Engineering buffer layers to improve temperature resilience of magnetic tunnel junction sensors.

Improving the thermal resilience of magnetic tunnel junctions (MTJs) broadens their applicability as sensing devices and is necessary to ensure their operation under harsh environments. In this work, we are address the impact of temperature on the degradation of the magnetic reference in field sensor stacks based on MgO-MTJs. Our study starts by simple MnIr/CoFe bilayers to gather enough insights into the role of critical morphological and magnetic parameters and their impact in the temperature dependent behavior. The exchange bias coupling field (Hex), coercive field (Hc), and blocking temperature (Tb) distribution are tuned, combining tailored growth conditions of the antiferromagnet and different buffer layer materials and stackings. This is achieved by a unique combination of ion beam deposition and magnetron sputtering, without vaccum break. Then, the work then extends beyond bilayers into more complex state-of-the-art MgO MTJ stacks as those employed in commercial sensing applications. We systematically address their characteristic fields, such as the width of the antiferromagnetic coupling plateau ΔH, and study their dependence on temperature. Although, [Ta/CuN] buffers showed higher key performance indications (e.g.Hex) at room temperature in both bilayers and MTJs, [Ta/Ru] buffers showed an overall wider ΔHup to 200 °C, more suitable to push high temperature operations. This result highlights the importance of properly design a suitable buffer layer system and addressing the complete MTJ behavior as function of temperature, to deliver the best stacking design with highest resilience to high temperature environments.

Morning serum cortisol role in the adrenal insufficiency diagnosis with modern cortisol assays.

PURPOSE: To investigate the accuracy of cutoff values of the morning serum cortisol (MSC) using the cortisol stimulus test (CST) insulin tolerance test (ITT) and 250 mcg short Synacthen test (SST) as the reference standard tests, to better define its clinical role as a tool in the diagnostic investigation of adrenal insufficiency (AI) AI. METHODS: An observational study was conducted with a retrospective analysis of MSC in adult patients who had been submitted to a CST to investigate AI between January 2014 and December 2020. The normal cortisol response (NR) to stimulation was defined based on the cortisol assay. RESULTS: 371 patients underwent CST for suspected AI, 121/371 patients (32.6%) were diagnosed with AI. ROC curve analysis showed an area under the curve (AUC) for MSC of 0.75 (95% CI 0.69 - 0.80). The best MSC cutoff values to confirm AI were < 3.65, < 2.35 and < 1.5 mcg/dL with specificity of 98%, 99%, and 100%, respectively. MSC > 12.35, > 14.2 and > 14.5 mcg/dL had sensitivity of 98%, 99%, and 100%, respectively, being the best cutoff values to exclude AI. Almost 25% of patients undergoing CST for possible AI had MSC values between < 3.65 mcg/dL (6.7% of patients) and > 12.35 mcg/dL (17.5% of patients), making the formal CST testing unnecessary if we consider these cutoff values. CONCLUSION: With the most modern cortisol assays, MSC could be used as a diagnostic tool, with high accuracy to confirm or exclude AI, avoiding unnecessary CST; thus, reducing expenses and safety risks during AI investigation.

Effects of prenatal hypoxia-ischemia on male rat periaqueductal gray matter: Hyperalgesia, astrogliosis and nitrergic system impairment.

Prenatal hypoxic-ischemic insult (HI) may lead to a variety of neurological consequences that may persist throughout adulthood. In the most severe cases, HI is known to increase pain sensitivity which profoundly impacts quality of life. Periaqueductal gray matter (PAG) is a relevant region of the descending pain pathway and its function may be modulated by a complex network that includes nitrergic neurons and glial response, among other factors. Astrocytes, central players in pain modulation, are known to respond to HI by inducing hyperplasia, hypertrophy and increasing the number of their processes and the staining of glial fibrillary acidic protein (GFAP). In this work we investigated the effects of prenatal HI on touch and pain sensitivity, besides the distribution of the neuronal isoform of Nitric Oxide Synthase (nNOS) and GFAP in the PAG of young and adult male rats. At 18 days of gestation, rats had their uterine arteries clamped for 45 min (HI group). SHAM-operated animals were also generated (SHAM group). At post-natal day 30 (P30) or 90 (P90), the offspring was submitted to the behavioral tests of Von Frey and formalin or histological processing to perform immunohistochemistry for nNOS and GFAP. Although there was no significant difference between the groups concerning touch sensitivity, we observed an increase in pain sensitivity in HI P30 and HI P90. The number of nNOS + cells was reduced in HI adult animals in dlPAG and vlPAG. GFAP immunostaining was increased in HI P90 in dlPAG and dmPAG. Our results demonstrated for the first time an increase in pain sensitivity as a consequence of prenatal HI in an animal model. It reinforces the relevance of this model to mimic the effects of prenatal HI, as hyperalgesia.

