Global neonatal perioperative mortality: A systematic review and meta-analysis.

STUDY OBJECTIVE: There are large differences in health care among countries. A higher perioperative mortality rate (POMR) in neonates than in older children and adults has been recognized worldwide. The aim of this study was to provide a systematic review of published 24-h and 30-day POMRs in neonates from 2011 to 2022 in countries with different Human Development Index (HDI) levels. DESIGN AND SETTING: A systematic review with a meta-analysis of studies that reported 24-h and 30-day POMRs in neonates was performed. We searched the databases from January 2011 to July 30, 2022. MEASUREMENTS: The POMRs (per 10,000 procedures under anesthesia) were analyzed according to country HDI. The HDI levels ranged from 0 to 1, representing the lowest and highest levels, respectively (very-high-HDI: ≥ 0.800, high-HDI: 0.700-0.799, medium-HDI: 0.550-0.699, and low-HDI: < 0.550). The magnitude of the POMRs by country HDI was studied using meta-analysis. MAIN RESULTS: Eighteen studies from 45 countries were included. The 24-h (n = 96 deaths) and 30-day (n = 459 deaths) POMRs were analyzed from 33,729 anesthetic procedures. The odds ratios (ORs) of the 24-h POMR in low-HDI countries were higher than those in very-high- (OR 8.4, 95% CI 1.7-40.4; p = 0.008), high- (OR 7.3, 95% CI 2.2-24.4; p = 0.001) and medium-HDI countries (OR 7.7, 95% CI 3.1-18.7; p < 0.0001) but with no odds differences between very-high- and high-HDI countries (p = 0.879), very-high- and medium-HDI countries (p = 0.915) and high- and medium-HDI countries (p = 0.689). The odds of a 30-day POMR in low-HDI countries were higher than those in very-high-HDI countries (OR 6.9, 95% CI 1.9-24.6; p = 0.002) but not in high-HDI countries (OR 1.4, 95% CI 0.6-3.0; p = 0.396). CONCLUSIONS: The review demonstrated very high global POMRs in a surgical population of neonates independent of the country HDI level. We identified differences in 24-h and 30-day POMRs between low-HDI countries and other countries with higher HDI levels.

Efficient blue-phosphorescent trans-bis(acyclic diaminocarbene) platinum(ii) acetylide complexes.

The lack of efficient and robust deep-blue phosphorescent metal complexes remains a significant challenge in the context of electroluminescent color displays. The emissive triplet states of blue phosphors are deactivated by low-lying metal-centered (3MC) states, which can be ameliorated by increasing the σ-donating ability of the supporting ligands. Here we unveil a synthetic strategy to access blue-phosphorescent complexes with two supporting acyclic diaminocarbenes (ADCs), known to be even stronger σ-donors than N-heterocyclic carbenes (NHCs). This new class of platinum complexes has excellent photoluminescence quantum yields, with four of six complexes affording deep-blue emission. Experimental and computational analyses are consistent with a pronounced destabilization of the 3MC states by the ADCs.

Ecology and natural infection of phlebotomine sand flies in different ecotopes and environments in the municipality of Pains, Minas Gerais, Brazil.

Phlebotomines (Diptera: Psychodidae) are vectors of protozoa of the genus Leishmania and distributed throughout Brazil, formerly restricted to rural areas, have expanded including to periurban and urban regions, been recorded in different habitats. This study aimed to understand the dynamics of sand flies in different ecotopes in the municipality of Pains. Sand flies were captured during thirty samplings using HP light traps installed in seven different ecotopes for two consecutive nights, once a month, from August 2018 to July 2019. A total of 1,352 sand flies were captured, representing 24 species belong to ten genera. Evandromyia edwardsi was the most abundant species, followed by Evandromyia lenti and Micropygomyia quinquefer. Leishmania DNA was detected in seven female sand flies in four ecotopes, for an infection rate of 0.9%. Sand flies were collected in all seven ecotopes, although forest (23.04%), cave (20.88%) and pasture (17.75%) had higher abundance and richness. Similarity was found among ecotopes, indicating that they are all important for the maintenance of the sand fly community. Spatial analysis indicated high densities of sand flies in areas with natural characteristics. All ecotopes in the municipality were evidenced to have an adequate and harmonious epidemiological profile for the transmission and expansion of leishmaniasis throughout the territory. Because of the increasing environmental changes and deforestation in the municipality, the risk of generating ecological imbalance and increased cases of leishmaniasis is imminent, which highlights the importance of developing preventive and control strategies.

Sand fly bioecological aspects and risk mapping of leishmaniasis by geographical information systems approach in a mineral exploration area of Brazil.

