RESUMEN
We report two new cyanido-bridged Fe(II)-Ag(I) coordination polymers using different acetylpyridine isomers, {Fe(4acpy)2[Ag(CN)2]2} 1 and {Fe(3acpy)[Ag(CN)2]2} 2 (4acpy = 4-acetylpyridine; 3acpy = 3-acetylpyridine) displaying thermally and photoinduced spin crossover (SCO). In both cases, the acetylpyridine ligand directs the coordination polymer structure and the SCO of the materials. Using 4-acetylpyridine, a two-dimensional (2D) structure is observed in 1 made of layers stacked on each other by silver-ketone interactions leading to a complete SCO and reversible thermally and photoswitching of the magnetic and optical properties. Changing the acetyl group to a 3-position, a completely different structure is obtained for 2. The unexpected coordination of the carbonyl group to the Fe(II) centers induces a three-dimensional (3D) structure, leading to statistical disorder around the Fe(II) with three different coordination spheres, [N6], [N4O2], and [N5O]. This disorder gives rise to an incomplete thermally induced SCO with a poor photoswitchability. These results demonstrate that the choice of the acetyl position on the pyridine dictates the structural characteristics of the compounds with a direct impact on the SCO behavior. Remarkably, this work opens interesting perspectives for the future design of Fe-Ag cyanido coordination polymers with judiciously substituted pyridine ligands to tune the thermally and photoinduced SCO properties.
RESUMEN
An innovative supramolecular architecture is reported for bienzymatic glucose biosensing based on the use of a nanohybrid made of multi-walled carbon nanotubes (MWCNTs) non-covalently functionalized with a Schiff base modified with two phenylboronic acid residues (SB-dBA) as platform for the site-specific immobilization of the glycoproteins glucose oxidase (GOx) and horseradish peroxidase (HRP). The analytical signal was obtained from amperometric experiments at - 0.050 V in the presence of 5.0 × 10-4 M hydroquinone as redox mediator. The concentration of GOx and HRP and the interaction time between the enzymes and the nanohybrid MWCNT-SB-dBA deposited at glassy carbon electrodes (GCEs) were optimized through a central composite design (CCD)/response surface methodology (RSM). The optimal concentrations of GOx and HRP were 3.0 mg mL-1 and 1.50 mg mL-1, respectively, while the optimum interaction time was 3.0 min. The bienzymatic biosensor presented a sensitivity of (24 ± 2) × 102 µA dL mg-1 ((44 ± 4) × 102 µA M-1), a linear range between 0.06 mg dL-1 and 21.6 mg dL-1 (3.1 µM-1.2 mM) (R2 = 0.9991), and detection and quantification limits of 0.02 mg dL-1 (1.0 µM) and 0.06 mg dL-1 (3.1 µM), respectively. The reproducibility for five sensors prepared with the same MWCNT-SB-dBA nanohybrid was 6.3%, while the reproducibility for sensors prepared with five different nanohybrids and five electrodes each was 7.9%. The GCE/MWCNT-SB-dBA/GOx-HRP was successfully used for the quantification of glucose in artificial human urine and commercial human serum samples.
Asunto(s)
Técnicas Biosensibles , Ácidos Borónicos , Enzimas Inmovilizadas , Glucosa Oxidasa , Peroxidasa de Rábano Silvestre , Nanotubos de Carbono , Bases de Schiff , Nanotubos de Carbono/química , Bases de Schiff/química , Técnicas Biosensibles/métodos , Ácidos Borónicos/química , Glucosa Oxidasa/química , Glucosa Oxidasa/metabolismo , Peroxidasa de Rábano Silvestre/química , Peroxidasa de Rábano Silvestre/metabolismo , Humanos , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/metabolismo , Glucosa/análisis , Electrodos , Límite de Detección , Técnicas Electroquímicas/métodos , Glucemia/análisisRESUMEN
Core-shell micro/nanomotors have garnered significant interest in biomedicine owing to their versatile task-performing capabilities. However, their effectiveness for photothermal therapy (PTT) still faces challenges because of their poor tumor accumulation, lower light-to-heat conversion, and due to the limited penetration of near-infrared (NIR) light. In this study, we present a novel core-shell micromotor that combines magnetic and photothermal properties. It is synthesized via the template-assisted electrodeposition of iron (Fe) and reduced graphene oxide (rGO) on a microtubular pore-shaped membrane. The resulting Fe-rGO micromotor consists of a core of oval-shaped zero-valent iron nanoparticles with large magnetization. At the same time, the outer layer has a uniform reduced graphene oxide (rGO) topography. Combined, these Fe-rGO core-shell micromotors respond to magnetic forces and near-infrared (NIR) light (1064 nm), achieving a remarkable photothermal conversion efficiency of 78% at a concentration of 434 µg mL-1. They can also carry doxorubicin (DOX) and rapidly release it upon NIR irradiation. Additionally, preliminary results regarding the biocompatibility of these micromotors through in vitro tests on a 3D breast cancer model demonstrate low cytotoxicity and strong accumulation. These promising results suggest that such Fe-rGO core-shell micromotors could hold great potential for combined photothermal therapy.
RESUMEN
We report a nanohybrid material obtained by non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with the new ligand (((1E,1'E)-(naphthalene-2,3-diylbis(azaneylylidene))bis(methaneylylidenedene)) bis(4-hydroxy-3,1-phenylene))diboronic acid (SB-dBA), rationally designed to mimic some recognition properties of biomolecules like concanavalin A, for the development of electrochemical biosensors based on the use of glycobiomolecules as biorecognition element. We present, as a proof-of-concept, a hydrogen peroxide biosensor obtained by anchoring horseradish peroxidase (HRP) at a glassy carbon electrode (GCE) modified with the nanohybrid prepared by sonication of 2.0 mg mL-1 MWCNTs and 0.50 mg mL-1 SB-dBA in N,N-dimethyl formamide (DMF) for 30 min. The hydrogen peroxide biosensing was performed at -0.050 V in the presence of 5.0 × 10-4 M hydroquinone. The analytical characteristics of the resulting biosensor are the following: linear range between 0.175 µM and 6.12 µM, detection limit of 58 nM, and reproducibility of 2.0 % using the same nanohybrid (6 biosensors), and 9.0 % using three different nanohybrids. The sensor was successfully used to quantify hydrogen peroxide in enriched milk and human blood serum samples and in a commercial disinfector.