Supramolecular porphyrin as an improved photocatalyst for chloroform decomposition.

In this work, the outlying decoration of the free-base meso-(4-tetra) pyridyl porphyrin (H2TPyP) with the RuCl(dppb)(5,5'-Me-bipy) ruthenium complex (here named Supra-H2TPyP) is observed as an improved molecular photocatalyst for dye-mediated chloroform (CHCl3) decomposition via one-photon absorption operating in the visible spectral range (532 nm and 645 nm). Supra-H2TPyP offers a better option for CHCl3 photodecomposition when compared to the same process mediated by pristine H2TPyP, which requires either excited-state- or UV absorption. The chloroform photodecomposition rates for Supra-H2TPyP as well as its excitation mechanisms are explored as a function of distinct laser irradiation conditions.

Setting up regional diagnostic reference levels for pediatric interventional cardiology in Latin America and the Caribbean countries: preliminary results and identified challenges.

The goal of the present study was to propose a set of preliminary regional diagnostic reference levels (DRLs) for pediatric interventional cardiology (IC) procedures in Latin America and the Caribbean countries, classified by age and weight groups. The study was conducted in the framework of the Optimization of Protection in Pediatric Interventional Radiology in Latin America and the Caribbean program coordinated by the World Health Organization and the Pan American Health Organization in cooperation with the International Atomic Energy Agency. The first step of the program was focused on pediatric IC. Dose data from diagnostic and therapeutic procedures were collected between December 2020 and December 2021. Regional DRLs were set as the third quartile of patient dose data (kerma area product) collected in 18 hospitals from 10 countries in an initial sample of 968 procedures. DRLs were set for four age bands and five weight ranges. The values obtained for the four age bands (<1 yr, 1 to <5 yr, 5 to <10 yr and 10 to <16 yr) were 2.9, 6.1, 8.8 and 14.4 Gy cm2for diagnostic procedures, and 4.0, 5.0, 10.0 and 38.1 Gy cm2for therapeutic procedures, respectively. The values obtained for the five weight bands (<5 kg, 5 to <15 kg, 15 to <30 kg, 30 to <50 kg and 50 to <80 kg) were 3.0, 4.5, 8.1, 9.2 and 26.8 Gy cm2for diagnostic procedures and 3.7, 4,3, 7.3, 16.1 and 53.4 Gy cm2for therapeutic procedures, respectively. While initial data were collected manually as patient dose management systems (DMSs) were not available in most of the hospitals involved in the program, a centralized automatic DMS for the collection and management of patient dose indicators has now been introduced and is envisaged to increase the sample size. The possibility of alerting on high dose values and introducing corrective actions will help in optimization.

Effects of stress exposure in captivity on physiology and infection in avian hosts: no evidence of increased Borrelia burgdorferi s.l. infectivity to vector ticks.

Exposure to environmental stressors, an increasingly recurring event in natural communities due to anthropogenic-induced environmental change, profoundly impacts disease emergence and spread. One mechanism through which this occurs is through stress-induced immunosuppression increasing disease susceptibility, prevalence, intensity and reactivation in hosts. We experimentally evaluated how exposure to stressors affected both the physiology of avian hosts and the prevalence of the zoonotic bacteria Borrelia burgdorferi sensu lato (s.l.), in two model species-the blackbird Turdus merula and the robin Erithacus rubecula captured in the wild, using xenodiagnoses and analysis of skin biopsies and blood. Although exposure to stressors in captivity induced physiological stress in birds (increased the number of circulating heterophils), there was no evidence of increased infectivity to xenodiagnostic ticks. However, Borrelia detection in the blood for both experimental groups of blackbirds was higher by the end of the captivity period. The infectivity and efficiency of transmission were higher for blackbirds than robins. When comparing different methodologies to determine infection status, xenodiagnosis was a more sensitive method than skin biopsies and blood samples, which could be attributed to mild levels of infection in these avian hosts and/or dynamics and timing of Borrelia infection relapses and redistribution in tissues.

