NHC-Cu Three-Coordinate Complex as a Promising Photocatalyst for Energy and Electron Transfer Reactions.

Herein, we describe a simple three-coordinate complex of Cu(I) with an NHC and 1,10-phenanthroline ligands as an effective photocatalyst for energy (e.g., olefin E/Z isomerization) and electron transfer (e.g., aryl halide dehalogenation) reactions under blue-light irradiation. This complex can be obtained in a one-pot procedure starting from commercially available reagents and green solvents (EtOH, water). We hereby present a study of its activity and mechanistic insight into its mode of operation.

Unlocking the reactivity of diazo compounds in red light with the use of photochemical tools.

Structurally diversified diazoalkanes can be activated under red light irradiation relying on direct photolysis, photosensitization or photoredox catalysis.

Electrochemical Cycloaddition Reactions of Alkene Radical Cations: A Route toward Cyclopropanes and Cyclobutanes.

Herein, we describe a mild and efficient electrochemical method for cycloaddition reactions of alkene radical cations. Anodic oxidation of olefins produces electrophilic alkene radical cations, which further react with either diazo compounds in a [2 + 1] cycloaddition toward cyclopropane synthesis, or styrene derivatives in a [2 + 2] cycloaddition producing cyclobutanes. Both processes are green, metal- and catalyst-free, and scalable and tolerate a broad range of electron-rich olefins.

Site-Selective, Photocatalytic Vinylogous Amidation of Enones.

Despite the broad interest in organic compounds possessing a γ-aminocarbonyl motif, limited strategies for their synthesis have been reported. Herein, we describe a mild and efficient method for the site-selective amidation of unsaturated enones with electrophilic N-centered radicals as a key intermediate. The photocatalytic vinylogous reaction of dienolates with N-amino pyridinium salts affords γ-amido carbonyl compounds. This process is high-yielding, scalable, and tolerates a broad range of unsaturated α,ß-unsaturated carbonyls, including biologically relevant compounds, as starting materials.

Psychological Interventions and Bariatric Surgery among People with Clinically Severe Obesity-A Systematic Review with Bayesian Meta-Analysis.

AIM: To assess the effectiveness of perioperative psychological interventions provided to patients with clinically severe obesity undergoing bariatric surgery regarding weight loss, BMI, quality of life, and psychosocial health using the Bayesian approach. METHODS: We considered randomised trials that assessed the beneficial and harmful effects of perioperative psychological interventions in people with clinically severe obesity undergoing bariatric surgery. We searched four data sources from inception to 3 October 2021. The authors independently selected studies for inclusion, extracted data, and assessed the risk of bias. We conducted a meta-analysis using a Bayesian approach. PROSPERO: CRD42017077724. RESULTS: Of 13,355 identified records, we included nine studies (published in 27 papers with 1060 participants (365 males; 693 females, 2 people with missing data)). Perioperative psychological interventions may provide little or no benefit for BMI (the last reported follow-up: MD [95% credible intervals] = -0.58 [-1.32, 0.15]; BF01 = 0.65; 7 studies; very low certainty of evidence) and weight loss (the last reported follow-up: MD = -0.50 [-2.21, 0.77]; BF01 = 1.24, 9 studies, very low certainty of evidence). Regarding psychosocial outcomes, the direction of the effect was mainly inconsistent, and the certainty of the evidence was low to very low. CONCLUSIONS: Evidence is anecdotal according to Bayesian factors and uncertain whether perioperative psychological interventions may affect weight-related and psychosocial outcomes in people with clinically severe obesity undergoing bariatric surgery. As the results are ambiguous, we suggest conducting more high-quality studies in the field to estimate the true effect, its direction, and improve confidence in the body of evidence.

Porphyrins as Promising Photocatalysts for Red-Light-Induced Functionalizations of Biomolecules.

