Switchable Polyacrylic Acid Polyelectrolyte Brushes for Surface Plasmon Resonance Applications.

Imaging wide-field surface plasmon resonance (SPR) microscopy sensors based on polyacrylic acid polyelectrolyte brushes (PAA PEBs) were designed to enhance the sensitivity of nano-object detection. The switching behavior of the PAA PEBs against changes in the pH values was investigated by analyzing the chemical, morphological, optical, and electrical properties. At pH ~1, the brushes collapse on the surface with the dominance of carboxylic groups (COOH). Upon the increase in the pH to nine, the switching process completes, and the brushes swell from dissociating most of the COOH groups and converting them into COO- groups. The domination of the negatively charged COO- groups increases the electrostatic repulsion in the polymer chains and stretches the brushes. The sensitivity of the SPR sensing device was investigated using a theoretical approach, as well as experimental measurements. The signal-to-noise ratio for a Au layer increases from six to eighteen after coating with PAA PEBs. In addition, the linewidth of the recorded image decreases from six pixels to five pixels by using the Au-PAA layers, which results from the enhanced spatial resolution of the recorded images. Coating a Au-layer with PAA PEBs enhances the sensitivity of the SPR sensing device, and improves the spatial resolution of the recorded image.

Size Effect in Hybrid TiO2:Au Nanostars for Photocatalytic Water Remediation Applications.

TiO2:Au-based photocatalysis represents a promising alternative to remove contaminants of emerging concern (CECs) from wastewater under sunlight irradiation. However, spherical Au nanoparticles, generally used to sensitize TiO2, still limit the photocatalytic spectral band to the 520 nm region, neglecting a high part of sun radiation. Here, a ligand-free synthesis of TiO2:Au nanostars is reported, substantially expanding the light absorption spectral region. TiO2:Au nanostars with different Au component sizes and branching were generated and tested in the degradation of the antibiotic ciprofloxacin. Interestingly, nanoparticles with the smallest branching showed the highest photocatalytic degradation, 83% and 89% under UV and visible radiation, together with a threshold in photocatalytic activity in the red region. The applicability of these multicomponent nanoparticles was further explored with their incorporation into a porous matrix based on PVDF-HFP to open the way for a reusable energy cost-effective system in the photodegradation of polluted waters containing CECs.

Synthesis and characterization of photocatalytic polyurethane and poly(methyl methacrylate) microcapsules for the controlled release of methotrexate.

The aim of this work is to prepare ultraviolet (UV) triggered controlled release of compounds from microcapsule systems (MCs). Polyurethane (PU) and poly(methyl methacrylate) (PMMA) microcapsules were studied with/without chemical functionalization using photocatalytic TiO2 nanoparticles (NPs) on their surface. Once TiO2 nanoparticles are illuminated with UV light (λ = 370 nm), they initiate the rupture of the polymeric bonds of the microcapsule and subsequently initiate the encapsulated compound release, methotrexate (MTX) or rhodamine (Rh), in the present work. The size, polydispersity, charge, and yield of all MCs were measured, being the methotrexate drug release for all systems determined and compared with and without functionalization with TiO2 NPs, under dark, visible light and UV illumination in vitro. Finally, the Rh release was characterized using fluorescence microscopy. The TiO2 NPs size is around 10 nm, as determined by X-ray diffraction experiments. The PU MCs average size is around 60 µm, its electric charge +3.11 mV and yield around 85%. As for the PMMA MCs, the average size is around 280 µm, its electric charge -7.2 mV and yield around 25% and 30% for both MTX and Rh, respectively. In general, adding TiO2 NPs or the encapsulated products to the MCs does not affect the size but functionalization with TiO2 NPs lowers the electric charge. Microcapsules functionalized with TiO2 nanoparticles and irradiated with UV light presented the highest release of MTX and Rh. All other samples showed lower drug release levels when studied under the same conditions.

Preparation of robust polyamide microcapsules by interfacial polycondensation of p-phenylenediamine and sebacoyl chloride and plasticization with oleic acid.

Microcapsules produced by interfacial polycondensation of p-phenylenediamine (PPD) and sebacoyl chloride (SC) were studied. The products were characterized in terms of morphology, mean diameter and effectiveness of dodecane encapsulation. The use of Tween 20 as dispersion stabilizer, in comparison with polyvinyl alcohol (PVA), reduced considerably the mean diameter of the microcapsules and originated smoother wall surfaces. When compared to ethylenediamine (EDA), microcapsules produced with PPD monomer were more rigid and brittle, prone to fracture during processing and ineffective retention of the core liquid. The use of diethylenetriamine (DETA) cross-linker in combination with PPD did not decrease capsule fragility. On the other hand, addition of a small fraction of oleic acid to the organic phase remarkably improved wall toughness and lead to successful encapsulation of the core-oil. Oleic acid is believed to act as a plasticizer. Its incorporation in the polymeric wall was demonstrated by FTIR and (1)H-NMR.

Surface plasmon coupling between wide-field SPR microscopy and gold nanoparticles.

The coupling behavior of the wide field surface plasmon microscopy (WF-SPRM) with single-, two-, and multiple-gold nanoparticles (AuNPs) with different AuNPs sizes is investigated using theoretical, simulation, and experimental approaches. The signal intensity of a single AuNP increases from 208 a.u. to 583 a.u. as particle size increases from 40 to 80 nm, which evidences the signal-building mechanism of Rayleigh scattering theory. A discrete particle model of SPR is used to understand the interaction between an Au-layer and a single AuNP. The calculated intensity profile of the single AuNP from the discrete particle model is accepted with the experimental data. In addition, the superposition between 2-AuNPs surface plasmon waves is studied using the finite element method as well as experimental data from WF-SPRM. The surface plasmon waves around the two particles generate an interference pattern. Finally, it is demonstrated that plasmonic multiple particles scattering can be represented by an effective media, which is described by Maxwell-Garnet equations.