Assessment of biofilm formation by Campylobacter spp. isolates mimicking poultry slaughterhouse conditions.

This research aimed to assess the biofilm formation ability of Campylobacter strains under temperature and oxygen stress conditions, similar to those found in the industrial environment, to explain the persistence of this pathogen on the poultry slaughter line. A collection of C. jejuni and C. coli isolates (n = 143) obtained from poultry samples (cecal content and neck skin), collected at slaughterhouse level, from diverse flocks, on different working days, was genotyped by flaA-restriction fragment length polymorphism (RFLP) typing method. A clustering analysis resulted in the assignment of 10 main clusters, from which 15 strains with different flaA-RFLP genotypes were selected for the assessment of biofilm formation ability and antimicrobial susceptibility. Biofilm assays, performed by crystal violet staining method, were conducted with the goal of mimicking some conditions present at the slaughterhouse environment, based on temperature, atmosphere, and contamination levels. Results indicated that many C. jejuni strains with similar flaA-RFLP profiles were present at the slaughterhouse on different processing days. All the strains tested (n = 15) were multidrug-resistant except for one. Biofilm formation ability was strain-dependent, and it appeared to have been affected by inoculum concentration, temperature, and tolerance to oxygen levels. At 10°C, adherence levels were significantly lower than at 42°C. Under microaerobic and aerobic atmospheres, at 42°C, 3 strains (C. jejuni 46E, C. jejuni 61C, and C. coli 65B) stood out, exhibiting significant levels of biofilm formation. C. jejuni strains 46E and 61C were inserted in clusters with evidence of persistence at the slaughterhouse for a long period of time. This study demonstrated that Campylobacter strains from broilers are capable of forming biofilms under conditions resembling the slaughterhouse environment. These results should be seen as a cue to improve the programs of hygiene implemented, particularly in those zones that can promote biofilm formation.

Photophysics and visible light photodissociation of supramolecular meso-tetra(4-pyridyl) porphyrin/RuCl2(CO)(PPh3)2 structures.

In the last decades, supramolecular structures have been explored in many technological efforts. One example of such supramolecules is attained when ruthenium complexes are attached in the outer sites of a porphyrin. Ruthenium complexes act as modulators of the photophysical processes of macrocyclic molecules. Besides the investigation of the main changes introduced by the ruthenium complexes in the electronic and vibronic properties, and in the excited state deactivation processes of porphyrins, discussions concerning the photostability of these supramolecules are much needed. Here, we investigate the supramolecular free-base meso-tetra(4-pyridyl) porphyrin decorated with "RuCl2(CO)(PPh3)2" ruthenium species linked at each of its (4-pyridyl) moieties. The modifications in the photophysical processes introduced by the metallic outlying species are discussed and our results suggest an energy transfer process from the porphyrin B-band to the ruthenium complex MLCT-band. The demonstration of visible light photodissociation of the supramolecule, via both pulsed and continuous laser, is also addressed.

Influence of the meso-substituents on the spectral features of free-base porphyrin.

The role of meso-substituents on the spectral features of free-base porphyrins is explored. Meso-tetra(4-pyridyl)porphyrin is compared with meso-tetra(2-thienyl)porphyrin and meso-tetra(pentafluorophenyl)porphyrin. Our results indicate that some of the asymmetric Q-bands in the free-base porphyrin tend to become symmetric relative to the adopted meso-substituent. The results show that the outlying perturbations lead the free-base quasi-degenerated Qx1, Qx2, Qy1, and Qy2 bands to be closer in energy. Combined, absorption, fluorescence and Raman spectroscopies endorse our conclusions showing that both the frequencies and the Huang-Rhys factors associated with every vibronic progression are noticeably affected by the investigated meso-substituents. Our results confirm that the B-band is also multi-featured in agreement with what is found for the Q-bands.

