Origin of Small Barriers in Jahn–Teller Systems:Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni⁺

Despite its relevance, the microscopic origin of the energy barrier, B, between the compressed and elongated geometries of Jahn–Teller (JT) systems is not well understood yet because of a lack of quantitative data about its various contributions. Seeking to clear up this matter, we have carried out both periodic and cluster ab initio calculations on the model system NaCl:Ni+. This system is particularly puzzling because, according to experimental data, its barrier is much smaller than that for other d9 and d7 ions in similar lattices. All calculations performed on the model system lead, in fact, to values |B| ≤ 160 cm–1, which are certainly smaller than B = 500 cm–1 derived for NaCl:M2+ (M = Ag, Rh) or B = 1024 cm–1 obtained for KCl:Ag2+. As a salient feature, analysis of calculations carried out as a function of the Qθ (3z2 – r2) coordinate unveils the microscopic origin of the barrier. It is quantitatively proven that the elongated geometry observed for NaCl:Ni+ is due to the 3d–4s vibronic admixture, which is slightly larger than the anharmonicity in the eg JT mode that favors a compressed geometry. The existence of these two competing mechanisms explains the low value of B for the model system, contrary to cases where the complex formed by d9 or d7 ions is elastically decoupled from the host lattice. Although the magnitude of B for NaCl:Ni+ is particularly small, the tunneling splitting, 3Γ, is estimated to be below 9 cm–1, thus explaining why the coherence is easily destroyed by random strains and thus a static JT effect is observed experimentally. As a main conclusion, the barrier in JT systems cannot be understood neglecting the tiny changes of the electronic density involved in small distortions. The present calculations reasonably explain the experimental g tensor of NaCl:Ni+, pointing out that the d–d transitions in NiCl65– are much smaller than those for CuCl64– and the optical electronegativity of Ni+ is only around 1.</p

Sinterização de argilas provenientes da Formação Corumbataí (região do Pólo Cerâmico de Santa Gertrudes, SP) frente à adição de calcário dolomítico da Formação Irati

This work researched the sintering variation, related to the addition of varied percentages of dolomitic limestones, from a formulation composed essentially by local raw materials from Corumbataí Formation and dolomitic limestones from Irati Formation. Samples from both formations were collected to experimental studies, which were consisted by X-Ray Diffraction and X-Ray Fluorescence analysis, to determine crystalline phases and chemical composition, respectively, essential feature to the formulation of masses. Test bodies were made with the obtained masses, so that the ceramic characterization physical assays could be realized. With the results of the ceramic characterization we concluded that there is a sensible variation in the sintering of the raw materials of Corumbataí Formation, when the amount of calcareous rock increases, modifying the firing properties of these. When the calcareous additions increase, there is an increment in the values of water´s absorption and reduction in the linear retraction of firing, in all the tested temperatures. In general, the mixtures tested show similarities characteristics to the masses produced for dry milling in the region, able to be implemented with easiness.Este trabalho pesquisou a variação de sinterização, relacionada à adição de porcentagens variadas de calcário dolomítico a partir de uma formulação composta essencialmente por matérias-primas locais da Formação Corumbataí e calcários dolomíticos da Formação Irati. Amostras de ambas as unidades foram recolhidas para estudos experimentais, constituídospor difração e fluorescência de raios X, para determinar, respectivamente, as fases cristalinas e composição química, características essenciais para a formulação de massas. Corpos de teste foram confeccionados com as massas obtidas, para a realização de ensaios de caracterização de cerâmica. Com base nos resultados cerâmicos concluiu-se que há uma variação sensível na sinterização das matérias-primas de Formação Corumbataí, com o incremento da quantidade de calcário, modificando as propriedades de queima destas. Conforme aumenta a adição de calcário, há incremento nos valores de absorção de água e redução da retração linear de queima, em todas as temperaturas testadas. Em geral, as misturas testadas mostram características similares às massas produzidas por moagem a seco na região, podendo ser implantadas com facilidade

Effect of SO2 and steam on CO2 capture performance of biomass-templated calcium aluminate pellets

Four types of synthetic sorbents were developed for high-temperature post-combustion calcium looping CO2 capture using Longcal limestone. Pellets were prepared with: lime and cement (LC); lime and flour (LF); lime, cement and flour (LCF); and lime, cement and flour, doped with seawater (LCFSW). Flour was used as a templating material. All samples underwent 20 cycles in a TGA under two different calcination conditions. Moreover, the prepared sorbents were tested for 10 carbonation/calcination cycles in a 68-mm-internal-diameter bubbling fluidized bed (BFB) under three environments: with no sulphur and no steam; in the presence of sulfur; and with steam. When compared to limestone, all the synthetic sorbents exhibited enhanced CO2 capture performance in both a TGA and BFB, with the exception of the sample doped with seawater. In the BFB tests, the addition of cement binder during the pelletisation process resulted in the increase of CO2 capture capacity from 0.08 gCO2/gsorbent (LF) to 0.15 gCO2/gsorbent (LCF) by the 10th cycle. The CO2 uptake in the presence of SO2 dramatically declined by the 10th cycle; for example, from 0.22 gCO2/gsorbent to 0.05 gCO2/gsorbent in the case of the untemplated material (LC). However, as expected all samples showed improved performance in the presence of steam and the decay of reactivity during the cycles was less pronounced. Nevertheless, in the BFB environment, the templated pellets showed poorer CO2 capture performance. This is presumably because of material loss due to attrition under the FB conditions. Namely, by contrast, the templated materials performed better than untemplated materials under TGA conditions. This indicates that reduction in attrition is critical in the case of employment of templated materials in realistic systems with FB reactors

