Detection of Waterborne and Airborne Microorganisms in a Rodent Facility.

This study aimed to evaluate the air and water contamination level and to identify the microbes isolated from a rodent facility located at the Federal University of Uberlândia, Minas Gerais, Brazil. Colony forming units (CFU) per milliliter was used for monitoring water quantitatively; CFU per cubic meter was used for air monitoring. The isolated colonies were identified for qualitative monitoring. Due to absence of specific parameters for these facilities, the results were analyzed according to Brazilian and international standards, depending on which best suited each sample. The mean total number of microorganisms in water ranged from 0.015 ± 0.02 to 0.999 ± 0.91 CFU/mL. The number of microorganisms in air ranged from 9.1 ± 4.6 to 351.56 ± 158.2 CFU/m³. Forty-one microorganisms identified in the samples obtained from the rodent facility were potentially pathogenic or opportunistic for animals and humans (e.g., Corynebacterium spp.). We concluded that the water and air samples were contaminated with potentially pathogenic or opportunistic microorganisms that can harm rodents and humans. On the basis of our observations, specific sanitary standards suitable for these facilities should be developed for controlling microbial contamination, which will prevent zoonosis and ensure the reliability of scientific results obtained from animal experiments.

NHC Effects on Reduction Dynamics in Iron-Catalyzed Organic Transformations*.

The high abundance, low toxicity and rich redox chemistry of iron has resulted in a surge of iron-catalyzed organic transformations over the last two decades. Within this area, N-heterocyclic carbene (NHC) ligands have been widely utilized to achieve high yields across reactions including cross-coupling and C-H alkylation, amongst others. Central to the development of iron-NHC catalytic methods is the understanding of iron speciation and the propensity of these species to undergo reduction events, as low-valent iron species can be advantageous or undesirable from one system to the next. This study highlights the importance of the identity of the NHC on iron speciation upon reaction with EtMgBr, where reactions with SIMes and IMes NHCs were shown to undergo ß-hydride elimination more readily than those with SIPr and IPr NHCs. This insight is vital to developing new iron-NHC catalyzed transformations as understanding how to control this reduction by simply changing the NHC is central to improving the reactivity in iron-NHC catalysis.

Synthesis and Characterization of a Sterically Encumbered Homoleptic Tetraalkyliron(III) Ferrate Complex.

Homoleptic iron-alkyl complexes have been implicated as key intermediates in iron-catalyzed cross-coupling with simple iron salts. Tetraalkyliron(III) ferrate species have been shown to be accessible with either methyl or benzyl ligands, where the former complex is S = 3/2 and distorted square planar while the latter is a S = 5/2 distorted tetrahedral species. In the current study, a new tetraalkyliron(III) complex is synthesized containing modified methylene substituents that incorporate large trimethylsilyl (TMS) groups to further probe steric and electronic ligand effects in tetraalkyliron(III) complexes by increasing the electron-donating ability of the ligand while retaining steric bulk. Detailed structural and DFT studies provide insight into electronic structure and bonding of the four-coordinate trimethylsilylmethyl iron(III) complex compared to the previously reported analogs containing methyl and benzyl ligands.

The Effect of ß-Hydrogen Atoms on Iron Speciation in Cross-Couplings with Simple Iron Salts and Alkyl Grignard Reagents.

The effects of ß-hydrogen-containing alkyl Grignard reagents in simple ferric salt cross-couplings have been elucidated. The reaction of FeCl3 with EtMgBr in THF leads to the formation of the cluster species [Fe8 Et12 ]2- , a rare example of a structurally characterized metal complex with bridging ethyl ligands. Analogous reactions in the presence of NMP, a key additive for effective cross-coupling with simple ferric salts and ß-hydrogen-containing alkyl nucleophiles, result in the formation of [FeEt3 ]- . Reactivity studies demonstrate the effectiveness of [FeEt3 ]- in rapidly and selectively forming the cross-coupled product upon reaction with electrophiles. The identification of iron-ate species with EtMgBr analogous to those previously observed with MeMgBr is a critical insight, indicating that analogous iron species can be operative in catalysis for these two classes of alkyl nucleophiles.

