Bioremoval of Yttrium (III), Cerium (III), Europium (III), and Terbium (III) from Single and Quaternary Aqueous Solutions Using the Extremophile Galdieria sulphuraria (Galdieriaceae, Rhodophyta).

The lanthanides are among the rare earth elements (REEs), which are indispensable constituents of modern technologies and are often challenging to acquire from natural resources. The demand for REEs is so high that there is a clear need to develop efficient and environmentally-friendly recycling methods. In the present study, living cells of the extremophile Galdieria sulphuraria were used to remove four REEs, Yttrium, Cerium, Europium, and Terbium, from single- and quaternary-metal aqueous solutions. Two different strains, SAG 107.79 and ACUF 427, were exposed to solutions buffered at pH 2.5, 3.5, 4.5, and 5.5. Our data demonstrated that the removal performances were strain and pH dependent for all metal ions. At lower pH, ACUF 427 outperformed SAG 107.79 considerably. By increasing the pH of the solutions, there was a significant surge in the aqueous removal performance of both strains. The same trend was highlighted using quaternary-metal solutions, even if the quantities of metal removed were significantly lower. The present study provided the first insight into the comparative removal capacity of the Galdieria sulphuraria strains. The choice of the appropriate operational conditions such as the pH of the metal solutions is an essential step in developing efficient, rapid, and straightforward biological methods for recycling REEs.

High-Energy-Density Materials: An Amphoteric N-Rich Bis(triazole) and Salts of Its Cationic and Anionic Species.

The synthesis and characterization of the N-rich bis(triazole) compound 1H,4'H-[3,3'-bis(1,2,4-triazole)]-4',5,5'-triamine (C4H7N9) with a N content of 69.6% by weight is reported. The compound exhibits a rich acid-base behavior because it can accept up to two protons, forming a monocation and a dication, and can lose one proton, forming an anion. Measurement of the acid constants has shown that there exist well-defined pH intervals in which each of the four species is predominant in solution, opening the way to their isolation and characterization by single-crystal X-ray analysis as salts with different counterions. Some energetic salts of the monocation or dication containing oxidizing inorganic counterions (dinitramide, perchlorate, and nitrate) were also prepared and characterized in the solid state for their sensitivity. In particular, the neutral compound shows a very remarkable thermal stability in air, with Td = 347 °C, and is insensitive to impact and friction. Salts of the dication with energetic counterions, in particular perchlorate and nitrate, show increased sensitivities and reduced thermal stability. The salt of the monocation with dinitramide as the counterion outperforms other dinitramide salts reported in the literature because of its higher thermal stability (Td = 230 °C in air) and friction insensitiveness.

Potential roles of mitochondrial cofactors in the adjuvant mitigation of proinflammatory acute infections, as in the case of sepsis and COVID-19 pneumonia.

BACKGROUND: The mitochondrial cofactors α-lipoic acid (ALA), coenzyme Q10 (CoQ10) and carnitine (CARN) play distinct and complementary roles in mitochondrial functioning, along with strong antioxidant actions. Also termed mitochondrial nutrients (MNs), these cofactors have demonstrated specific protective actions in a number of chronic disorders, as assessed in a well-established body of literature. METHODS: Using PubMed, the authors searched for articles containing information on the utilization of MNs in inflammatory disorders as assessed from in vitro and animal studies, and in clinical trials, in terms of exerting anti-inflammatory actions. RESULTS: The retrieved literature provided evidence relating acute pathologic conditions, such as sepsis and pneumonia, with a number of redox endpoints of biological and clinical relevance. Among these findings, both ALA and CARN were effective in counteracting inflammation-associated redox biomarkers, while CoQ10 showed decreased levels in proinflammatory conditions. MN-associated antioxidant actions were applied in a number of acute disorders, mostly using one MN. The body of literature assessing the safety and the complementary roles of MNs taken together suggests an adjuvant role of MN combinations in counteracting oxidative stress in sepsis and other acute disorders, including COVID-19-associated pneumonia. CONCLUSIONS: The present state of art in the use of individual MNs in acute disorders suggests planning adjuvant therapy trials utilizing MN combinations aimed at counteracting proinflammatory conditions, as in the case of pneumonia and the COVID-19 pandemic.

