Two birds with one stone: integrating exfoliation and immunoaffinity properties in multi-walled carbon nanotubes by non-covalent functionalization with human immunoglobulin G.

An innovative strategy is proposed to simultaneously exfoliate multi-walled carbon nanotubes (MWCNTs) and generate MWCNTs with immunoaffinity properties. This strategy was based on the non-covalent functionalization of MWCNTs with human immunoglobulin G (IgG) by sonicating 2.5 mg mL-1 MWCNTs in 2.0 mg mL-1 IgG for 15 min with sonicator bath. Impedimetric experiments performed at glassy carbon electrodes (GCE) modified with the resulting MWCNT-IgG nanohybrid in the presence of anti-human immunoglobulin G antibody (Anti-IgG) demonstrated that the immunoglobulin retains their biorecognition properties even after the treatment during the MWCNT functionalization. We proposed, as proof-of-concept, two model electrochemical sensors, a voltammetric one for uric acid quantification by taking advantages of the exfoliated MWCNTs electroactivity (linear range, 5.0 × 10-7 M - 5.0 × 10-6 M; detection limit, 165 nM) and an impedimetric immunosensor for the detection of Anti-IgG through the use of the bioaffinity properties of the IgG present in the nanohybrid (linear range, 5-50 µg mL-1; detection limit, 2 µg mL-1).

Simultaneous degradation of 30 pharmaceuticals by anodic oxidation: Main intermediaries and by-products.

The anodic oxidation (AO) of 30 pharmaceuticals including antibiotics, hormones, antihistaminics, anti-inflammatories, antidepressants, antihypertensives, and antiulcer agents, in solutions containing different supporting electrolytes media (0.05 M Na2SO4, 0.05 M NaCl, and 0.05 M Na2SO4 + 0.05 M NaCl) at natural pH was studied. A boron-doped diamond (BDD) electrode and a stainless-steel electrode were used as anode and cathode, respectively, and three current densities of 6, 20, and 40 mA cm-2 were applied. The results showed high mineralization rates, above 85%, in all the tested electrolytic media. 25 intermediaries produced during the electrooxidation were identified, depending on the supporting electrolyte together with the formation of carboxylic acids, NO3-, SO42- and NH4+ ions. The formation of intermediates in chloride medium produced an increase in absorbance. Finally, a real secondary effluent spiked with the 30 pharmaceuticals was treated by AO applying 6 mA cm-2 at natural pH and without addition of supporting electrolyte, reaching c.a. 90% mineralization after 300 min, with an energy consumption of 18.95 kW h m-3 equivalent to 2.90 USD m-3. A degradation scheme for the mixture of emerging contaminants in both electrolytic media is proposed. Thus, the application of anodic oxidation generates a high concentration of hydroxyl radicals that favors the mineralization of the pharmaceuticals present in the spiked secondary effluent sample.

Degradation of oxamic acid using dimensionally stable anodes (DSA) based on a mixture of RuO2 and IrO2 nanoparticles.

Dimensionally stable anodes (DSA) have been widely used to degrade organic compounds because these surfaces promote the electrogeneration of active chlorine species in the bulk of the solution, as well as in the vicinity of the anode when NaCl is used as supporting electrolyte. In this work, the nanoparticles synthesis of IrO2 and RuO2 was performed to obtain two types of DSA electrodes named Class I and II to degrade oxamic acid. For Class I and II DSA, the nanoparticles used were synthesized separately and in the same reaction medium, respectively. Electrolysis were carried out in an open cylindrical cell without division at 25 °C, DSAs were used as anodes and a stainless-steel electrode as cathode, both elements have a geometric area of 2.8 cm2 immersed in 0.05 mol L-1 of NaCl or Na2SO4 and a current density of 3 mA cm-2 was applied for 6 h. Active chlorine species generated in the absence of oxamic acid in NaCl were also detected and quantified through ion chromatography. In Na2SO4 there was no degradation of the compound, but in NaCl the oxamic acid concentration reaching 85% with Class I DSA. The same tendency is observed in mineralization, in which Class I DSA allowed reaching a CO2 transformation close to 73%. The difference in the results occurs because with Class I DSA, more hypochlorite is generated than with Class II and therefore there is a larger amount of oxidizing species in the solution that enables the degradation and mineralization of oxamic acid.

Nafcillin degradation by heterogeneous electro-Fenton process using Fe, Cu and Fe/Cu nanoparticles.

Heterogeneous electro-Fenton (HEF) is as an alternative to the conventional electro-Fenton (EF) process. HEF uses a solid phase catalyst, whereas EF employs a solubilized one. This implies that in HEF, material can be recovered through a simple separation process such as filtration or magnetic separation in HEF. HEF also has the advantage of not requires a previous pH adjustment, which facilitates working in a higher pH range. In this work, Fe, Cu and Fe/Cu bimetallic nanoparticles (Fe/Cu NPs) were synthesized, characterized and used for the degradation of Nafcillin (NAF). The effect of the adsorption and the anodic oxidation (AO-H2O2) process was tested to assess their influence on HEF. NAF adsorption did not exceed 24% of antibiotic removal and the AO-H2O2 process eliminated the total NAF after 240 min of electrolysis. Through the HEF process, the antibiotic was completely removed using Fe/Cu NPs after 7.0 min of electrolysis, while these NPs, mineralization reached 41% after 240 min. In this case, NAF degradation occurs mainly due to the generation of hydroxyl radicals in the BDD electrode, and the Fenton reaction with Fe and Cu NPs. The main organic intermediates produced during the degradation of NAF by HEF were identified allowing the proposal of degradation pathway. Finally, the antibiotic was also completely eliminated from a wastewater from slaughterhouse after 15 min of treatment by HEF and using Fe/Cu bimetallic NPs.

Treatment of winery wastewater by anodic oxidation using BDD electrode.

The effective removal of organics from winery wastewater was obtained in real residual effluents from the wine industry using anodic oxidation (AO). The effluent had an initial organic load of [COD]0 of 3490 mg L-1 equal to [TOC]0 of 1320 mg L-1. In addition, more than 40 organic compounds were identified by means of GC-MS. Different density currents as well as the addition of electrolytes were tested during electrolysis. The results show the decay of [COD]t by 63.6% when no support electrolyte was added, whereas almost total mineralization and disinfection was reached after adding of 50 mM of sodium sulfate and sodium chloride and applying higher density currents. The presence of sulfate and chloride in large concentration favors the production of oxidants such as hydroxyl radicals and active chlorine species that react with organics in solution. Moreover, the addition of a supporting electrolyte to industrial wastewater increases conductivity, reduces cell potential and therefore, decreases the energy consumption of the AO process.