Red-light enables deeper material penetration, which is important for biological applications and has consequences for chemical synthesis. Therefore, the search for new photocatalysts that absorb in this region is crucial. Despite the undeniable utility of porphyrins in blue- and green-light-induced energy- and electron-transfer processes, they are also perfectly suited for red-light applications. Herein, we describe free-base porphyrins as photoredox catalysts for red-light-induced organic transformations. They can act as both photooxidants and photoreductants and can accomplish the synthesis of biaryls once merged with Pd-catalysis. The developed methodology holds promise for broader applications, as the heme-based protoporphyrin is used as a photocatalyst and reactions can be realized in aqueous conditions.

Making Nitronaphthalene Fluoresce.

Nitroaromatic compounds are inherently nonfluorescent, and the subpicosecond lifetimes of the singlet excited states of many small nitrated polycyclic aromatic hydrocarbons, such as nitronaphthalenes, render them unfeasible for photosensitizers and photo-oxidants, despite their immensely beneficial reduction potentials. This article reports up to a 7000-fold increase in the singlet-excited-state lifetime of 1-nitronaphthalene upon attaching an amine or an N-amide to the ring lacking the nitro group. Varying the charge-transfer (CT) character of the excited states and the medium polarity balances the decay rates along the radiative and the two nonradiative pathways and can make these nitronaphthalene derivatives fluoresce. The strong electron-donating amine suppresses intersystem crossing (ISC) but accommodates CT pathways of nonradiate deactivation. Conversely, the N-amide does not induce a pronounced CT character but slows down ISC enough to achieve relatively long lifetimes of the singlet excited state. These paradigms are key for the pursuit of electron-deficient (n-type) organic conjugates with promising optical characteristics.

Mutual Arrangements of Coronary Blood Vessels within the Right Atrial Appendage Vestibule.

BACKGROUND: The aim of our study was to investigate the presence and mutual relationships of coronary vessels within the right atrial appendage (RAA) vestibule. METHODS: We examined 200 autopsied hearts. The RAA vestibule was cross-sectioned along its isthmuses (superior, middle, and inferior). RESULTS: The right coronary artery (RCA) was present in 100% of the superior RAA isthmuses but absent in 2.0% of hearts within the middle isthmus and in 6.5% of hearts within the inferior RAA isthmus. Its diameter was quite uniform along the superior (2.6 ± 0.8 mm), middle (2.9 ± 1.1 mm), and inferior (2.7 ± 0.9 mm) isthmuses (p = 0.12). The location of the RCA varied significantly, and it was sometimes accompanied by other accessory coronary vessels. In all the isthmuses, the RCA ran significantly closer to the endocardial surface than to the epicardial surface (p < 0.001). At the superior RAA isthmus, the artery was furthest from the right atrial endocardial surface and this distance gradually decreased between the middle RAA isthmus and the inferior RAA. CONCLUSIONS: This study was the most complex analysis of the mutual arrangements and morphometric characteristics of coronary blood vessels within the RAA vestibule. Awareness of additional blood vessels within the vestibule can help clinicians plan and perform safe and efficacious procedures in this region.

Morphology and Position of the Right Atrioventricular Valve in Relation to Right Atrial Structures.

The right atrioventricular valve (RAV) is an important anatomical structure that prevents blood backflow from the right ventricle to the right atrium. The complex anatomy of the RAV has lowered the success rate of surgical and transcatheter procedures performed within the area. The aim of this study was to describe the morphology of the RAV and determine its spatial position in relation to selected structures of the right atrium. We examined 200 randomly selected human adult hearts. All leaflets and commissures were identified and measured. The position of the RAV was defined. Notably, 3-leaflet configurations were present in 67.0% of cases, whereas 4-leaflet configurations were present in 33.0%. Septal and mural leaflets were both significantly shorter and higher in 4-leaflet than in 3-leaflet RAVs. Significant domination of the muro-septal commissure in 3-leflet valves was noted. The supero-septal commissure was the most stable point within RAV circumference. In 3-leaflet valves, the muro-septal commissure was placed within the cavo-tricuspid isthmus area in 52.2% of cases, followed by the right atrial appendage vestibule region (20.9%). In 4-leaflet RAVs, the infero-septal commissure was located predominantly in the cavo-tricuspid isthmus area and infero-mural commissure was always located within the right atrial appendage vestibule region. The RAV is a highly variable structure. The supero-septal part of the RAV is the least variable component, whereas the infero-mural is the most variable. The number of detected RAV leaflets significantly influences the relative position of individual valve components in relation to right atrial structures.

