal titration calorimeter, aliquots of TTAB were added to a dilute solution of NaSal. The energy involved in each addition was then integrated and the variation of enthalpy was determined. In the same range of concentrations and molar ratios, the surface tensiometry and time-resolved emission spectroscopy experiments were performed. FINDINGS: A very characteristic calorimetric signal associated with wormlike micelle formation was obtained, being the enthalpy variation of this process, ΔWLMH2980 < 0. When 1.2 mmol L-1 of NaSal is titrated with 11.0 mmol L-1 of TTAB at 298.15 K, ΔfH2980 = -10.31 kJ per mol of injectant. By adding TTAB to NaSal solution, two fluorescence lifetimes of salicylate were observed solely after wormlike micelle being formed. The correspondent lifetime values of 4.0 ns and 7.2 ns are respectively associated with the free and associated species of salicylate. The new results demonstrated that wormlike micelles are the first aggregate formed when TTAB is added to salicylate. This aspect is relevant for understanding the mechanism of wormlike micelles formation.

White-light generation from all-solution-processed OLEDs using a benzothiazole-salophen derivative reactive to the ESIPT process.

A salicylidene derivative, N,N'-bis(salicylidene)-(2-(3',4'-diaminophenyl)benzothiazole) (BTS), reactive in the Excited State Intramolecular Proton Transfer (ESIPT) process, was synthesized and its photophysical properties were evaluated, presenting an emission covering the entire range of the visible spectrum. Due to its broad emission band, BTS was successfully tested as an active layer in solution-processed organic light-emitting diodes with white-light emission. These diodes were prepared using solution-based protocols with the dye solubilized in a poly(9-vinylcarbazole) matrix. Different guest : host (polymer : BTS) molar ratios were used to optimize the diode performance. The optimized architecture rendered the best so far all-solution-processed ESIPT OLED with a luminance of 34 cd m-2 at 13.5 V with CIE coordinates 0.31, 0.40.

Photoacidity as a tool to rationalize excited state intramolecular proton transfer reactivity in flavonols.

This work presents the determination of acidic strengths at the electronic ground and excited states (pKa and ) of three flavonol derivatives using electronic absorption and fluorescence emission spectroscopy. The differences of the pKa and values were successfully correlated with the molecular structures according to the substitution pattern at the flavonol structure (hydrogen, diethylamino or fluoro moieties). In order to obtain more information about the observed photoacidity of these superacids, geometry optimizations and excitation energy calculations were performed at the CAM-B3LYP/6-311++G(d,p) level for their neutral, protonated and deprotonated species.