Luis Henrique Mendes da Silva

Application of hydrophobic extractant in aqueous two-phase systems for selective extraction of cobalt, nickel and cadmium.

This work developed a new and efficient method of extracting and separating Co(II), Ni(II) and Cd(II) in aqueous two-phase systems (ATPS) composed of triblock copolymer (L64)+Na(2)C(4)H(4)O(6)+water and L64+Li(2)SO(4)+water using the hydrophobic extractant 1-nitroso-2-naphtol, which complexes the metal ions and partitions in the triblock copolymer micelles in the ATPS top phase. Metal extraction from the salt-rich phase to the copolymer - rich phase is strongly affected by the fine-tuning of the following parameters: amount of added extractant, type of electrolyte, pH, and tie-line length. Excellent separation factors (S(i,j)) between the metals were obtained at pH=3.00 (S(Co,Cd)=1550 and S(Ni,Cd)=16,700) and pH=1.00 (S(Co,Ni)=826). In the interference study, Co(II) was selectivity extracted in the top phase in the presence of Ni(II) and Cd(II) in a concentration of up to 20 times the cobalt level in the system.

Application of aqueous two-phase systems for the development of a new method of cobalt(II), iron(III) and nickel(II) extraction: A green chemistry approach

We have investigated the extraction behavior of the metallic ions Co(II), Fe(III) and Ni(II) as a function of the amount of potassium thiocyanate used as an extracting agent, using the following aqueous two-phase systems (ATPS): PEO + (NH(4))(2)SO(4) + H(2)O, PEO + Li(2)SO(4) + H(2)O, L35 + (NH(4))(2)SO(4) + H(2)O and L35 + (Li)(2)SO(4)+H(2)O. Metal extraction from the salt-rich phase to the polymer-rich phase is affected by the following parameters: amount of added extractant, pH, and the nature of the electrolyte and polymer that forms the ATPS. Maximal extraction percentages were obtained for Co(II) (99.8%), Fe(III) (12.7%) and Ni(II) (3.17%) when the ATPS was composed of PEO1500 + (NH(4))(2)SO(4) + H(2)O containing 1.4 mmol of KSCN at pH 4.0, providing separation factors as high as S(Co, Fe) = 3440 and S(Co, Ni) = 15,300. However, when the same ATPS was used at pH 2.0, the maximal extraction percentages for iron and nickel were 99.5% and 4.34%, respectively, with S(Fe, Ni) equal to 4380. The proposed technique was shown to be efficient in the extraction of Co(II) and Fe(III), with large viability for the selective separation of Co(II) and Fe(III) ions in the presence of Ni(II).

Thermodynamic study of colorimetric transitions in polydiacetylene vesicles induced by the solvent effect.

We report the synthesis of 10,12-pentacosadyinoic acid (PCDA) and PCDA + cholesterol (CHO) + sphingomyelin (SPH) vesicles dispersed in water and the determination of their colorimetric response induced by small amount of organic solvents. In the absence of solvent, PCDA and PCDA/CHO/SPH vesicles showed an intense blue color. The addition of CHCl(3), CH(2)Cl(2), and CCl(4) caused a colorimetric transition (CT) in both structures with the following efficiency: CHCl(3) > CH(2)Cl(2) ≅ CCl(4). However, CH(3)OH did not cause a blue-to-red transition. By microcalorimetric technique we also determined, for the first time, the enthalpy change associated with the CT process and the energy of interaction between solvent molecules and vesicle self-assembly. We observed that the chloride solvents induced a colorimetric transition, but the thermodynamic mechanism was different for each of them. CT induced by CHCl(3) was enthalpically driven, while that caused by CH(2)Cl(2) or CCl(4) was entropically driven.

Copper recovery from ore by liquid-liquid extraction using aqueous two-phase system.

We investigated the extraction behavior of Cu(II) in the aqueous two-phase system (ATPS) formed by (L35+MgSO(4)+H(2)O) or (L35+(NH(4))(2)SO(4)+H(2)O) in the presence of the extracting agent 1-(2-pyridylazo)-2-naphthol (PAN). At pH=3 and a PAN concentration of 0.285 mmol kg(-1), both ATPS lead to the effective separation of Cu(II) from other metallic ions (Zn(II), Co(II), Ni(II) and Fe(III)). High separation factors range between 1000 and 10,000 were obtained for the extraction of Cu(II) and concomitant metallic ions. This ATPS was used for the extraction of Cu(II) from a leached ore concentrate with a extraction percentage of 90.4 ± 1.1%; other metals were mainly located in the bottom phase.