Stock discrimination of two European squids (Illex coindetii, Loligo forbesii) by statolith shape analysis

We evaluated the feasibility of classifying ommastrephid and loliginid squid species by statolith shape analysis into fisheries management units or stocks. Statoliths of Illex coindetii (Verany, 1839) and Loligo forbesii (Steenstrup, 1856) were studied from multiple areas of the North East Atlantic and Northern Mediterranean Sea during 2021–2022. I. coindetii and L. forbesii individuals were categorized into multiple stocks across the areas studied. Stocks migrating between fishing areas as well as multiple stocks in the same area, as identified for L. forbesii in this study, need to be considered for sustainable fisheries management

Antimicrobial resistance profiling of Salmonella enterica distinct serotypes isolated from pork in São Paulo

Salmonellosis still is one of the most important worldwide zoonosis due to its high endemicity, mortality, and difficulty in control (Stevens et al., 2009). In the São Paulo city, different realities regarding good production practices and quality control of animal products coexists, especially when considering points of direct consumer sales. The aim of this study was to evaluate the antimicrobial resistance profiles of Salmonella enterica distinct serotypes isolated from pork in São Paulo

Combination of Pneumococcal Surface Protein A (PspA) with Whole Cell Pertussis Vaccine Increases Protection Against Pneumococcal Challenge in Mice

Streptococcus pneumoniae is the leading cause of respiratory acute infections around the world. In Latin America, approximately 20,000 children under 5 years of age die of pneumococcal diseases annually. Pneumococcal surface protein A (PspA) is among the best-characterized pneumococcal antigens that confer protection in animal models of pneumococcal infections and, as such, is a good alternative for the currently available conjugated vaccines. Efficient immune responses directed to PspA in animal models have already been described. Nevertheless, few low cost adjuvants for a subunit pneumococcal vaccine have been proposed to date. Here, we have tested the adjuvant properties of the whole cell Bordetella pertussis vaccine (wP) that is currently part of the DTP (diphtheria-tetanus-pertussis) vaccine administrated to children in several countries, as an adjuvant to PspA. Nasal immunization of BALB/c mice with a combination of PspA5 and wP or wPlow – a new generation vaccine that contains low levels of B. pertussis LPS – conferred protection against a respiratory lethal challenge with S. pneumoniae. Both PspA5-wP and PspA5-wPlow vaccines induced high levels of systemic and mucosal antibodies against PspA5, with similar profile, indicating no essential requirement for B. pertussis LPS in the adjuvant properties of wP. Accordingly, nasal immunization of C3H/HeJ mice with PspA5-wP conferred protection against the pneumococcal challenge, thus ruling out a role for TLR4 responses in the adjuvant activity and the protection mechanisms triggered by the vaccines. The high levels of anti-PspA5 antibodies correlated with increased cross-reactivity against PspAs from different clades and also reflected in cross-protection. In addition, passive immunization experiments indicated that antibodies played an important role in protection in this model. Finally, subcutaneous immunization with a combination of PspA5 with DTPlow protected mice against challenge with two different pneumococcal strains, opening the possibility for the development of a combined infant vaccine composed of DTP and PspA

A compact multifunctional microfluidic platform for exploring cellular dynamics in real-time using electrochemical detection

Downscaling of microfluidic cell culture and detection devices for electrochemical monitoring has mostly focused on miniaturization of the microfluidic chips which are often designed for specific applications and therefore lack functional flexibility. We present a compact microfluidic cell culture and electrochemical analysis platform with in-built fluid handling and detection, enabling complete cell based assays comprising on-line electrode cleaning, sterilization, surface functionalization, cell seeding, cultivation and electrochemical real-time monitoring of cellular dynamics. To demonstrate the versatility and multifunctionality of the platform, we explored amperometric monitoring of intracellular redox activity in yeast (Saccharomyces cerevisiae) and detection of exocytotically released dopamine from rat pheochromocytoma cells (PC12). Electrochemical impedance spectroscopy was used in both applications for monitoring cell sedimentation and adhesion as well as proliferation in the case of PC12 cells. The influence of flow rate on the signal amplitude in the detection of redox metabolism as well as the effect of mechanical stimulation on dopamine release were demonstrated using the programmable fluid handling capability. The here presented platform is aimed at applications utilizing cell based assays, ranging from e.g. monitoring of drug effects in pharmacological studies, characterization of neural stem cell differentiation, and screening of genetically modified microorganisms to environmental monitoring