Microanatomy of the myocardial extensions of the pulmonary valve in light of modern catheter ablation methodology.

INTRODUCTION: The muscular sleeves (or myocardial extensions) derived from the right ventricle infundibulum myocardium are considered the true anatomic substrate for right ventricular outflow tract arrhythmias. METHODS: Pulmonary valve specimens obtained from 65 donors (24.6% females, mean age 45.9 ± 15.8 years) were investigated micro-anatomically. Specimens were histologically processed, stained with Masson's Trichrome, and examined under a light microscope. RESULTS: The myocardial extensions were present in the left anterior pulmonary valve sinus in 86.2% of cases, in the right anterior sinus in 89.2% of cases and in 90.7% of cases in the posterior sinus (p = .699). In 69.2% of examined hearts, the myocardial extensions were present in all sinuses. The mean height of the extensions was 4.12 ± 1.76 (left anterior) versus 3.69 ± 1.47 (right anterior) versus 4.28 ± 1.73 mm (posterior) (p = .137). The myocardial extensions occupied an average of 28.9 ± 10.4% of the left anterior sinus, 26.7 ± 11.2% of the right anterior sinus, and 31.9 ± 11.3% of the posterior sinus (p = .044). Sleeves extending beyond the fibro-arterial transition zone were present in at least one sinus in 33.8% of hearts (in 7.7% (5/65) of the left and right anterior sinuses and 21.5% (14/65) of posterior sinus, p = .021). CONCLUSIONS: The myocardial extensions of the pulmonary valve are common anatomical entities. Although the length of the myocardial sleeves is similar in all pulmonary valve sinuses, their relative extent is greatest in the posterior sinus. Long sleeves that spread beyond the fibro-arterial transition zone were observed in one-third of hearts, predominantly in the posterior sinus. Myocardial and fibrous tissue layer thicknesses varied considerably.

On the Search of a Silver Bullet for the Preparation of Bioinspired Molecular Electrets with Propensity to Transfer Holes at High Potentials.

Biological structure-function relationships offer incomparable paradigms for charge-transfer (CT) science and its implementation in solar-energy engineering, organic electronics, and photonics. Electrets are systems with co-directionally oriented electric dopes with immense importance for CT science, and bioinspired molecular electrets are polyamides of anthranilic-acid derivatives with designs originating from natural biomolecular motifs. This publication focuses on the synthesis of molecular electrets with ether substituents. As important as ether electret residues are for transferring holes under relatively high potentials, the synthesis of their precursors presents formidable challenges. Each residue in the molecular electrets is introduced as its 2-nitrobenzoic acid (NBA) derivative. Hence, robust and scalable synthesis of ether derivatives of NBA is essential for making such hole-transfer molecular electrets. Purdie-Irvine alkylation, using silver oxide, produces with 90% yield the esters of the NBA building block for iso-butyl ether electrets. It warrants additional ester hydrolysis for obtaining the desired NBA precursor. Conversely, Williamson etherification selectively produces the same free-acid ether derivative in one-pot reaction, but a 40% yield. The high yields of Purdie-Irvine alkylation and the selectivity of the Williamson etherification provide important guidelines for synthesizing building blocks for bioinspired molecular electrets and a wide range of other complex ether conjugates.

Correction: Multifaceted aspects of charge transfer.

Correction for 'Multifaceted aspects of charge transfer' by James B. Derr et al., Phys. Chem. Chem. Phys., 2020, 22, 21583-21629, DOI: .

Effect of targeted vs standard fortification of breast milk on growth and development of preterm infants (≤ 32 weeks): study protocol for a randomized controlled trial.