The N-Methylpyrrolidone (NMP) Effect in Iron-Catalyzed Cross-Coupling with Simple Ferric Salts and MeMgBr.

The use of N-methylpyrrolidone (NMP) as a co-solvent in ferric salt catalyzed cross-coupling reactions is crucial for achieving the highly selective, preparative scale formation of cross-coupled product in reactions utilizing alkyl Grignard reagents. Despite the critical importance of NMP, the molecular level effect of NMP on in situ formed and reactive iron species that enables effective catalysis remains undefined. Herein, we report the isolation and characterization of a novel trimethyliron(II) ferrate species, [Mg(NMP)6 ][FeMe3 ]2 (1), which forms as the major iron species in situ in reactions of Fe(acac)3 and MeMgBr under catalytically relevant conditions where NMP is employed as a co-solvent. Importantly, combined GC analysis and 57 Fe Mössbauer spectroscopic studies identified 1 as a highly reactive iron species for the selective formation generating cross-coupled product. These studies demonstrate that NMP does not directly interact with iron as a ligand in catalysis but, alternatively, interacts with the magnesium cations to preferentially stabilize the formation of 1 over [Fe8 Me12 ]- cluster generation, which occurs in the absence of NMP.

Isolation, Characterization, and Reactivity of Fe8Me12(-): Kochi's S = 1/2 Species in Iron-Catalyzed Cross-Couplings with MeMgBr and Ferric Salts.

Iron-catalyzed cross-couplings with simple ferric salts have been known since the 1970s, pioneered by Kochi for cross-coupling using alkylmagnesium nucleophiles including MeMgBr. While Kochi observed the formation of a S = 1/2 iron species in reactions of simple ferric salts with MeMgBr proposed to be an iron(I) species, the identity of this species has remained undefined for nearly 40 years. Herein, we report the isolation and characterization of [MgCl(THF)5][Fe8Me12], which combined with EPR and MCD studies is shown to be consistent with Kochi's S = 1/2 species. Reaction studies with ß-bromostyrene demonstrate that this species alone displays minimal reactivity but, when combined with additional MeMgBr, leads to rapid and selective formation of cross-coupled product.

Styrene Aziridination by Iron(IV) Nitrides.

Thermolysis of the iron(IV) nitride complex [PhB(tBuIm)3Fe≡N] with styrene leads to formation of the high-spin iron(II) aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)]. Similar aziridination occurs with both electron-rich and electron-poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)] acts as a nitride synthon, reacting with electron-poor styrenes to generate their corresponding aziridino complexes, that is, aziridine cross-metathesis. Reaction of [PhB(tBuIm)3Fe-N(CH2CHPh)] with Me3SiCl releases the N-functionalized aziridine Me3SiN(CH2CHPh) while simultaneously generating [PhB(tBuIm)3FeCl]. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex [PhB(MesIm)3Fe≡N] reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products.

Reaction of an iron(IV) nitrido complex with cyclohexadienes: cycloaddition and hydrogen-atom abstraction.

The iron(IV) nitrido complex PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(η(5)-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels-Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product.

Ligand modification transforms a catalase mimic into a water oxidation catalyst.

The catalytic reactivity of the high-spin Mn(II) pyridinophane complexes [(Py2NR2)Mn(H2O)2](2+) (R=H, Me, tBu) toward O2 formation is reported. With small macrocycle N-substituents (R=H, Me), the complexes catalytically disproportionate H2O2 in aqueous solution; with a bulky substituent (R=tBu), this catalytic reaction is shut down, but the complex becomes active for aqueous electrocatalytic H2O oxidation. Control experiments are in support of a homogeneous molecular catalyst and preliminary mechanistic studies suggest that the catalyst is mononuclear. This ligand-controlled switch in catalytic reactivity has implications for the design of new manganese-based water oxidation catalysts.

