Synthesis of a New Polyanion Possessing Dense 1,2,3-Triazole Backbone

Polyanions are an important class of water-soluble polymers because polyanions are utilized in a wide range of industrial fields. It is thus a great challenge to develop polyanions with novel structures to make their applications broader. In this study, a new polyanion with a dense 1,2,3-triazole backbone, poly(4-azido-5-hexanoic acid) (poly(AH)), was synthesized by copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerization of t-butyl 4-azido-5-hexanoate followed by hydrolysis of the t-butyl ester groups. Turbidimetric and potentiometric titration data indicated that poly(AH) was well soluble in water under basic conditions (pH < 7) and a weaker polyanion (apparent pKa = 5.4) than polyacrylic acid (apparent pKa = 4.5). Adsorption tests exhibited that sodium salt of poly(AH) (poly(AH)Na) adsorbed most preferably Fe3+ among the four metal ions examined, i.e., Cu2+, Pb2+, Li+, and Fe3+. 1H spin-lattice relaxation time measurements indicated that Fe3+ ions were adsorbed favorably onto the 1,2,3-triazole residues.

Thermodynamic Study on the Dissociation and Complexation of Coumarinic Acid with Neodymium(III) and Dioxouranium(VI) in Aqueous Media

In the frame of a systematic study on the sequestering ability of natural antioxidants towards metal cations, the complexation of coumarin-3-carboxilic acid (HCCA) with neodymium(III) and dioxouranium(VI) (uranyl, UO22+), and overall stability constants of the resulting complexes, were evaluated from the pH-potentiometric titration data at 37 °C and in an aqueous solution (i.e., 0.16 mol/L NaClO4). The graphic representation of the complex’s concentration curves is given by the distribution diagrams, which provide a depiction of all the species present in the solution in the selected pH ranges. The protonation constant of HCCA was also determined to evaluate the competition of the ligand for the metal cations and H+. The ligand-to-metal concentration ratio was varied between 1 and 10, and the hydrogen ion concentration was decreased stepwise until the incipient precipitation of a basic salt of the metal, which occurred at different values depending on the specific metal cation and the ligand to metal ratio. Speciation profiles obtained by potentiometric titrations and supported by UV-Vis data show that a complexation occurs at a ligand-to-Nd(III) and to –UO22+ ratio of 1:1 and 2:1, with different degrees of deprotonation: Nd(OH)(CCA)+, UO2(OH)(CCA), UO2(OH)2(CCA)−, and Nd(OH)(CCA)2, UO2(CCA)2 and (UO2)2(OH)2(CCA)2.

Human Plasma and Recombinant Hemopexins: Heme Binding Revisited

Plasma hemopexin (HPX) is the key antioxidant protein of the endogenous clearance pathway that limits the deleterious effects of heme released from hemoglobin and myoglobin. During intra-vascular hemolysis, heme partitioning to protein and lipid increases as the plasma concentration of HPX declines. Therefore, the development of HPX as a replacement therapy during high heme stress could be a relevant intervention for hemolytic disorders. A logical approach to enhance HPX yield involves recombinant production strategies from human cell lines. The present study focuses on a biophysical assessment of heme binding to recombinant human HPX (rhHPX) produced in the Expi293FTM (HEK293) cell system. In this report, we examine rhHPX in comparison with plasma HPX using a systematic analysis of protein structural and functional characteristics related to heme binding. Analysis of rhHPX by UV/Vis absorption spectroscopy, circular dichroism (CD), SEC-HPLC and catalase-like activity demonstrated a similarity to HPX fractionated from plasma. In particular, the titration of HPX apo-protein(s) with heme was performed for the first time using a wide range of heme concentrations to model HPX-heme interactions to approximate physiological conditions (from extremely low to more than 2-fold heme excess). The CD titration data showed an induced bisignate CD Soret band pattern typical for plasma and rhHPX versions at low heme-to-protein molar ratios and demonstrated that further titration is dependent on the amount of protein-bound heme to the extent that the arising opposite CD couplet results in a complete inversion of the observed CD pattern. The data generated in this study suggests more than one binding site in both plasma and rhHPX. Further, our study provides a useful analytical platform for detailed characterization of HPX-heme interactions and potentially, novel HPX fusion constructs.