BACKGROUND: Human milk is recommended for all very low birth weight infants. Breastmilk is highly variable in nutrient content, failing to meet the nutritional demands of this group. Fortification of human milk is recommended to prevent extrauterine growth retardation and associated poor neurodevelopmental outcome. However, standard fortification with fixed dose multicomponent fortifier does not account for the variability in milk composition. Targeted fortification is a promising alternative and needs further investigation. METHODS: This randomized controlled trial will recruit preterm infants (≤ 32 weeks of gestation) within the first 7 days of life. After reaching 80 ml/kg/day of enteral feeding, patients will be randomized to receive standard fortification (HMF, Nutricia) or targeted fortification (modular components: Bebilon Bialka, Nutricia-protein; Polycal, Nutricia-carbohydrates; Calogen, Nutricia-lipids). The intervention will continue until 37 weeks of post-conception age or hospital discharge. Parents and outcome assessors will be blinded to the intervention. The primary outcome measure is velocity of weight, length, and head growth until 36 weeks post-conceptional age or discharge. Secondary outcomes include neurodevelopment at 12 months assessed with Bayley Scale of Development III, repeated at 36 months; body composition at discharge and at 4 months; and incidence of necrotizing enterocolitis, sepsis, retinopathy of prematurity, and bronchopulmonary dysplasia. DISCUSSION: Targeted fortification has previously been shown as doable in the neonatal intensive care unit context. If it shows to improve growth and neonatal outcome, choosing the targeted fortification as a first line nutritional approach in very low birth weight infants may become a recommendation. TRIAL REGISTRATION: ClinicalTrials.gov NCT03775785 , Registered on July 2019.

Topographical anatomy of the right atrial appendage vestibule and its isthmuses.

INTRODUCTION: The right atrial appendage (RAA) vestibule is an area located in the right atrium between the RAA orifice and the right atrioventricular valve annulus and may be a target for invasive transcatheter procedures. METHODS AND RESULTS: We examined 200 autopsied human hearts. Three isthmuses (an inferior, a middle, and a superior isthmus) were detected. The average length of the vestibule was 67.4 ± 10.1 mm. Crevices and diverticula were observed within the vestibule in 15.3% of specimens. The isthmuses had varying heights: superior: 14.0 ± 3.4 mm, middle: 11.2 ± 3.1 mm, and inferior: 10.1 ± 2.7 mm (p < .001). The superior isthmus had the thickest atrial wall (at midlevel: 16.7 ± 5.6 mm), the middle isthmus had the second thickest wall (13.5 ± 4.2 mm), and the inferior isthmus had the thinnest wall (9.3 ± 3.0 mm; p < .001). This same pattern was observed when analyzing the thickness of the adipose layer (superior isthmus had a thickness of 15.4 ± 5.6 mm, middle: 11.7 ± 4.1 mm and inferior: 7.1 ± 3.1 mm; p < .001). The average myocardial thickness did not vary between isthmuses (superior isthmus: 1.3 ± 0.5 mm, middle isthmus: 1.8 ± 0.8 mm, inferior isthmus: 1.6 ± 0.5 mm; p > .05). Within each isthmus, there were variations in the thickness of the entire atrial wall and of the adipose layer. These were thickest near the valve annulus and thinnest near the RAA orifice (p < .001). The thickness of the myocardial layer followed an inverse trend (p < .001). CONCLUSIONS: This study was the first to describe the detailed topographical anatomy of the RAA vestibule and that of its adjoining isthmuses. The substantial variability in the structure and dimensions of the RAA isthmuses may play a role in planning interventions within this anatomic region.

Efficacy of probiotics in patients with morbid obesity undergoing bariatric surgery: a systematic review and meta-analysis.