[Facing fever in the pediatric patient: Checklist as a tool for parents]. / Checklist como herramienta para los padres ante la fiebre en el paciente pediátrico.

INTRODUCTION: In Western Europe, 20%-40% of children with fever request health care. Most of them present trivial viral infections, however, it is essential in pediatrics to distinguish patients who present a severe infection. This process begins with the recognition of the seriousness and the subsequent search for medical attention by the parents. METHODOLOGY: Analytical and cross-sectional observational study. One hundred patients were selected in two health centers. Sociodemographic data were collected, together with the responses to a checklist containing the signs and symptoms to request health care in case of fever. Subsequently, the checklist was filled out by the pediatrician. RESULTS: The mean age of the patients was 5.41 years. 50% consulted in the first 48h of fever evolution. In 42%, the response to all the items on the checklist was exactly the same between the companion and the pediatrician. There were no significant differences according to variables: first episode of fever (P=.262), age of the patient (P=.859), having a sibling (P=.880), family relationship of the companion (P=.648) or educational level of the companion (P=.828). CONCLUSIONS: Medical consultations for fever in pediatrics are carried out very early. A high percentage do not present alarm signs when they consult. There is a need to expand training on the alarm signs of fever in all parents, regardless of the number of children, age or educational level. The checklist as a tool for home assessment of fever has received high marks for its usefulness.

[Telematic attention in a neuropediatrics consultation during the COVID-19 alarm state. Cross-sectional study and satisfaction survey]. / Valoración de la atención telemática en una consulta de Neuropediatría durante el estado de alarma por COVID-19. Estudio transversal y encuesta de satisfacción.

INTRODUCTION: Crisis caused by the SARS-CoV-2 virus limit face-to-face consultation to the minimum necessary, this was a change toward telephone activity. OBJECTIVE: To analyze the experience of a neuropediatric consultation, INRPC, and satisfaction survey with the telephone consultation during COVID-19 crisis. MATERIAL AND METHODS: Observational, cross-sectional, descriptive and analytical study of healthcare activity, as well as user satisfaction, during the State of Alarm in a neuropediatric consultation in a regional referral hospital. To measure satisfaction, a survey is conducted with parents and guardians. RESULTS: 416 children were attended by telephone. Most frequent diagnoses: neurodevelopmental disorder (27.8%), isolated ADD/ADHD (26.8%), and epilepsy (9.2%). 32.2% responded to the survey: 66.6% prior satisfaction. Global satisfaction with telephone consultation 59.9%; 77% would return to make the telephone consultation. CONCLUSIONS: User satisfaction with the telephone consultation, in a crisis situation, is similar to that perceived with the face-to-face consultation. 32% respond to the survey, and 60% are satisfied.

Experimental dataset of the impact assessment of vegetable intercropping on agroeconomic performances, pests and beneficials, and soil resources.

The data presented in this article were collected in the field at an experimental station in southern France under a Mediterranean climate. Experiments were conducted under three plastic walk-in tunnels used as blocks with organic farming practices over two successive years in a completely randomized design. The aim was to compare the intercropping of sweet pepper with basil, onion, lettuce, parsley or French bean to a sole crop of sweet pepper used as a control. The dataset provides information on cultural practices with details on inputs and working times used to estimate economic costs. The data also describe the climatic conditions under tunnels as well as the dynamics of soil nitrate concentration and water tension over time through treatments. Yields, economic benefits and the rates of products with visual defects are presented. In addition, some variables applied exclusively to sweet pepper crops, namely nitrate concentration in petiole sap, growth parameters, abundance of aerial pests and beneficials, incidence of root necrosis, arbuscular mycorrhizal fungi colonization rates and diversity in roots. The field dataset is made publicly available to allow free and easy access for the scientific and professional community to enable analysis and reuse. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

['Wait and see' in paediatric epilepsy. Our experience]. / Wait and see en epilepsia pediátrica. Nuestra experiencia.