Water Soluble Host–Guest Chemistry Involving Aromatic N-Oxides and Sulfonateresorcinarene

Resorcinarenes decorated with sulfonate groups are anionic in nature and water soluble with a hydrophobic electron-rich interior cavity. These receptors are shown to bind zwitterionic aromatic mono-N-oxides and cationic di-N-oxide salts with varying spacer lengths. Titration data fit a 1:1 binding isotherm for the mono-N-oxides and 2:1 binding isotherm for the di-N-oxides. The first binding constants for the di-N-oxides (K1: 104 M−1) are higher compared to the neutral mono-N-oxide (K: 103 M−1) due to enhanced electrostatic attraction from a receptor with an electron-rich internal cavity and cationic and electron deficient N-oxides. The interaction parameter α reveals positive cooperativity for the di-N-oxide with a four-carbon spacer and negative cooperativity for the di-N-oxides that have spacers with more four carbons. This is attributed to shape complementarity between the host and the guest.

Electrochemical Sensor Based on a Carbon Veil Modified by Phytosynthesized Gold Nanoparticles for Determination of Ascorbic Acid

An original voltammetric sensor (Au-gr/CVE) based on a carbon veil (CV) and phytosynthesized gold nanoparticles (Au-gr) was developed for ascorbic acid (AA) determination. Extract from strawberry leaves was used as source of antioxidants (reducers) for Au-gr phytosynthesis. The sensor was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy and electrochemical methods. Optimal parameters of AA determination were chosen. The sensor exhibits a linear response to AA in a wide concentration range (1 μM–5.75 mM) and a limit of detection of 0.05 μM. The developed sensor demonstrated a high intra-day repeatability of 1 μM AA response (RSD = 1.4%) and its stability during six weeks, selectivity of AA determination toward glucose, sucrose, fructose, citric, tartaric and malic acids. The proposed sensor based on Au-gr provides a higher sensitivity and a lower limit of AA detection in comparison with the sensor based on gold nanoparticles synthesized by the Turkevich method. The sensor was successfully applied for the determination of AA content in fruit juices without samples preparation. The recovery of 99%–111% and RSD no more than 6.8% confirm the good reproducibility of the juice analysis results. A good agreement with the potentiometric titration data was obtained. A correlation (r = 0.9867) between the results of AA determination obtained on the developed sensor and integral antioxidant activity of fruit juices was observed.

Synthesis and Binding Studies of a Novel Highly Selective Ag(I) Ligand

Ligands bearing <i>S</i>- and <i>N</i>- donors are an important class of extractants with demonstrated efficiency and selectivity for Ag⁺ extraction over metals with similar chemistries. However, the synthesis of some of these ligands can be complicated and low yielding. Here, we report the synthesis of a novel ligand - <i>N</i>-(2-((4-vinylbenzyl)thio)ethyl)acetamide, over two simple steps and in a good yield. The extractant was observed to demonstrate excellent selectivity for Ag⁺, extracting only Ag⁺ from an aqueous solution also containing Cu²⁺ and Pb²⁺. Moderate extraction efficiencies of 36 % for Ag⁺ and 0% each for Cu²⁺ and Pb²⁺ were observed. From mass spectrometry and proton NMR titration data, the extractant was found to form both the 1:1 and 1:2 (Ag⁺:ligand) complexes with Ag⁺indicating that ligand forms bent linear and tetrahedral coordination complexes with Ag⁺. Overall, the results indicate that the novel amide-based ligand is highly selective for Ag⁺ removal from aqueous solutions containing Cu²⁺ and Pb²⁺. These results indicate the ligand could be easily synthesized and applied for selective silver recovery from low grade ores.

Synthesis and Binding Studies of a Novel Highly Selective Ag(I) Ligand

Ligands bearing <i>S</i>- and <i>N</i>- donors are an important class of extractants with demonstrated efficiency and selectivity for Ag⁺ extraction over metals with similar chemistries. However, the synthesis of some of these ligands can be complicated and low yielding. Here, we report the synthesis of a novel ligand - <i>N</i>-(2-((4-vinylbenzyl)thio)ethyl)acetamide, over two simple steps and in a good yield. The extractant was observed to demonstrate excellent selectivity for Ag⁺, extracting only Ag⁺ from an aqueous solution also containing Cu²⁺ and Pb²⁺. Moderate extraction efficiencies of 36 % for Ag⁺ and 0% each for Cu²⁺ and Pb²⁺ were observed. From mass spectrometry and proton NMR titration data, the extractant was found to form both the 1:1 and 1:2 (Ag⁺:ligand) complexes with Ag⁺indicating that ligand forms bent linear and tetrahedral coordination complexes with Ag⁺. Overall, the results indicate that the novel amide-based ligand is highly selective for Ag⁺ removal from aqueous solutions containing Cu²⁺ and Pb²⁺. These results indicate the ligand could be easily synthesized and applied for selective silver recovery from low grade ores.