Bariatric surgery is considered effective for morbid obesity, and probiotic supplementation might provide some benefits. We aimed to revise the evidence regarding probiotic supplementation in patients with morbid obesity undergoing bariatric surgery. MEDLINE, Embase, Web of Science, CENTRAL, and trial registers were searched up to April 1, 2020. We included randomized controlled trials and controlled clinical trials, and outcomes of interest were weight change, quality of life, gastrointestinal symptoms, and adverse events. All stages of the review were done by 2 authors independently and we followed Cochrane Handbook guidance. We screened 2541 references and included 5 studies. Probiotics may have minor to no effect regarding percentage excess weight loss (%EWL) at 6 weeks (mean difference [MD], .28; 95% CI, -9.53 to 10.09; 44 participants, 2 studies), 3 months (MD, 5.47; 95% CI, -3.22 to 14.17; 165 participants, 3 studies), 6 months (MD, .46; 95% CI, -8.14 to 9.07; 115 participants, 2 studies), and 12 months post surgery (MD, .35; 95% CI, -8.66 to 9.37; 123 participants, 2 studies). We observed short-term improvement in gastrointestinal symptoms. There was no important effect on quality of life and no meaningful adverse events. Because probiotic supplementation might provide some benefit with respect to weight loss, might alleviate some gastrointestinal symptoms, and is associated with minor or no adverse events, continuous supplementation might be worth considering in certain individuals. Our findings are based on the body of evidence of very low certainty, and further well-designed randomized controlled trials are required to elucidate the effect and strengthen the certainty in the estimates.

Systematic review and meta-analysis of perioperative behavioral lifestyle and nutritional interventions in bariatric surgery: a call for better research and reporting.

Bariatric surgery is considered the most effective treatment for people with morbid obesity, and certain interventions could enhance its long-term results. We searched MEDLINE, Embase, Web of Science, CENTRAL, and trial registers up to January 1, 2020. Randomized controlled trials, where behavioral lifestyle or nutritional interventions were provided perioperatively were included. Primary outcome was weight change. Two reviewers independently performed each stage of the review. Altogether 6652 references were screened. 31 studies were included for qualitative synthesis and 22 studies for quantitative synthesis. Interventions varied greatly, thus limiting possibility of synthesizing all results. Six groups of interventions were discerned, and we used standardized mean differences for synthesis. Low to very-low certainty evidence suggests that physical activity, nonvitamin nutritional interventions, vitamins, psychotherapy, and counseling but not combined interventions might bring some benefit regarding short-term postsurgery follow-ups (up to 12 mo), but the estimates varied and results were not statistically significant, except for 12 months follow-ups regarding counseling. Psychotherapy and counseling, but not vitamins and combined interventions, may provide some benefit at longer follow-ups (over 12 mo), but the certainty of evidence was low to very-low and statistically significant results were observed in comparisons including data from single studies with small sample sizes only. Included studies expressed an outcome "weight change" using 20 different measures. Misreporting of data and huge variety of outcomes do not benefit systematic analyses and may possibly lead to confusion of both researchers and readers. We suggest that authors follow a predefined set of outcomes when reporting the results of their studies. The initiative to produce "core outcome set" for clinical trials in bariatric surgery trials is currently underway.

Multifaceted aspects of charge transfer.

Charge transfer and charge transport are by far among the most important processes for sustaining life on Earth and for making our modern ways of living possible. Involving multiple electron-transfer steps, photosynthesis and cellular respiration have been principally responsible for managing the energy flow in the biosphere of our planet since the Great Oxygen Event. It is impossible to imagine living organisms without charge transport mediated by ion channels, or electron and proton transfer mediated by redox enzymes. Concurrently, transfer and transport of electrons and holes drive the functionalities of electronic and photonic devices that are intricate for our lives. While fueling advances in engineering, charge-transfer science has established itself as an important independent field, originating from physical chemistry and chemical physics, focusing on paradigms from biology, and gaining momentum from solar-energy research. Here, we review the fundamental concepts of charge transfer, and outline its core role in a broad range of unrelated fields, such as medicine, environmental science, catalysis, electronics and photonics. The ubiquitous nature of dipoles, for example, sets demands on deepening the understanding of how localized electric fields affect charge transfer. Charge-transfer electrets, thus, prove important for advancing the field and for interfacing fundamental science with engineering. Synergy between the vastly different aspects of charge-transfer science sets the stage for the broad global impacts that the advances in this field have.

Impact of Protoporphyrin Lysine Derivatives on the Ability of Nosema ceranae Spores to Infect Honeybees.