INTRODUCTION: Pharmacological treatment of epilepsy is not healing; it tries to avoid seizures, as far as possible, in children who probably would still have them. PATIENTS AND METHODS: Our purpose is to analyse our experience with epileptic children and those who have a first non-symptomatic seizure without pharmacological treatment. Patients seen in a paediatric neurology consultation, from 2017 to 2021, who had suffered one or more acute non-symptomatic crises and who had not been treated pharmacologically, were analysed. RESULTS: Sixty-five patients meet the selection criteria. Twenty-four patients had had a single crisis with a mean duration of 12 minutes (1-60). In 66.7% it was nocturnal. 41.7% presented pathological electroencephalogram, and 21% pathological findings in neuroimaging. The mean control time was 2.7 years (0.003-13.6 years). Forty-one presented more than one crisis, with a mean duration of nine minutes (1-60). Five patients presented more than 20 seizures, the rest between two and 17. Twenty-four (58.5%) presented only nocturnal seizures. An electroencephalogram was performed in all: epileptiform graphoelements in 63.4%; and neuroimaging in all: pathological in 4.9%. Mean control time was 3.8 years (0.01-9.1 years). CONCLUSIONS: Seizure frequency, underlying pathology or test results should not be the only variables to take into consideration when starting antiepileptic drug treatment. The repercussion on their quality of life and neurodevelopment should prevail, agreeing on this decision with the parents.

TITLE: Wait and see en epilepsia pediátrica. Nuestra experiencia.El tratamiento farmacológico de la epilepsia no es curativo; pretende, en lo posible, evitar crisis en niños que probablemente van a seguir teniéndolas. Pacientes y métodos. El objeto es analizar nuestra experiencia en niños con epilepsia y con primera crisis no sintomática aguda no tratados con antiepilépticos. Se analizó a pacientes atendidos en una consulta de neuropediatría, desde 2017 hasta 2021, que habían sufrido una o más crisis no sintomáticas agudas y a los que no se les había tratado farmacológicamente. Resultados. Sesenta y cinco pacientes cumplieron los criterios de selección. Veinticuatro habían tenido una única crisis, con un tiempo medio de duración de 12 minutos (1-60). En un 66,7% fue nocturna. Un 41,7% presentó electroencefalograma patológico, y un 21%, hallazgos patológicos en la neuroimagen. El tiempo medio de control fue de 2,7 años (0,003-13,6 años). Cuarenta y uno presentaron más de una crisis, con una duración media de nueve minutos (1-60). Cinco pacientes presentaron más de 20 crisis, y el resto, entre dos y 17. Veinticuatro (58,5%) presentaron únicamente crisis nocturnas. Se realizó un electroencefalograma en todos: grafoelementos epileptiformes en el 63,4%; y neuroimagen en todos: patológica en el 4,9%. El tiempo medio de control fue de 3,8 años (0,01-9,1 años). Conclusiones. La frecuencia de las crisis, la patología de base o los resultados de las pruebas complementarias no deberían ser las únicas variables que habría que considerar para iniciar el tratamiento farmacológico antiepiléptico en los niños. Debería prevalecer, por encima de aquéllos, el potencial perjuicio sobre la calidad de vida y el neurodesarrollo, las funciones atencionales y el comportamiento del niño, y siempre consensuar esta decisión con los padres.

Monkeypox vaccination in the global south: Fighting a war without a weapon.