Tautomeric and conformational switching in a new versatile N-rich heterocyclic ligand.

A new N-rich triazolo-triazole derivative, 4-methyl-7-(pyrazin-2-yl)-2H-[1,2,4]triazolo[3,2-c][1,2,4]triazole (C8H7N7), bearing a pyrazine residue at 7-position of the triazolo-triazole bicycle, was synthesized, and its acid-base and metal coordination properties were evaluated in solution. The results showed amphoteric behavior and the formation of stable complexes with Cu(ii) and Zn(ii) in pH intervals in which the ligand is neutral or deprotonated. Computational studies were performed in order to evaluate the stability of the different tautomers/conformers of the ligand, and the proton position in the neutral and acidic forms. Single crystal X-ray analysis of the free neutral ligand (2H/s-trans tautomer/conformer), and of its singly protonated (2H-3H/s-trans), doubly protonated (2H-3H-7H/s-trans) and deprotonated forms showed that the influence of the pyrazine ring on the triazolo-triazole system is mainly as electron withdrawing and chelating group, and proton acceptor. Different coordination modes have been evidenced for the neutral and deprotonated ligand. Upon metal coordination, the neutral ligand switches from 2H/s-trans to 3H/s-cis tautomer/conformer forming five-membered chelate rings, while the anionic deprotonated ligand forms six-membered chelate rings in the s-trans conformation. Altogether, five different tautomers/conformers of the ligand were isolated and characterized. In vitro tests confirmed the general antiproliferative activity of triazolo-triazole compounds and the importance of substitution in position 7 for their selectivity.

Solid State Separation and Isolation of Tautomers of Fused-Ring Triazolotriazoles.

Fine control of the tautomeric forms of [1,2,4]triazolo[3,2-c][1,2,4]triazole derivatives in acidic conditions has been achieved by acting on the electronic character of the substituent at position 7 of the heterobicycle and on the counterion. Strong electron releasing or electron withdrawing substituents lead almost exclusively to a single tautomeric form, the 1H-3H or the 2H-3H, respectively. In the case of the phenol substituent, both tautomeric forms are present in comparable amount in solution; the two tautomers can also be selectively precipitated in different crystalline salts using suitable counterions.

Modeling the acid-base properties of bacterial surfaces: A combined spectroscopic and potentiometric study of the gram-positive bacterium Bacillus subtilis.

In this study, macroscopic and spectroscopic data were combined to develop a surface complexation model that describes the acid-base properties of Bacillus subtilis. The bacteria were freeze-dried and then resuspended in 0.1 M NaCl ionic medium. Macroscopic measurements included potentiometric acid-base titrations and electrophoretic mobility measurements. In addition, ATR-FTIR spectra of wet pastes from suspensions of Bacillus subtilis at different pH values were collected. The least-squares program MAGPIE was used to generate a surface complexation model that takes into account the presence of three acid-base sites on the surface: tripple bond COOH, tripple bond NH+, and tripple bond PO-, which were identified previously by XPS measurements. Both potentiometric titration data and ATR-FTIR spectra were used quantitatively, and electrostatic effects at the charged bacterial surface were accounted for using the constant capacitance model. The model was calculated using two different approaches: in the first one XPS data were used to constrain the ratio of the total concentrations of all three surface sites. The capacitance of the double layer, the total buffer capacity, and the deprotonation constants of the tripple bond NH+, tripple bond POH, and tripple bond COOH species were determined in the fit. A second approach is presented in which the ratio determined by XPS of the total concentrations of tripple bond NH+ to tripple bond PO- sites is relaxed. The total concentration of tripple bond PO- sites was determined in the fit, while the deprotonation constant for tripple bond POH was manually varied until the minimization led to a model which predicted an isoelectric point that resulted in consistency with electrophoretic mobility data. The model explains well the buffering capacity of Bacillus subtilis suspensions in a wide pH range (between pH=3 and pH=9) which is of considerable environmental interest. In particular, a similar quantitative use of the IR data opens up possibilities to model other bacterial surfaces at the laboratory scale and help estimate the buffering capacity of carboxylate-containing compounds in natural samples.

