Kraft lignin and its derivates - A study on the adsorption of mono and multielement metals, potential use for noble metal recycling and an alternative material for solid base catalyst.

Lignin is a natural polymer containing diverse functional groups and displaying an affinity for metals. Kraft lignin can be used as a carbon source, as a cleaving lignin structure for aromatic macromers or in the addition and modification of functional groups by the development of new active chemical sites. In this context, the aim of the present study is to investigate the adsorption of mono and multi-element metals solutions on lignin derivatives (unmodified Kraft lignin, acetylated Kraft lignin, charcoal Kraft lignin and activated carbon Kraft lignin). Parameters that affect adsorption processes, such as pH, contact time and adsorbent dose, were optimized in each case. The best adsorption condition was obtained at pH 7.00, a contact time of 120 min and with adsorbent dose of 30 mg. Also, unmodified Kraft lignin shows high adsorption selectivity (99%) for gold and palladium in acidic solutions. Acetylated and charcoal Kraft lignin resulted in lower adsorption levels in comparison with unmodified Kraft lignin. Activated carbon, however, reached adsorptions of over 86% for all metals. Finally, unmodified Kraft lignin impregnated with palladium presents a promising heterogeneous support in the Suzuki-Miyaura reaction.

Sol-gel-derived 58S bioactive glass containing holmium aiming brachytherapy applications: A dissolution, bioactivity, and cytotoxicity study.

Bioactive glasses containing rare earth elements have been proposed as promising candidates for applications in brachytherapy of bone cancer. However, their safety relies on a proper dissolution to avoid radioactive materials in the human body, and desirable bioactive properties to regenerate the bone defect caused by the tumor. In this work, we proposed a new series of sol-gel-derived bioactive glasses containing holmium oxide, based on the system (100-x)(58SiO2-33CaO-9P2O5)-xHo2O3 (x = 1.25, 2.5 and 5 wt%). The glasses were characterized regarding their dissolution behavior, bioactivity, and cytotoxicity with pre-osteoblastic cells. Also, in the dissolution experiments, the Arrhenius and Eyring equations were used to obtain some thermodynamic properties of glass dissolution. The results evidenced that the addition of holmium ions in the glass structure decreased the energy barrier of hydrolysis reactions, which favors glass dissolution in an early-stage. However, in the long-term, the strength of Si-O-Ho bonds may be the cause of more stable dissolution. Besides, glasses containing holmium were as bioactive as the 58S bioactive glasses, a highly bioactive composition. Cytotoxicity results showed that all glasses were not cytotoxic, and the composition containing 5 wt.% of Ho2O3 enhanced cell viability. Finally, these results suggest that these glasses are suitable materials for brachytherapy applications due to their proper dissolution behavior, high bioactivity, and high cell viability.

Removal of Orange II (OII) dye by simulated solar photoelectro-Fenton and stability of WO2.72/Vulcan XC72 gas diffusion electrode.

The objectives of this study were to determine the viability of removing Orange II (OII) dye by simulated solar photoelectro-Fenton (SSPEF) and to evaluate the stability of a WO2.72/Vulcan XC72 gas diffusion electrode (GDE) and thus determine its best operating parameters. The GDE cathode was combined with a BDD anode for decolorization and mineralization of 350 mL of 0.26 mM OII by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF) at 100, 150 and 200 mA cm-2 and SSPEF at 150 mA cm-2. The GDE showed successful operation for electrogeneration, good reproducibility and low leaching of W. Decolorization and OII decay were directly proportional to the current density (j). AO-H2O2 had a reduced performance that was only half of the SSPEF, PEF and EF treatments. The mineralization efficiency was in the following order: AO-H2O2 < EF < PEF ≈ SSPEF. This showed that the GDE, BDD anode and light radiation combination was advantageous and indicated that the SSPEF process is promising with both a lower cost than using UV lamps and simulating solar photoelectro-Fenton process. The PEF process with the lowest j (100 mA cm-2) showed the best performance-mineralization current efficiency.

Matte photographic paper as a low-cost material for metal ion retention and elemental measurements with laser-induced breakdown spectroscopy.

Matte photographic paper was explored as a low-cost material for metal-ion retention. The extraction was promoted by ultrasound, the mechanical waves of which forced adhesion to the photographic paper surface of an ion pair formed by DTAB (dodecyltrimethylammonium bromide) with the anionic coordination complex formed by metal ions and SPADNS (1,8-dihydroxy-2-(4-sulfophenylazo)naphthalene-3,6-disulfonic acid trisodium salt). As a proof of concept, the migration of copper ions present in aqueous solution to the solid phase and their direct measurement by laser-induced breakdown spectroscopy (LIBS) was evaluated. The main parameters that affected the extraction (paper type and sonication time) and analyte detection in the solid phase (delay, spot size and accumulated number of pulses) were optimised in a univariate way. The conditions influencing the complexation reaction and formation of the ion pair in aqueous solution (pH and copper, SPADNS and DTAB concentrations) were set according to a previous study. Under the optimised conditions, it was possible to use this extraction technology as an alternative in determining copper content in aqueous solutions by LIBS, overcoming the intrinsic difficulties of this instrumental technique in the analysis of liquid samples. The calibration curves were obtained in a linear range of 0.50-7.50 mg L-1 copper in solution, with detection and quantification limits estimated at 0.08 and 0.24 mg L-1, respectively. The precision of the method was less than 4.3% and the accuracy was checked by spike and recovery tests on liquid samples with different chemical compositions and by comparison of LIBS results with graphite furnace atomic absorption spectrometry data. The potential of the proposed method for extraction of Al3+, Ag+, Fe3+, Mn2+, Ni2+ and Zn2+ was also evaluated and adequate extraction efficiencies were obtained. The proposed method stands out due to its low cost and ease of execution.