Background: The Mpox outbreak awakened countries worldwide to renew efforts in epidemiological surveillance and vaccination of susceptible populations. In terms of Mpox vaccination, various challenges exist in the global south, which impede adequate vaccine coverage, especially in Africa. This paper reviewed the situation of Mpox vaccination in the global south and potential ameliorative approaches. Methods: A review of online literature from PubMed and Google Scholar concerning Mpox vaccination in countries belonging to the 'global south' category was done between August and September, 2022. The major focus areas included inequity in global vaccine distribution, challenges impeding vaccine coverage in the global south, and potential strategies for bridging the gap in vaccine equity. The papers that met the inclusion criteria were collated and narratively discussed. Results: Our analysis revealed that, while the high-income countries secured large supplies of the Mpox vaccines, the low- and middle-income countries were unable to independently access substantial quantities of the vaccine and had to rely on vaccine donations from high-income countries, as was the case during the COVID-19 pandemic. The challenges in the global south particularly revolved around inadequate vaccine production capacity due to lack of qualified personnel and specialized infrastructure for full vaccine development and manufacturing, limited cold chain equipment for vaccine distribution, and consistent vaccine hesitancy. Conclusion: To tackle the trend of vaccine inequity in the global south, African governments and international stakeholders must invest properly in adequate production and dissemination of Mpox vaccines in low- and middle-income countries.

Classification of samples into two or more ordered populations with application to a cancer trial.

In many applications, especially in cancer treatment and diagnosis, investigators are interested in classifying patients into various diagnosis groups on the basis of molecular data such as gene expression or proteomic data. Often, some of the diagnosis groups are known to be related to higher or lower values of some of the predictors. The standard methods of classifying patients into various groups do not take into account the underlying order. This could potentially result in high misclassification rates, especially when the number of groups is larger than two. In this article, we develop classification procedures that exploit the underlying order among the mean values of the predictor variables and the diagnostic groups by using ideas from order-restricted inference. We generalize the existing methodology on discrimination under restrictions and provide empirical evidence to demonstrate that the proposed methodology improves over the existing unrestricted methodology. The proposed methodology is applied to a bladder cancer data set where the researchers are interested in classifying patients into various groups.

Tris(carbene)borate ligands featuring imidazole-2-ylidene, benzimidazol-2-ylidene, and 1,3,4-triazol-2-ylidene donors. Evaluation of donor properties in four-coordinate {NiNO}10 complexes.

The synthesis and characterization of new tris(carbene)borate ligand precursors containing substituted benzimidazol-2-ylidene and 1,3,4-triazol-2-ylidene donor groups, as well as a new tris(imidazol-2-ylidene)borate ligand precursor are reported. The relative donor strengths of the tris(carbene)borate ligands have been evaluated by the position of ν(NO) in four-coordinate {NiNO}(10) complexes, and follow the order: imidazol-2-ylidene > benzimidazol-2-ylidene > 1,3,4-triazol-2-ylidene. There is a large variation in ν(NO), suggesting these ligands to have a wide range of donor strengths while maintaining a consistent ligand topology. All ligands are stronger donors than Tp* and Cp*.

Replication of Integrative Data Analysis for Adipose Tissue Dysfunction, Low-Grade Inflammation, Postprandial Responses and OMICs Signatures in Symptom-Free Adults.

We previously reported preliminary characterization of adipose tissue (AT) dysfunction through the adiponectin/leptin ratio (ALR) and fasting/postprandial (F/P) gene expression in subcutaneous (SQ) adipose tissue (AT) biopsies obtained from participants in the GEMM study, a precision medicine research project. Here we present integrative data replication of previous findings from an increased number of GEMM symptom-free (SF) adults (N = 124) to improve characterization of early biomarkers for cardiovascular (CV)/immunometabolic risk in SF adults with AT dysfunction. We achieved this goal by taking advantage of the rich set of GEMM F/P 5 h time course data and three tissue samples collected at the same time and frequency on each adult participant (F/P blood, biopsies of SQAT and skeletal muscle (SKM)). We classified them with the presence/absence of AT dysfunction: low (<1) or high (>1) ALR. We also examined the presence of metabolically healthy (MH)/unhealthy (MUH) individuals through low-grade chronic subclinical inflammation (high sensitivity C-reactive protein (hsCRP)), whole body insulin sensitivity (Matsuda Index) and Metabolic Syndrome criteria in people with/without AT dysfunction. Molecular data directly measured from three tissues in a subset of participants allowed fine-scale multi-OMIC profiling of individual postprandial responses (RNA-seq in SKM and SQAT, miRNA from plasma exosomes and shotgun lipidomics in blood). Dynamic postprandial immunometabolic molecular endophenotypes were obtained to move towards a personalized, patient-defined medicine. This study offers an example of integrative translational research, which applies bench-to-bedside research to clinical medicine. Our F/P study design has the potential to characterize CV/immunometabolic early risk detection in support of precision medicine and discovery in SF individuals.

