Rapid initiation of nasal saline irrigation to reduce severity in high-risk COVID+ outpatients.

OBJECTIVE: To determine whether initiating saline nasal irrigation after COVID-19 diagnosis reduces hospitalization and death in high-risk outpatients compared with observational controls, and if irrigant composition impacts severity. METHODS: Participants 55 and older were enrolled within 24 hours of a + PCR COVID-19 test between September 24 and December 21, 2020. Among 826 screened, 79 participants were enrolled and randomly assigned to add 2.5 mL povidone-iodine 10% or 2.5 mL sodium bicarbonate to 240 mL of isotonic nasal irrigation twice daily for 14 days. The primary outcome was hospitalization or death from COVID-19 within 28 days of enrollment by daily self-report confirmed with phone calls and hospital records, compared to the CDC Surveillance Dataset covering the same time. Secondary outcomes compared symptom resolution by irrigant additive. RESULTS: Seventy-nine high-risk participants were enrolled (mean [SD] age, 64 [8] years; 36 [46%] women; 71% Non-Hispanic White), with mean BMI 30.3. Analyzed by intention-to-treat, by day 28, COVID-19 symptoms resulted in one ED visit and no hospitalizations in 42 irrigating with alkalinization, one hospitalization of 37 in the povidone-iodine group, (1.27%) and no deaths. Of nearly three million CDC cases, 9.47% were known to be hospitalized, with an additional 1.5% mortality in those without hospitalization data. Age, sex, and percentage with pre-existing conditions did not significantly differ by exact binomial test from the CDC dataset, while reported race and hospitalization rate did. The total risk of hospitalization or death (11%) was 8.57 times that of enrolled nasal irrigation participants (SE = 2.74; P = .006). Sixty-two participants completed daily surveys (78%), averaging 1.8 irrigations/day. Eleven reported irrigation-related complaints and four discontinued use. Symptom resolution was more likely for those reporting twice daily irrigation (X2 = 8.728, P = .0031) regardless of additive. CONCLUSION: SARS-CoV-2+ participants initiating nasal irrigation were over 8 times less likely to be hospitalized than the national rate.

Effect of axially projected oligothiophene pendants and nitro-functionalized diimine ligands on the lowest excited state in cationic Ir(III) bis-cyclometalates.

The novel terthiophene (3T) oligomer 6 and a series of cationic Ir(III) bis-cyclometalates [Ir(C^N)(2)(N^N)]PF(6) 9-12 were prepared. The synthesis, characterization, electrochemical, and photophysical properties are reported. The cyclometalating ligands (C^N) are 2-phenylpyridinato (ppy) or the 3T oligomer (3T-ppy), asymmetrically capped in the 5 and 5" positions with the ppy and mesityl groups. The diimine ligands (N^N) are 2,2'-bipyridine (bpy) or 4-NO(2)-bipyridine (4-NO(2)-bpy). Hybrid metal-organic complexes 11 and 12 bear 3T-pendants ligated through the ppy cap, 10 and 12 contain NO(2) functionalized diimines, whereas 9 contains neither. Structural characterization of 10 by single crystal X-ray diffraction confirms the presence of the NO(2) substituent and pseudo-octahedral coordination geometry about the Ir(III) ion. Cyclic voltammetry highlights the large electron withdrawing effect of the NO(2) substituent, providing an 850 mV shift toward lower potentials for the first diimine centered reduction of 10 and 12. Strong overlap of the intense π → π* absorptions of the 3T-pendants with Ir(III) charge transfer bands is evident in complexes of 11 and 12, precluding the possibility for selective excitation of either chromophore. Photoexcitation (λ(ex) = 400 nm) of the series affords strong luminescence from the 3T oligomer 6 and the unsubstituted 9, with φ(em) = 0.11. In stark contrast the NO(2) and 3T functionalized complexes 10-12 display near total quenching of luminescence. Computations of the ground and excited state electronic structure using density functional theory (DFT) and time-dependent DFT (TD-DFT) indicate that both the NO(2) and 3T substituents play an important role in excited state deactivation of complexes 10-12. A substantial electronic contribution of the NO(2) substituent results in stabilization of the diimine based molecular orbital (MO) and offers an efficient nonradiative decay pathway for the excited state. Spin-orbit coupling effects of the Ir(III) ion lead to efficient population of the low lying, nonluminescent, triplet states centered on the 3T-pendants.

Optical response of a cyclometalated iridium(III) hydrazino complex to carbon dioxide: generation of a strongly luminescent iridium(III) carbazate.

A system pairing the luminescent core of [Ir(ppy)(2)L(2)](+) (ppy = 2-phenylpyridine) with simple hydrazino ancillary ligands (L = N(2)H(4)) has been prepared for the direct optical detection of carbon dioxide (CO(2)). Silver-assisted and silver-free techniques were used for the successful introduction of N(2)H(4) into the [Ir(ppy)(2)Cl](2) coordination sphere at room temperature to give the corresponding biscyclometalated iridium(III) hydrazino species as either a CF(3)SO(3)(-) (OTf(-), 2a) or Cl(-) (2b) salt. The silver-free route was accomplished by the direct replacement of the ligated Cl(-) using a slight excess of hydrazine. The luminescence profile of the cationic iridium(III) hydrazino complex 2a (λ(max) = 501 nm) undergoes a red shift (λ(max) = 524 nm), accompanied by a change in the peak shape during exposure to CO(2) in solution. The spectral changes observed are attributed to the formation of the corresponding neutral carbazate species Ir(ppy)(2)(H(2)NNHCOO) (3) and are not consistent with protonation of the ligated hydrazine. Conversion of the hydrazino species to the carbazate species is solvent-dependent and irreversible. The hydrazino and carbazate species have been structurally characterized by single-crystal X-ray diffraction; both compounds exhibit long-lived and intense room temperature luminescence in solution with τ = 1.56 and 1.80 µs and φ(em) = 0.42 and 0.45, respectively.