Butan-1-ol as an extractant solvent in dispersive liquid-liquid microextraction in the spectrophotometric determination of aluminium.

Determining aluminium ions at µg L-1 scale currently requires either costly analytical techniques such as inductively coupled plasma, and/or graphite furnace atomic absorption spectrometry. Dispersive liquid-liquid microextraction (DLLME) is designed to promote separation and preconcentration, thus making it possible to determine the analyte of interest without significant matrix influence. This study was aimed at the development of a spectrophotometric method to determine Al3+ after microextraction of its complex with quercetin. Butan-1-ol was used as a novel extractant solvent in the DLLME process. The parameters influencing complexation and microextraction, such as the amount of quercetin and volume of extractant were evaluated by univariate analysis. In optimised conditions were estimated for the proposed method: linear range from 7.5 to 165.0 µg L-1, LOD of 2.0 µg L-1, and LOQ of 7.0 µg L-1. The accuracy was checked by applying the proposed method to water (NIST SRM-1643e) and rice flour (NIST SRM-1568c) certified reference materials and spike-and-recovery trials with distinct samples (mineral water, green tea, thermal spring water, contact lens disinfecting solution, saline concentrate for hemodialysis and urine).

Melted Paraffin Wax as an Innovative Liquid and Solid Extractant for Elemental Analysis by Laser-Induced Breakdown Spectroscopy.

This work proposes a new development in the use of melted paraffin wax as a new extractant in a procedure designed to aggregate the advantages of liquid phase extraction (extract homogeneity, fast, and efficient transfer, low cost and simplicity) to solid phase extraction. As proof of concept, copper(II) in aqueous samples was converted into a hydrophobic complex of copper(II) diethyldithiocarbamate and subsequently extracted into paraffin wax. Parameters which affect the complexation and extraction (pH, DDTC, and Triton X-100 concentration, vortex agitation time and complexation time) were optimized in a univariate way. The combination of the extraction proposed procedure with laser-induced breakdown spectroscopy allowed the precise copper determination (coefficient of variation = 3.1%, n = 10) and enhanced detectability because of the concentration factor of 18 times. A calibration curve was obtained with a linear range of 0.50-10.00 mg L-1 (R2 = 0.9990, n = 7), LOD = 0.12 mg L-1, and LOQ = 0.38 mg L-1 under optimized conditions. An extraction procedure efficiency of 94% was obtained. The accuracy of the method was confirmed through the analysis of a reference material of human blood serum, by the spike and recovery trials with seawater, tap water, mineral water, and alcoholic beverages and by comparing with those results obtained by graphite furnace atomic absorption spectrometry.

A green and efficient procedure for the preconcentration and determination of cadmium, nickel and zinc from freshwater, hemodialysis solutions and tuna fish samples by cloud point extraction and flame atomic absorption spectrometry.

Cloud point extraction (CPE) was used to simultaneously preconcentrate trace-level cadmium, nickel and zinc for determination by flame atomic absorption spectrometry (FAAS). 1-(2-Pyridilazo)-2-naphthol (PAN) was used as a complexing agent, and the metal complexes were extracted from the aqueous phase by the surfactant Triton X-114 ((1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol). Under optimized complexation and extraction conditions, the limits of detection were 0.37µgL(-1) (Cd), 2.6µgL(-1) (Ni) and 2.3µgL(-1) (Zn). This extraction was quantitative with a preconcentration factor of 30 and enrichment factor estimated to be 42, 40 and 43, respectively. The method was applied to different complex samples, and the accuracy was evaluated by analyzing a water standard reference material (NIST SRM 1643e), yielding results in agreement with the certified values.

The interaction of an azo compound with a surfactant and ion pair adsorption to solid phases.

The adsorption of SPADNS (trisodium salt of 2-(p-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid) onto resins XAD 2, XAD 7 and silica gel was studied in the presence and in the absence of the cationic surfactant CTAB (cetyl trimethylammonium bromide). At a ratio of 2.5 CTAB to 1 SPADNS, the surfactant caused a marked increase in SPADNS adsorption. The experimental results for adsorption versus time were applied on the basis of three kinetic models (pseudo-first-order Lagergren, pseudo-second-order, and intraparticle diffusion). The interaction between CTAB and SPADNS was investigated using spectrophotometric, conductometric, and computational techniques. Theoretical results point to the formation of an ion pair between CTAB and SPADNS that influences the solution spectra, in agreement with conductometric and spectrophotometric data.

Spectrophotometric flow injection methods for zinc determination in pharmaceutical and biological samples.

Zinc ions form a yellow complex with di-2-pyridyl ketone salicyloylhydrazone (DPKSH). This complex showed maximum absorption at 376 nm, and it was used to develop spectrophotometric flow injection methods for Zn(II) determination in different samples. Two types of flow systems were proposed. In the first system, a linear analytical curve was obtained in a concentration range from 0.217 to 4.60 mg L(-1) Zn(II), with a detection limit of 48.8 microg L(-1). In the second system, a minicolumn packed with an anion exchanger resin was used to concentrate Zn(II) as a chlorocomplex, and a linear analytical curve within a concentration range from 0.0824 to 2.06 mg L(-1) Zn(II) was obtained, having a detection limit of 13.9 microg L(-1). The developed methods were applied to biological and pharmaceutical samples, and a great compliance was observed by comparing the results with ones obtained by an atomic absorption technique.