New Records of Ticks of Genus Amblyomma Koch, 1844 (Acari: Ixodidae) for Ecuador.

PURPOSE: In Ecuador, knowledge of the diversity and geographic distribution of ticks, as well as their importance as vectors, is scarce. Within the family Ixodidae, the genus Amblyomma is the most diverse and parasitizes wild and domestic animals. This genus is represented by 19 species in Ecuador, 12 of which occur in the continental territory and 7 in the Galapagos Islands. In this way, the objective of this work was to update the diversity of ticks reported for Ecuador on wild and domestic animals. METHODS: The specimens were collected manually on mammals and birds, in four localities belonging to the Sierra and Amazon of Ecuador and were kept in tubes with 96% ethyl alcohol. After that, all specimens were separated into immatures, males and females and were identified using their morphological characters. RESULTS: This study records Amblyomma coelebs Neumann, 1899, Amblyomma longirostre (Koch, 1844) Neumann, 1905 and Amblyomma varium Koch, 1844 for the first time in Ecuador. Thus, the genus Amblyomma is currently represented by 22 species. In addition, their hosts, distribution, and importance are also discussed. CONCLUSIONS: Knowing the diversity of ticks that wildlife possesses, its interrelation with the domestic fauna, and the possible pathogens that could be transmitting could significantly contribute to wildlife's conservation.

Dosagem sérica do marcador tumoral CA 15. 3 em cadelas portadoras de neoplasias mamárias pelo método de eletroquimioluminescência / Serum dosage of the tumor marker Ca 15. 3 in bitches presenting mammary neoplasia with the chemiluminescence method

The objective of the present study was to analyze the serum levels of the tumor marker Ca15.3 in healthy bitches and those with mammary neoplasms, correlating results with tumor type, clinical staging, time until presentation, and presence of ulceration and vascularization. For the study, 30 bitches with mammary tumors and 30 healthy bitches (control group) were selected. Histopathology was performed for identification of tumor type, and blood was collected for measurement of serum concentration of the marker via the chemiluminescence method using a commercial kit. A higher frequency of malignant neoplasms was observed (76.7%), with a higher quantity of carcinoma in mixed tumor (26.7%). Regarding serum concentration of the marker Ca15.3, there was no difference in serum values when comparing the means from bitches with neoplasia and healthy bitches, nor when comparing the other characteristics. The majority of results for serum concentration of Ca15.3, whether in bitches with neoplasia or in healthy bitches, was zero. It is concluded that the measurement of the marker Ca15.3 using the chemiluminescence method and commercial kits for humans did not offer significant results that would make this method or this marker a useful tool for patient monitoring and evaluation of the prognosis of bitches with mammary neoplasms.(AU)

[External fixation with reconstruction rail system as a treatment for pseudoarthrosis of the distal femur]. / Fijación externa con sistema de riel de reconstrucción como tratamiento para seudoartrosis del fémur distal.

Distal femur pseudoarthrosis also called «distal femur non-union¼ (DFNU) represents a rare complication associated with a fracture caused by high-energy trauma; its treatment is controversial, as there is a wide variety of surgical techniques that can be implemented, from open reduction plus internal fixation with plates, to the use of fixed angle plates combined with bone autograft. We expose the case of a 24-year-old man who shows up for consultation with the history of having presented a left femoral supracondylar fracture with a year of evolution, treated by osteosynthesis of the distal femur with dynamic condylar screws (DCS plate); developed a torpid evolution with severe pain in the distal third of the left thigh and functional limitation, developed a progressive varus deformity of the left thigh that caused a shortening of 3.8 cm of the limb. A focus of pseudoarthrosis was identified, which was surgically removed, the intramedullary canal was recanalized, and a lateral closed wedge osteotomy was performed to correct the angulation and allow reduction. 5.5 mm (three proximal and three distal) hydroxyapatite screws and an external fixator were placed. In addition, a review of the literature focused on the use of external fixation was carried out as a treatment for the pseudoarthrosis of the distal femur.