The effect of two protoporphyrin IX derivatives conjugated with single (PP[Lys(TFA)-OH)]2) or double (PP[Lys(TFA)-Lys(TFA)-OH]2) lysine moieties on the infectious capacity of Nosema ceranae spores was examined, and their efficacies were compared with those of a cationic porphyrin (H2TTMePP). Honeybees were inoculated with spores preincubated with porphyrins or with untreated spores (control). A significantly lower level of infection was observed in the bees infected with the porphyrin-treated spores than in the infected control. Porphyrins 1 and 2 reduced the infectious capability of microsporidia more efficiently than porphyrin 3, with bee mortality declining to almost 50%. Confocal analysis of the midguts of infected bees revealed distinct differences in the number of spores between the control group and the group infected with PP[Lys(TFA)-Lys(TFA)-OH]2-treated spores. Notably, bees with a reduced level of infection consumed less sucrose syrup than the control bees, indicating a reduction in digestive disorders and an improvement in food absorption.

Mortality in patients after acute myocardial infarction managed by cardiologists and primary care physicians: a systematic review.

INTRODUCTION: Mortality following acute myocardial infarction (AMI) remains high despite of progress in invasive and noninvasive treatments. OBJECTIVES: This study aimed to compare the outcomes of ambulatory treatment provided by cardiologists versus general practitioners (GPs) in post­AMI patients. PATIENTS AND METHODS: We conducted a systematic search in 3 electronic databases for interventional and observational studies that reported all­cause mortality, mortality from cardiovascular causes, stroke, and myocardial infarction at long­term follow­up following AMI. We assessed the risk of bias of the included studies using the Risk of Bias in Nonrandomized Studies of Interventions (ROBINS­I) tool. For randomized trials, we used the revised Cochrane risk of bias tool (RoB 2.0). RESULTS: Two nonrandomized studies fulfilled the inclusion criteria. We assessed these studies as having a moderate risk of bias. We did not pool the results owing to significant heterogeneity between the studies. Patients consulted by both a cardiologist and a GP were at lower risk of all­cause death as compared with patients consulted by a cardiologist only (risk ratio [RR], 0.92; 95% CI, 0.85-0.99). Patients consulted by a cardiologist with or without GP consultation were at lower risk of all­cause death compared with those consulted by a GP only in both studies (RR, 0.8; 95% CI, 0.75-0.85 and RR, 0.44; 95% CI, 0.41-0.47). CONCLUSIONS: Patients after AMI consulted by both a cardiologist and a GP may be at lower risk of death compared with patients consulted by a GP or a cardiologist only. However, these findings are based on moderate­quality nonrandomized studies. We found no evidence on the relation between the specialization of the physician and the risk of cardiovascular death, stroke, or myocardial infarction in AMI survivors.

Bioactivity studies of porphyrinoids against microsporidia isolated from honeybees.

Microsporidian infections are dangerous to honeybees due to the absence of an efficient treatment for nosemosis. In the present work, the abilities of several porphyrins to directly inactivate microsporidia derived from Nosema-infected honeybees were studied in vitro. Amide derivatives of protoporphyrin IX (PPIX) conjugated with one and two amino acid moieties were synthesized, and their activities were compared with those of two cationic porphyrins, TMePyP and TTMePP. The most active porphyrins, PP[Lys-Asp]2, PP[Lys-TFA]2, PP[Asp(ONa)2]2 and PP[Lys-Lys]2 at concentrations as low as 10-50 µM exerted significant effects on microsporidia, reducing the number of spores by 67-80% compared to the control. Live-cell imaging of the spores treated with porphyrins showed that only 1.6% and 3.0% of spores remained alive after 24 h-incubation with 50 µM PP[Asp(ONa)2]2 and PP[Lys-Asp]2, respectively. The length of the amino acid side chains and their identity in the PPIX molecules affected the bioactivity of the porphyrin. Importantly, the irradiation of the porphyrins did not enhance their potency in destroying Nosema spores. We showed that the porphyrins accumulated inside the living spores but not inside dead spores, thus the destruction of the microsporidia by non-metallated porphyrins is not dependent on photosensitization, but is associated with their active transport into the spore cell. When administered to honeybees in vivo, PPIX[Lys-TFA]2 and PPIX[Lys-Lys]2 reduced spore loads by 69-76% in infected individuals. They both had no toxic effect on honeybees, in contrast to zinc-coordinated porphyrin.