Potentiometric determination of the total acidity of humic acids by constant-current coulometry.

A straightforward method for both the quantitative and the equilibrium analysis of humic acids in solution, based on the combination of potentiometry with coulometry, is presented. The method is based on potentiometric titrations of alkaline solutions containing, besides the humic acid sample, also NaClO(4) 1M; by means of constant current coulometry the analytical acidity in the solutions is increased with a high precision, until the formation of a solid phase occurs. Hence, the total acid content of the macromolecules may be determined from the e.m.f. data by using modified Gran plots or least-squares sum minimization programs as well. It is proposed to use the pK(w) value in the ionic medium as a check of the correctness of each experiment; this datum may be readily obtained as a side-result in each titration. Modelling acid-base equilibria of the HA samples analysed was also performed, on the basis of the buffer capacity variations occurring during each titration. The experimental data fit, having the least standard deviation, was obtained assuming a mixture of three monoprotic acids (HX, HY, HZ) having about the same analytical concentration, whose acid dissociation constants in NaClO(4) 1M at 25 degrees C were pK(HX)=3.9+/-0.2, pK(HY)=7.5+/-0.3, pK(HZ)=9.5+/-0.2, respectively. With the proposed method the handling of alkaline HA solutions, the titration with very dilute NaOH or HCl solutions and the need for the availability of very small volumes of titrant to be added by microburettes may be avoided.

On the hydrolysis of the dioxouranium(VI) ion in oxalate solutions.

The complex formation between the dioxouranium (VI) and the oxalate ions has been investigated by measuring the potential of a glass electrode, at 25.00 degrees C, in 1 and 3 M NaClO4, at lower acidities than 10(-4.5) M, in order to favour the formation of (mixed) ternary species. The upper limits of concentration of all the analytical parameters have been imposed by the modest solubility of Na2C2O4 in the ionic media. The experimental measurements at different ionic strengths have been treated by means of the computerised least square programme LETAGROP - ETITR. Ternary complexes of general composition (p, q, r) are formed according to reaction (1), in addition to the already reported binary complexes. pUO2(2+) + qH2O + rC2O4(2-) <==> (UO2)p(OH)q(C2O4)r(2p-q-2r)(+) + qH+ (1). The stoichiometric compositions of the ternary species are (1, 1, 1), (2, 4, 2), (2, 2, 4). Their formation constants, expressed in molality, obtained in the two ionic media, are listed below. [table: see text]. For reasons discussed in the present work in the last column only the value of the constant in 1 M ionic medium is reported for the species (2, 4, 2). Additional evidence on the stoichiometric composition of the species formed is afforded by the mass-spectrometric measurements, collected in solutions of known composition.

Complex formation between phytic acid and divalent metal ions: a solution equilibria and solid state investigation.

An investigation on the complex formation equilibria between divalent metal ions Me (with Me=Mn, Co, Ni, Cu, Cd, and Pb) and phytic acid (H(12)L) is presented. Experiments were performed through a potentiometric methodology by measuring, at 25 degrees C, the proton and, in some cases (Cu(2+), Cd(2+), and Pb(2+)), also the metal ion activity at equilibrium in solutions containing, besides the metal and the ligand, 3 M NaClO(4) as the ionic medium. Unhydrolyzed solutions of the metal ion at millimolar concentration levels were titrated with solutions of about 10 mM sodium phytate, until the formation of a solid phase took place (always at pH approximately 2.5, except in the case of Cu(2+), which formed soluble complexes up to pH approximately 3.3). Coulometry was employed to produce very dilute solutions of either Cu(2+), Cd(2+), or Pb(2+) of accurately known composition. The emf data were explained by assuming, in the acidity interval explored, the formation of the complexes of general stoichiometry MeH(5)L(5-) and Me(2)H(3)L(5-). Coordination compounds in the solid state were also synthesized and characterized by elemental analysis, thermal analysis, and ICP spectroscopy. The solids had a general stoichiometry Me(6)H (t)LCl (t). x H(2)O, with the following t and x values for each metal investigated: Me ( t; x) = Mn (4; 2); Co (4; 2); Ni (4; 2); Cu (2; 2.5); Zn (2; 1); Sn (6; 6).