Calculation of the ligand–lanthanide ion energy transfer rate in coordination compounds: contributions of exchange interactions

Recently, one of us (O.L.M.) developed a theoretical approach to the energy transfer process between a ligand and a lanthanide ion in luminescent compounds. This approach takes into account the direct Coulomb interaction only. Here we present further calculations which also include the exchange Coulomb interaction (isotropic and anisotropic). The selection rules on the total angular momentum, J, of the lanthanide 4f states, derived from each interaction are different. They are in fact complementary. We discuss the case of energy transfer to the ⁵D₁ manifold of the Eu³⁺ ion, which is forbidden when only the direct Coulomb interaction is considered but becomes allowed through the exchange interaction. In this case numerical estimates show that, depending on resonance conditions and the nature of the ligand donor state, the transfer rate may assume very high values. It is also emphasised that, according to the present approach, energy transfer to the ⁵D₀ level of the Eu³⁺ ion is forbidden by both mechanisms, provided J-mixing between the ⁷F₀ and ⁷F₂ manifolds is neglected.     

Studies of a novel conducting polymer by cyclic and square wave voltammetries: Its synthesis and characterization

A novel conducting polymer of polynaphthidine, poly(NAP), was synthesized electrochemically by direct anodic oxidation of naphthidine in aqueous media. The yield of the electropolymerization reaction depends on the temperature and pH of the solution. It was possible to differentiate two working regions: I (for pH < 0.5 and all temperatures) where the film yield tends to zero and II (for approximately 2.0 < pH < 2.8 and temperatures >15 °C) where the film production is maximum. Therefore, the naphthidine electrooxidation mechanism was studied under experimental conditions of region I by cyclic (CV) and square wave voltammetries (SWV) as well as by controlled potential electrolysis.The experimental conditions of region II were chosen to obtain the poly(NAP). The electrochemical response of the film was investigated in pH 1 HClO₄ + 0.1 M NaClO₄ electrolyte solution by CV and SWV. A plot of I_p,n/fvs. f from SW voltammograms showed the so-called “quasi-reversible maximum”. Formal potential, formal rate constant and anodic transfer coefficient for the surface redox process were also evaluated from the SWV.The poly(NAP) is insoluble in common organic solvents and shows electrochromic behaviour. Its probable structure was determined by FTIR spectroscopy.     

Comparison of the univariate and multivariate methods in the optimization of experimental conditions for determining Cu, Pb, Ni and Cd in biodiesel by GFAAS

Experimental design was used as a tool to define the optimum pyrolysis and atomization temperatures for four analytes (Cu, Pb, Ni and Cd) in biodiesel samples. Two chemical modifiers (Pd + Mg and W) and two distinct sample preparation procedures (microemulsion and wet digestion in a focused microwave system) were also investigated. The pyrolysis and atomization temperatures were optimized using 2⁴ factorial design for Cu, Pb, Ni and Cd, with 16 assays carried out for each analyte. The results for Cu and Pb indicated that variables of sample preparation for digestion by focused microwave was the most important one for both analytes. The pyrolysis and atomization temperatures applied were 1000 °C and 2200 °C for Cu and 500 °C and 2000 °C for Pb. None of the variables analyzed here were important for Ni, and the pyrolysis and atomization temperatures chosen for this element were 800 °C and 2300 °C. A different factorial design was used for Cd. The variables of medium and modifier were not important for this element, and the lowest temperatures, Tp-500 °C and Ta-1400 °C, were chosen based on this second design. The importance of factorial design in the simultaneous optimization of several variables studied by GFAAS was confirmed, for it involves fewer experiments and hence, lower costs, greater speed and higher efficiency.     

IL-33 and the Cytokine Storm in COVID-19: From a Potential Immunological Relationship towards Precision Medicine

Coronavirus SARS-CoV-2 has represented, and still represents, a real challenge from a clinical, diagnostic and therapeutic point of view. During acute infection, the increased levels of pro-inflammatory cytokines, which are involved in the pathology of disease and the development of SARS-CoV-2-induced acute respiratory disease syndrome, the life-threatening form of this infection, are correlated with patient survival and disease severity. IL-33, a key cytokine involved in both innate and adaptive immune responses in mucosal organs, can increase airway inflammation, mucus secretion and Th2 cytokine synthesis in the lungs, following respiratory infections. Similar to cases of exposure to known respiratory virus infections, exposure to SARS-CoV-2 induces the expression of IL-33, correlating with T-cell activation and lung disease severity. In this work, we analyse current evidence regarding the immunological role of IL-33 in patients affected by COVID-19, to evaluate not only the clinical impact correlated to its production but also to identify possible future immunological therapies that can block the most expressed inflammatory molecules, preventing worsening of the disease and saving patient lives.     