La seudoartrosis del fémur distal, también llamada «no unión del fémur distal¼ (NUFD), representa una complicación poco frecuente asociada a una fractura causada por un traumatismo de alta energía; su tratamiento es controversial, ya que existe una gran variedad técnicas quirúrgicas que pueden ser implementadas desde la reducción abierta más la fijación interna con placas hasta el uso de placas de ángulo fijo combinadas con autoinjerto óseo. Exponemos el caso de un hombre de 24 años de edad, el cual se presenta a la consulta con el antecedente de haber sufrido una fractura supracondílea femoral izquierda con un año de evolución, tratada mediante una osteosíntesis del fémur distal con tornillos condilares dinámicos (placa DCS); mostró una evolución tórpida con dolor severo en el tercio distal del muslo izquierdo y limitación funcional, desarrolló una deformidad en varo progresiva del muslo izquierdo que causó un acortamiento de 3.8 cm de la extremidad. Se identificó un foco de seudoartrosis, el cual se retiró quirúrgicamente, se recanalizó el canal intramedular y se realizó una osteotomía de cuña cerrada lateral para corregir la angulación y permitir la reducción. Se colocaron tornillos de hidroxiapatita de 5.5 mm (tres proximales y tres distales) y un fijador externo. Además se hizo una revisión de la literatura enfocada en el uso de la fijación externa como tratamiento de la seudoartrosis del fémur distal.

On the excitation dependence of fluorescence spectra of meso-tetrapyridyl zinc (II) porphyrin and its relation with hydrogen bonding and outlying decoration.

Zinc porphyrins are potential candidates for boosting the advancement of various technological applications, including those exploring the molecule's radiative emissions. In this work, the excitation dependence of fluorescence spectra from 5,10,15,20-meso-tetrapyridyl zinc(II) porphyrin dissolved in a binary solvent mixture of CHCl3: MeOH, is reported. Important modifications in the profiles of the fluorescence bands are observed after exciting the molecules in a broad wavelength range from 350 to 565 nm. We attribute such modifications to the existence of two distinct relaxation pathways, related to two quasi-degenerated potential energy surfaces (PES) in the ZnTPyP's first excited state whose population rates changes for different excitation wavelengths. We also observed that by changing the CHCl3:MeOH proportion in the binary mixture, a quenching mechanism mediated by the MeOH hydrogen bondings and ZnTPyP takes place, which allows for tuning the excitation dependence of the aforementioned relaxations pathways. Moreover, our data confirm that the addition of outlying RuCl(dppb)(bipy) ruthenium complex linked to the pyridyl moieties of the ZnTPyP ring is also an excellent strategy to modify the excitation dependence of the fluorescence relaxation pathways.

Evolution of electronic and vibronic transitions in metal(II) meso-tetra(4-pyridyl)porphyrins.

The changing of the electronic and vibronic states due to the insertion of Zn(II), Cu(II), Ni(II) or Co(II) ions in the meso-tetrakis(4-pyridyl)porphyrin ring center is investigated. The combination of absorption, photoluminescence, Raman and infrared spectroscopies with second-derivative-based spectral deconvolution analysis reveals that the structuration of both B- and Q-bands is very sensitive to the decorating ion. Similar to free base porphyrins, metal(II) meso-tetra(4-pyridyl)porphyrins also present their Q-band constituted of multiple electronic transitions, where the central ion plays an important role in the selection of vibration modes that mediate the vibronic transitions. Our novel results will expand and reinterpret current assignments for metal(II) meso-tetra(4-pyridyl)porphyrins vibrational modes available in the literature.

Pharyngeal airway space changes after maxillomandibular advancement: a five-year retrospective study.