Shortening in the Tp-e/QTc ratio after angioplasty in patients with acute coronary syndrome. / Acortamiento en la relación Tp-f/QTc tras angioplastia en pacientes con síndrome isquémico coronario agudo.

Objetivo: La dispersión transmural de la repolarización ventricular (DTMRV) es un factor de riesgo para muerte en pacientes con síndrome isquémico coronario agudo (SICA). Con el objetivo de conocer el efecto de la realización de angioplastia sobre la DTMRV, se estudió la relación Tp-f/QTc en pacientes con SICA sometidos a angioplastia. Método: Se diseñó un estudio observacional, retrospectivo y descriptivo. Se incluyeron 150 pacientes (N = 150) con diagnóstico de SICA. Se valoró la relación Tp-f/QTc inicial y se evaluó su acortamiento posangioplastia. Como objetivo secundario, se comparó la asociación de dichos cambios en la relación Tp-f/QTc con la mortalidad cardiovascular y los eventos adversos cardiovasculares. Resultados: El promedio en la relación Tp-f/QTc inicial fue de 0.2529, mientras que posangioplastia fue de 0.2397. Por medio de prueba de rangos de Wilcoxon se evidenció un descenso significativo en la relación Tp-f/QTc posterior a la angioplastia, con un valor Z de -2.051 y una p < 0.04. En el análisis secundario se encontró que una Tp-f/QTc ≥ 0.29 posangioplastia es factor de riesgo para presentación de los siguientes eventos adversos: muerte intrahospitalaria (7.4 vs 0%; p < 0.003), nuevo SICA en seguimiento a 1 año (25.9 vs. 18.5%; p < 0.006) y reintervención en seguimiento a 1 año (29.6 vs. 15.0%; p < 0.002). Conclusiones: Existe un acortamiento significativo en la relación Tp-f/QTc posangioplastia en pacientes con SICA. Esta medida de la DTMRV puede servir como un predictor de muerte intrahospitalaria, eventos cardiovasculares y reintervención a 1 año en pacientes con SICA tratados con angioplastia. Objective: Transmural Dispersion of Repolarization (TDR) is a Risk factor for Death in patients with Acute Coronary ­Syndrome (ACS). In order to know the effect of angioplasty on TDR, the Tp-e/QTc ratio was studied in patients with ACS undergoing angioplasty. Method: An observational, retrospective and descriptive study was designed. 150 patients (N = 150) with diagnosis of ACS were included. The initial Tp-e/QTc ratio was assessed and then its post-angioplasty shortening was evaluated. As a secondary objective, we compared the association of these Tp-e/QTc ratio changes with cardiovascular mortality and cardiovascular adverse events. Results: The average in the initial Tp-e/QTc ratio was 0.2529, while post-angioplasty was 0.2397. Through a Wilcoxon rage test, a significant decrease in the Tp-e/QTc ratio after angioplasty was observed, with a Z value of −2.051 and p < 0.04. In the secondary analysis, it was found that a Tp-e/QTc ≥ 0.29 post-angioplasty is a risk factor for presenting the following adverse events: in-hospital death (7.4 vs. 0%; p < 0.003), new ACS in 1-year follow-up (25.9 vs. 18.5%; p < 0.006), and reintervention in 1-year follow up (29.6 vs. 15%; p < 0.002). Conclusions: There is a significant shortening in the Tp-e/QTc ratio post-angioplasty in patients with ACS. This measure of TDR can serve as a predictor of in-hospital death, cardiovascular events and 1-year reintervention in patients with ACS treated initially by angioplasty.