Epidemiological studies of leishmaniasis in areas of great human influence and environmental change serve as important tools for the implementation of effective control plans. Mining is currently a major economic activity in Brazil with the municipality of Pains, in the state of Minas Gerais, being one of the main lime producing municipalities in the country. This study aimed to map areas of potential transmission risks within the municipality of Pains using an epidemiological approach in association with the ecological study of sand flies. Twelve samplings carried out between May 2015 and April 2016 collected a total of 12,728 sandflies, comprising 2,854 females (22.42%) and 9,874 males (77.58%), of 20 species belonging to ten genera. The most abundant species was Lutzomyia longipalpis (80%). Leishmania DNA was detected in seven pools of female sand flies with an infection rate of 0.37%. Geoprocessing and the use of maps revealed that vector sand flies are distributed throughout the urban area, as are cases of canine and human leishmaniasis. However, the greatest abundances of sand flies were at sampling points at the border of the urban area. Higher densities of sand flies and the presence of Leishmania DNA may be correlated with extensive degradation by limestone mining. Integrated and multidisciplinary research approaches are necessary to better understand how the impacts of environmental change influence these insect vectors of leishmaniasis.

Platinum(II)-Substituted Phenylacetylide Complexes Supported by Acyclic Diaminocarbene Ligands.

We introduce phosphorescent platinum aryl acetylide complexes supported by tert-butyl-isocyanide and strongly σ-donating acyclic diaminocarbene (ADC) ligands. The precursor complexes cis-[Pt(CNtBu)2(C≡CAr)2] (4a-4f) are treated with diethylamine, which undergoes nucleophilic addition with one of the isocyanides to form the cis-[Pt(CNtBu)(ADC)(C≡CAr)2] complexes (5a-5f). The new compounds incorporate either electron-donating groups (4-OMe and 4-NMe2) or electron-withdrawing groups [3,5-(OMe)2, 3,5-(CF3)2, 4-CN, and 4-NO2] on the aryl acetylide. Experimental HOMO-LUMO gaps, estimated from cyclic voltammetry, span the range of 2.68-3.61 eV and are in most cases smaller than the unsubstituted parent complex, as corroborated by DFT. In the ADC complexes, peak photoluminescence wavelengths span the range of 428 nm (2a, unsubstituted phenylacetylide) to 525 nm (5f, 4-NO2-substituted), with the substituents inducing a red shift in all cases. The phosphorescence E0,0 values and electrochemical HOMO-LUMO gaps are loosely correlated, showing that both can be reduced by either electron-donating or electron-withdrawing substituents on the aryl acetylides. The photoluminescence quantum yields in the ADC complexes are between 0.044 and 0.31 and the lifetimes are between 4.8 and 14 µs, a factor of 1.8-10× higher (for ΦPL) and 1.2-3.6× longer (for τ) than the respective isocyanide precursor (ΦPL = 0.014-0.12, τ = 2.8-8.2 µs).

Stereoelectronic interactions: A booster for 4 JHF transmission.

Long-range proton-fluorine coupling constants (n JHF ) are helpful for the structure elucidation of fluorinated molecules. However, their magnitude and sign can change with the relative position of coupled nuclei and the presence of substituents. Here, trans-4-tert-butyl-2-fluorocyclohexanone was used as a model compound for the study of the transmission of 4 JHF . In this compound, the 4 JH6axF was measured to be +5.1 Hz, which is five times larger than the remaining 4 JHF in the same molecule (4 JH4F = +1.0 Hz and 4 JH6eqF = +1.0 Hz). Through a combination of experimental data, natural bond orbital (NBO) and natural J-coupling (NJC) analyses, we observed that stereoelectronic interactions involving the π system of the carbonyl group are involved in the transmission pathway for the 4 JH6axF . Interactions containing the π system as an electron acceptor (e.g., σC6H6ax → π*C═O and σCF → π*C═O ) increase the value of the 4 JH6axF , while the interaction of the π system as an electron donor (e.g., πC═O → σ*CF ) decreases it. Additionally, the carbonyl group was shown not to be part of the transmission pathway of the diequatorial 4 JH6eqF coupling in cis-4-tert-butyl-2-fluorocyclohexanone, revealing that there is a crucial symmetry requirement that must be fulfilled for the π system to influence the value of the 4 JHF in these systems.

Selective Nuclear Magnetic Resonance Experiments for Sign-Sensitive Determination of Heteronuclear Couplings: Expanding the Analysis of Crude Reaction Mixtures.

State-of-the-art nuclear magnetic resonance (NMR) selective experiments are capable of directly analyzing crude reaction mixtures. A new experiment named HD-HAPPY-FESTA yields ultrahigh-resolution total correlation subspectra, which are suitable for sign-sensitive determination of heteronuclear couplings, as demonstrated here by measuring the sign and magnitude for proton-fluorine couplings (JHF) from major and minor isomer products of a two-step reaction without any purification. Proton-fluorine couplings ranging from 51.5 to -2.6 Hz could be measured using HD-HAPPY-FESTA, with the smallest measured magnitude of 0.8 Hz. Experimental JHF values were used to identify the two fluoroketone intermediates and the four fluoroalcohol products. Results were rationalized and compared with the density functional theory (DFT) calculations. Experimental data were further compared with the couplings reported in the literature, where pure samples were analyzed.