Amperometric biosensors based on the use of glucose oxidase (GOx) are able to combine the robustness of electrochemical techniques with the specificity of biological recognition processes. However, very little information can be found in literature about the fundamental analytical parameters of these sensors. In this work, the analytical behavior of an amperometric biosensor based on the immobilization of GOx using a hydrogel (Chitosan) onto highly ordered titanium dioxide nanotube arrays (TiO₂NTAs) has been evaluated. The GOx–Chitosan/TiO₂NTAs biosensor showed a sensitivity of 5.46 μA·mM⁻¹ with a linear range from 0.3 to 1.5 mM; its fundamental analytical parameters were studied using a commercial soft drink. The obtained results proved sufficient repeatability (RSD = 1.9%), reproducibility (RSD = 2.5%), accuracy (95–105% recovery), and robustness (RSD = 3.3%). Furthermore, no significant interferences from fructose, ascorbic acid and citric acid were obtained. In addition, the storage stability was further examined, after 30 days, the GOx–Chitosan/TiO₂NTAs biosensor retained 85% of its initial current response. Finally, the glucose content of different food samples was measured using the biosensor and compared with the respective HPLC value. In the worst scenario, a deviation smaller than 10% was obtained among the 20 samples evaluated.

Bioanalytical methods, in particular electrochemical biosensors, are increasingly used in different industrial sectors due to their simplicity, low cost, and fast response. However, to be able to reliably use this type of device, it is necessary to undertake in-depth evaluation of their fundamental analytical parameters. In this work, analytical parameters of an amperometric biosensor based on covalent immobilization of glucose oxidase (GOx) were evaluated. GOx was immobilized using plasma-grafted pentafluorophenyl methacrylate (pgPFM) as an anchor onto a tailored HEMA-co-EGDA hydrogel that coats a titanium dioxide nanotubes array (TiO₂NTAs). Finally, chitosan was used to protect the enzyme molecules. The biosensor offered outstanding analytical parameters: repeatability (RSD = 1.7%), reproducibility (RSD = 1.3%), accuracy (deviation = 4.8%), and robustness (RSD = 2.4%). In addition, the Ti/TiO₂NTAs/ppHEMA-co-EGDA/pgPFM/GOx/Chitosan biosensor showed good long-term stability; after 20 days, it retained 89% of its initial sensitivity. Finally, glucose concentrations of different food samples were measured and compared using an official standard method (HPLC). Deviation was lower than 10% in all measured samples. Therefore, the developed biosensor can be considered to be a reliable analytical tool for quantification measurements.

In the context of the ever-growing interest in the cyclic diaryliodonium salts, this work presents synthetic design principles for a new family of structures with two hypervalent halogens in the ring. The smallest bis-phenylene derivative, [(C₆H₄)₂I₂]²⁺, was prepared through oxidative dimerization of a precursor bearing the ortho-disposed iodine and trifluoroborate groups. We also report, for the first time, the formation of cycles containing two different halogen atoms. These present two phenylenes linked by hetero-(I/Br) or -(I/Cl) halogen pairs. This approach was also extended to the cyclic bis-naphthylene derivative [(C₁₀H₆)₂I₂]²⁺. The structures of these bis-halogen(III) rings were further assessed through X-ray analysis. The simplest cyclic phenylene bis-iodine(III) derivative features the interplanar angle of ∼120°, while a smaller angle of ∼103° was found for the analogous naphthylene-based salt. All dications form dimeric pairs through a combination of π-π and C-H/π interactions. As the largest member of the family, a bis-I(III)-macrocycle was also assembled using the quasi-planar xanthene backbone. Its geometry enables the two iodine(III) centers to be bridged intramolecularly by two bidentate triflate anions. In a preliminary manner, the interaction of the phenylene- and naphthalene-based bis-iodine(III) dications with a new family of rigid bidentate bis-pyridine ligands was studied in solution and the solid state, with an X-ray structure showing the chelating donor bonding to just one of the two iodine centers.

Hydroxyalkanoyloxyalkanoates (HAA) are lipidic surfactants with a number of potential applications, but more remarkably, they are the biosynthetic precursors of rhamnolipids (RL), which are preferred biosurfactants thanks to their excellent physicochemical properties, biological activities, and environmental biodegradability. Because the natural highest producer of RLs is the pathogenic bacterium Pseudomonas aeruginosa, important efforts have been dedicated to transfer production to heterologous non-pathogenic microorganisms. Unicellular photosynthetic microalgae are emerging as important hosts for sustainable industrial biotechnology due to their ability to transform CO₂ efficiently into biomass and bioproducts of interest. Here, we have explored the potential of the eukaryotic green microalgae Chlamydomonas reinhardtii as a chassis to produce RLs. Chloroplast genome engineering allowed the stable functional expression of the gene encoding RhlA acyltransferase from P. aeruginosa, an enzyme catalyzing the condensation of two 3-hydroxyacyl acid intermediaries in the fatty acid synthase cycle, to produce HAA. Four congeners of varying chain lengths were identified and quantified by UHPLC-QTOF mass spectrometry and gas chromatography, including C₁₀-C₁₀ and C₁₀-C₈, and the less abundant C₁₀-C₁₂ and C₁₀-C₆ congeners. HAA was present in the intracellular fraction, but also showed increased accumulation in the extracellular medium. Moreover, HAA production was also observed under photoautotrophic conditions based on atmospheric CO₂. These results establish that RhlA is active in the chloroplast and is able to produce a new pool of HAA in a eukaryotic host. Subsequent engineering of microalgal strains should contribute to the development of an alternative clean, safe and cost-effective platform for the sustainable production of RLs.

Preventing relapse after resection of a primary tumor continues to be an unmet clinical need. Development of adjuvant biomaterials with the capacity to kill residual cancer cells after tumor resection is of clinical importance. Here we developed a library of metallo-alginate hydrogels containing high concentrations of metallic ions such as Ca²⁺ in combination with Zn²⁺, Li⁺, or Mg²⁺ to disrupt Ca²⁺ homeostasis in the mitochondria of cancer cells by local hyperthermia. To synergistically kill tumor cells and suppress the growth of rechallenged tumors, we embedded oncogene-silencing nucleic acids (mTOR siRNA) loaded into polymerc nanoparticles (NPs) composed of poly (β-amino esters) in the metallo-alginate hydrogels, targeting cancer cells that activate multi-drug resistance pathways such PI3K/AKT/mTOR. Metabolomic studies showed alterations in the Warburg effect, mitochondrial transport, and the TCA cycle, confirming cancer cell damage. In vivo studies of this targeted therapy in mice demonstrated a sex-dependent effect. Male B16F10-tumor-bearing mice treated with the synergistic therapy showed restrained tumor growth. In contrast, no therapeutic effect was observed in female counterparts. Our results demonstrate that in situ-formed NP-loaded metallo-alginate hydrogels can modulate two distinct immune signaling networks that are relevant for enhancing cancer cell death. On the basis of our findings, this combination therapy emerges as a promising sex-dependent strategy for clinical translation.