The aim of this study was to compare the alterations in three regions of the airway-nasopharynx, oropharynx, and hypopharynx-in relation to the area of the midsagittal plane, volume, and minimal axial area after maxillomandibular advancement (MMA) surgery. Thirty patients who had undergone MMA surgery were evaluated at four time points: preoperative (T0), immediately postoperative (T1), 1year postoperative (T2), and ≥5 years postoperative (T3). All measurements were performed using computed tomography, analyzed in Dolphin Imaging 11.0 Premium 3D software. The area in the midsagittal plane presented a mean increase of 22.0% between T0 and T3 (P<0.001), with the highest increase in the oropharynx (24.1%, P<0.001). The total volumetric increase at T3 was 16.7% (P<0.001), with the highest increase in the nasopharynx (15.7%; P<0.001). The lowest minimal axial area was found for the oropharynx at all time points, and the highest increase in minimal axial area was found for the nasopharynx (114.9%; P<0.001). MMA surgery showed the highest increase in upper posterior airway between T0 and T1, and this was followed by a progressive reduction until T3, but with a statistically significant increase at T3 compared with T0 in all cases.

Inputs of rare earth elements in Brazilian agricultural soils via P-containing fertilizers and soil correctives.

The mineral exploration of rare earth elements (REEs) and their entry into the soil via fertilizers has generated concern about environmental impacts and human health risks. We evaluated 60 samples of limestone, gypsum and phosphate fertilizers marketed in Brazil in order to characterize their contents, signature and solubility of REEs. The fertilizers from igneous origin presented the largest accumulation of REEs. Accumulation of the light REEs Ce, La, Nd, Pr, Sm and Eu were larger than the heavy REEs (Y, Dy, Gd, Er, Yb, Ho, Tb and Lu). The solubility of fertilizers produced from sedimentary sources was greater than that of igneous sources. The mean annual REEs contribution of SSP and organo-mineral + phosphate rock (both of igneous origin) to soils was > 4000 t year-1, with highest additions for Ce, La, Nd and Y. Thus, phosphate fertilization and liming were considered to be significant sources of REEs and soils receiving continuously high doses of these inputs are likely to be enriched in REEs. Risk assessment studies are necessary to evaluate the impact of these REEs additions to soils on human health.

Key amino acid residues of the AGT1 permease required for maltotriose consumption and fermentation by Saccharomyces cerevisiae.

AIMS: The AGT1 gene encodes for a general α-glucoside-H+ symporter required for efficient maltotriose fermentation by Saccharomyces cerevisiae. In the present study, we analysed the involvement of four charged amino acid residues present in this transporter that are required for maltotriose consumption and fermentation by yeast cells. METHODS AND RESULTS: By using a knowledge-driven approach based on charge, conservation, location, three-dimensional (3D) structural modelling and molecular docking analysis, we identified four amino acid residues (Glu-120, Asp-123, Glu-167 and Arg-504) in the AGT1 permease that could mediate substrate binding and translocation. Mutant permeases were generated by site-directed mutagenesis of these charged residues, and expressed in a yeast strain lacking this permease (agt1∆). While mutating the Arg-504 or Glu-120 residues into alanine totally abolished (R504A mutant) or greatly reduced (E120A mutant) maltotriose consumption by yeast cells, as well as impaired the active transport of several other α-glucosides, in the case of the Asp-123 and Glu-167 amino acids, it was necessary to mutate both residues (D123G/E167A mutant) in order to impair maltotriose consumption and fermentation. CONCLUSIONS: Based on the results obtained with mutant proteins, molecular docking and the localization of amino acid residues, we propose a transport mechanism for the AGT1 permease. SIGNIFICANCE AND IMPACT OF THE STUDY: Our results present new insights into the structural basis for active α-glucoside-H+ symport activity by yeast transporters, providing the molecular bases for improving the catalytic properties of this type of sugar transporters.

Novel insights on the vibronic transitions in free base meso-tetrapyridyl porphyrin.

We present novel results on the free base 5,10,15,20-meso-tetra(pyridyl)-21H,23H-porphyrin (H2TPyP). This molecule presents complex electronic and vibrational properties and despite the vast literature reporting the transitions observed in its absorption and fluorescence spectra, a more accurate interpretation has been kept elusive. In particular, we show that the molecule's Q-band develops into many electronic and vibronic transitions, whose the well-known "four orbital model" finds it difficult to reconcile. Using distinct spectroscopy techniques, we conclude that both Qx- and Qy-bands comprise, in fact, two quasi-degenerated electronic states together with their respective vibronic progressions each. The analysis of the Huang-Rhys factors and complementary time- and polarization-resolved measurements reinforce the need for the proposed Q-band multi features remodeling.