A green and sensitive method to determine phenols in water and wastewater samples using an aqueous two-phase system

A greener and more sensitive spectrophotometric procedure has been developed for the determination of phenol and o-cresol that exploits an aqueous two-phase system (ATPS) using a liquid-liquid extraction technique. An ATPS is formed mostly by water and does not require organic solvent. Other ATPS components used in this study were the polymer, polyethylene oxide, and some salts (i.e., Li(2)SO(4), Na(2)SO(4) or K(2)HPO(4)+KOH). The method is based on the reaction between phenol, sodium nitroprusside (NPS) and hydroxylamine hydrochloride (HL) in an alkaline medium (pH 12.0), producing the complex anion [Fe(2)(CN)(10)](10-) that spontaneously concentrates in the top phase of the system. The linear range was 1.50-500microgkg(-1) (R>or=0.9997; n=8) with coefficients of variation equal to 0.38% for phenol and 0.30% for o-cresol (n=5). The method yielded limits of detection (LODs) of 1.27 and 1.88microgkg(-1) and limits of quantification (LOQs) of 4.22 and 6.28microgkg(-1) for phenol and o-cresol, respectively. Recoveries between 95.7% and 107% were obtained for the determination of phenol in natural water and wastewater samples. In addition, excellent agreement was observed between this new ATPS method and the standard 4-aminoantipyrine (4-AAP) method.

PEO-[M(CN)5NO](x-) (M = Fe, Mn, or Cr) interaction as a driving force in the partitioning of the pentacyanonitrosylmetallate anion in ATPS: strong effect of the central atom.

The partitioning behavior of pentacyanonitrosilmetallate complexes[Fe(CN) 5 NO] (2-), [Mn(CN) 5 NO] 3(-), and [Cr(CN) 5 NO] 3(-)has been studied in aqueous two-phase systems (ATPS) formed by adding poly(ethylene oxide) (PEO; 4000 g mol (-1)) to an aqueous salt solution (Li2 SO4, Na2 SO4, CuSO4, or ZnSO4). The complexes partition coefficients ( K complex) in each of these ATPS have been determined as a function of increasing tie-line length (TLL) and temperature. Unlike the partition behavior of most ions, [Fe(CN) 5 NO] 2(-) and [Mn(CN) 5 NO] 3(-) anions are concentrated in the polymer-rich phase with K values depending on the nature of the central atom as follows: K [Fe(C N) 5 NO] 2 - >> K [ Mn (CN 5 NO] 3 - > K [C r (C N) 5 NO ]3 - . The effect of ATPS salts in the complex partitioning behavior has also been verified following the order Li2 SO 4 > Na2 SO 4 > ZnSO4. Thermodynamic analysis revealed that the presence of anions in the polymer-rich phase is caused by an EO-[M(CN) 5 NO] ( x- ) (M = Fe, Mn, or Cr) enthalpic interaction. However, when this enthalpic interaction is weak, as in the case of the [Cr(CN) 5 NO]3(-) anion ( K [Cr(CN 5 NO] 3 - < 1), entropic driving forces dominate the transfer process, then causing the anions to concentrate in the salt-rich phase.

Increased presevation of sliced mozzarella cheese by antimibrobial sachet incorporated with allyl isothiocyanate

There is an increasing tendency to add natural antimicrobials of plant origin into food. The objective of this work was to develop a microbial sachet incorporated with allyl isothiocyanate (AIT), a volatile compound of plant origin, and to test its efficiency against growth of yeasts and molds, Staphylococcus sp. and psychrotrophic bacteria on sliced mozzarella cheese. Another objective was to quantify the concentration of AIT in the headspace of cheese packaging. A reduction of 3.6 log cycles was observed in yeasts and molds counts in the mozzarella packed with the antimicrobial sachet over 15-day storage time. The sachet also showed an antibacterial effect on Staphylococcus sp., reducing 2.4 log cycles after 12-day storage. Psychrotrophic bacteria species were the most resistant to the antimicrobial action. The highest concentration of AIT (0.08µg.mL(-1)) inside the active packaging system was observed at the 6(-)day of storage at 12 oC ± 2 oC. At the end of the storage time, AIT concentration decreased to only 10% of the initial concentration. Active packaging containing antimicrobial sachet has a potential use for sliced mozzarella, with molds and yeasts being the most sensitive to the antimicrobial effects.