Anti-inflammatory effect of aqueous extracts of roasted and green Coffea arabica L.

Green coffee contains a large quantity and variety of polyphenols and flavonoids. The roasting affects the composition of the polyphenols in coffee, due to the formation of compounds generated by Maillard reaction, which can have anti-inflammatory or antioxidant potential. The anti-inflammatory and antioxidant effects of aqueous extracts of green (AGCa) and roasted (ARCa) coffee beans were investigated in animal models and using a DPPH radical scavenging test. In the formalin test the extracts reduced licking activity only in the late phase. The inhibitory values of oedema at 3 h post-carrageenan were 53% and 74% for 100 and 300 mg/kg of the AGCa extract and 36% for ARCa (300 mg/kg). Leukocyte recruitment into the peritoneal cavity was inhibited by the extracts. The antioxidant activities of the extracts were higher than the reference antioxidants, ascorbic acid and butylated hydroxytoluene. These results indicate that coffee extracts exhibit anti-inflammatory and antioxidant properties.     

Primary structure of water buffalo alpha-lactalbumin variants A and B

A novel electrophoretic alpha-lactalbumin (alpha-la) variant was detected in the Italian water buffalo breed. The isoelectric point of the variant, labelled A, was lower than the most frequent variant B. It presented an allelic frequency of 0.5% compared with the 97.1% of the BB allele. From Liquid Chromatography-Electrospray Ionization/Mass spectrometry, the molecular mass of the two alpha-la A and B variants were measured as 14,235.1+/-0.8 and 14,236.1+/-0.9 Da, respectively. The two proteins were sequenced and differentiated from one another by a single amino acid substitution, Asn45(B)-->Asp45(A). As this amino acid substitution altered the N-glycosylation sequence consensus Asn45-X-Ser46 it may be deduced that the protein glycosylation level of the alpha-la A would decrease.     

Storage of green coffee in hermetic packaging injected with CO2

The objective of this study was to evaluate the physical, chemical, and sensory qualities of green coffee beans (Coffea arabica L.) during storage in different types of packaging. Coffee was stored from October 2008 to September 2009 in a warehouse of the Agriculture Society Ltda. (SAAG) in Santana da Vargem, southern Minas Gerais State, Brazil. The treatments in the factorial design consisted of two types of packaging (hermetic big bags with the injection of up to 60% CO₂ in a controlled atmosphere; similar bags but without the injection of CO₂ in a modified atmosphere) and three sampling positions in the bags (high, medium, and low). At 3-month intervals during a 12-month period, grains were analyzed to determine their water content, color, electrical conductivity, potassium lixiviation, and content of sugars. Sensory analysis was also conducted at these sampling times. The storage of green coffee beans in hermetic big bags on a commercial scale under modified and controlled atmospheric conditions is viable over a 12-month period. The coffee packed in big bags maintained its quality and exhibited an intensification of the green coloration of the grains during storage. Sensory analysis of coffee beans stored in a controlled atmosphere showed that the medium sampling position yielded the best ratings. The results of this analysis demonstrated that this storage technique can potentially increase the effectiveness of methods used to preserve the sensory quality of coffee beans.     

Codex dietary fibre definition – Justification for inclusion of carbohydrates from 3 to 9 degrees of polymerisation

The main controversy about the DF definition, adopted by the commission of Codex Alimentarius, refers to the inclusion of carbohydrates of 3–9 degrees of polymerisation (DP), decision which may be made individually by the authorities of each country. Due to the possibility of having two definitions and the negative impact it would cause over the harmonisation of nutritional information, a bibliographic review was carried, from 2009 to 2011, aiming to gather justifications for the inclusion of carbohydrates of 3–9 DP in the definition. The current review presents scientific bases that are directed to three topics: physiological aspects; repercussion over the analytical method; and impact on consumers and other users. The decision of including unavailable carbohydrates of 3–9 DP in the definition of DF may cause effective global harmonisation in the nutritional labelling, considering that the main goal is to help consumers choose healthy foods.