Application of the response surface methodology for optimization of whey protein partitioning in PEG/phosphate aqueous two-phase system.

In order to develop a new strategy for β-lactoglobulin (β-lg) removal from whey protein, partitioning of α-lactalbumin (α-la), β-lg and glycomacropeptide (Gmp) was studied using aqueous two phase systems (ATPS). A system composed of 13% (w/w) polyethylene glycol (PEG, average molar mass 2000 g/mol) and 13% (w/w) potassium phosphate was used at 25°C. A central composite rotatable design (CCRD) associated to the response surface methodology (RSM) was applied to investigate the effects of NaCl concentration and pH on the partition of these proteins. It was found that α-la and Gmp partitioned to the top phase rich in PEG, whereas β-lg partitioned to the bottom phase rich in salt. According to the RSM, optimal conditions for β-lg removal where found where pH was equal to 6.7 and salt concentration was 0.35 mol/L. Under these conditions, the partition coefficient K(α) was 0.48 and K(Gmp) was 0.92. On the other hand, the partition coefficient K(β) was only 0.01. In such conditions β-lg preferentially concentrates in the bottom phase, while the top phase exclusively contains the proteins α-la and Gmp. Fractionation of the proteins from fresh whey was performed in a three stage cross-flow extraction system. The extraction yield for β-lg in the bottom phase was 97.3%, while the yields for α-la and Gmp in the top phase were 81.1% and 97.8%, respectively.

Antimicrobial Effects of Silver Nanoparticles against Bacterial Cells Adhered to Stainless Steel Surfaces

Given the increasing number of antibiotic-resistant bacteria and the need to synthesize new antimicrobials, silver has attracted interest in the scientific community because of its recognized antimicrobial activity. This study aimed to evaluate the antimicrobial effects of silver nanoparticles (NP) obtained by a new method and tested at concentrations of 6 μg/ml and 60 μg/ml against the species Staphylococcus aureus, Listeria innocua, Salmonella Choleraesuis, Pseudomonas aeruginosa, Escherichia coli, and Bacillus cereus. The ability of these nanoparticles to remove or kill vegetative cells adhered to stainless steel surfaces was also evaluated. We observed that the NP obtained with the new method, concentrated silver nanoparticles (CNP), and silver nanoparticles with added sodium chloride (NPNaCl) had high antimicrobial activities (P < 0.05). We also verified that the most effective condition for the removal of P. aeruginosa cells on stainless steel coupons (10 by 10 mm) was immersion of the surfaces in CNP. The CNP treatment produced a 5-log reduction of the microbial population after 30 to 60 min of immersion. The CNP treatment also performed better than water and sodium carbonate, a compound commonly applied in clean-in-place procedures in the food industry, in removing adherent B. cereus cells from stainless steel cylinders. Therefore, these results suggest that NP synthesized by a new procedure may be used as antimicrobials in the food industry, for example, for the sanitization of utensils that come into contact with foods.

Thermodynamic studies of partitioning behavior of lysozyme and conalbumin in aqueous two-phase systems

The objective of this study was to determine the thermodynamic parameters (Delta(tr)G, Delta(tr)H and Delta(tr)S) associated with lysozyme and conalbumin partitioning in aqueous two-phases systems (ATPS). Influence of salt type and polyethylene glycol (PEG) concentrations on the partition coefficient of lysozyme and conalbumin from egg white was studied. The evaluated ATPS were composed of PEG 1500 and inorganic salts (sodium citrate and sodium sulfate) at a temperature of 25 degrees C and pH 7.0, with PEG 1500 g mol(-1) concentrations of 14%, 16% and 18% (mass basis). Partitioning of lysozyme in PEG-citrate ATPS was enthalpically driven, however the PEG-sulfate ATPS was entropically driven. The tested systems can be employed for the separation of these two proteins in egg white, due to the fact that lysozyme migrates toward the polymeric phase and conalbumin to the saline phase in both ATPS. A high recovery of conalbumin in the saline phase of the PEG-sulfate ATPS was determined to be enthalpically driven.