Surface Atomic Arrangement of Aluminum Ultra-Thin Layers Grown on Si(111).

Surface atomic arrangement and physical properties of aluminum ultrathin layers on c-Si(111)-7 × 7 and hydrogen-terminated c-Si(111)-1 × 1 surfaces deposited using molecular beam epitaxy were investigated. X-ray photoelectron spectroscopy spectra were collected in two configurations (take-off angle of 0° and 45°) to precisely determine the surface species. Moreover, 3D atomic force microscopy (AFM) images of the air-exposed samples were acquired to investigate the clustering formations in film structure. The deposition of the Al layers was monitored in situ using a reflection high-energy electron diffraction (RHEED) experiments to confirm the surface crystalline structure of the c-Si(111). The analysis of the RHEED patterns during the growth process suggests the settlement of aluminum atoms in Al(111)-1 × 1 clustered formations on both types of surfaces. The surface electrical conductivity in both configurations was tested against atmospheric oxidation. The results indicate differences in conductivity based on the formation of various alloys on the surface.

Hybrid TiO2:Au nanostars based polymeric membranes for photocatalytic degradation of ciprofloxacin in water samples.

Antibiotics represent one increasingly harmful type of contaminant of emerging concern in treated and non-treated water. They cause the generation of antibiotic-multiresistant organisms, one of the major challenges in current medicine. Plasmonic-photocatalysis using solar energy represents a promising solution for their removal with low energy consumption. Its successful application requires the improvement of photocatalysts' efficiency under sunlight and the development of robust, durable, and efficient substrates for photocatalysts immobilisation. In this work, hybrid TiO2:Au nanostars were initially synthesised. Then, two porous membranes were prepared to support this nanocatalyst based on poly (vinylidenefluoride-co-hexafluoropropylene) polymer. Doctor blade and salt leaching casting methods, combined with temperature-induced phase separation, were used to generate membranes with high porosity, 80-90%, which was maintained after nanoparticle incorporation (3, 8 and 10 wt%). The photocatalytic activity of the nanocomposite membranes was tested through the degradation of the antibiotic ciprofloxacin under UV and visible radiation. Salt-leaching membranes containing 10 wt% nanoparticles presented the highest degradation efficiencies, 45% under UV and 35% under visible radiation. In contrast, doctor blade membranes showed 36% and 32% degradation efficiencies, respectively. The reusability of the membranes was assessed in repeated cycles, presenting an average efficiency loss of only 2% after three uses. Finally, the reusability of these membranes was also tested in treated effluent water matrixes, presenting similar, or even better, degradation efficiencies, and a minimum reusability efficiency lost 0-1%. The results demonstrate that these membranes are a promising alternative for the degradation of a wide variety of contaminants under sunlight radiation.

PMMA Microcapsules for the Inactivation of SARS-CoV-2.

Surface disinfection currently plays a decisive role in the epidemiological situation caused by the SARS-CoV-2 coronavirus. However, most disinfection products available on the market have a high evaporation rate and only an immediate action and not continuous, creating the need for a high frequency of disinfection. To overcome this limitation, in the present work, poly(methyl methacrylate) (PMMA) microcapsules were developed with an active agent (hydrogen peroxide) encapsulated, which has the ability to inactivate/neutralize the SARS-CoV-2 virus. PMMA-H2O2 microcapsules have a spherical shape and a smooth structure with low porosity and were successfully attached to nonwoven fabrics, as observed from scanning electron microscopy. The thermogravimetric analysis shows that PMMA-H2O2 microcapsules have high thermal stability and can increase the stability of H2O2. Nonfabric substrates functionalized with PMMA-H2O2 microcapsules were tested by a highly sensitive and specific reverse transcription-quantitative real-time polymerase chain reaction (RT-qPCR)-based method to evaluate antiviral activity through the degradation of SARS-CoV-2 deoxyribonucleic acids. The highest percentage of viral nucleic acid elimination was obtained when exposing the viral sample for 1 h to PMMA-H2O2 microcapsules, resulting in an elimination of >97% of the coronavirus. In addition, the microcapsules are stable over a period of three weeks and retain the ability to eliminate SARS-CoV-2. Hence, it is demonstrated that this microcapsule system is efficient for SARS-CoV-2 elimination and inherent surface disinfection.

Multifunctional hybrid membranes for photocatalytic and adsorptive removal of water contaminants of emerging concern.

This work focuses on the combination of multifunctional photocatalytic and adsorbent materials in a unique polymeric membrane. For this purpose, Au/TiO2 and Y2(CO3)3 nanoparticles were immobilised onto a poly (vinylidene fluoride-hexafluoropropylene), (PVDF-HFP) membrane, and the physical-chemical characterisation of these materials was performed, as well as pollutant removal efficiency. An efficient TiO2 functionalisation with gold nanoparticles was achieved, endowing these particles with the capability to absorb visible radiation absorption. A favourable porous structure was obtained for the membranes, with an average pore size of 4 µm, and the nanoparticles immobilisation did not alter the chemical properties of the polymeric membrane. The produced hybrid materials, including both the Au/TiO2 and Y2(CO3)3 nanoparticles, presented an efficiency of 57% in the degradation of norfloxacin (5 mg/L) under ultraviolet radiation for 120 min, 80% under visible radiation for 300 min, and 58% in arsenic adsorption for 240 min. These membranes represent a new multifunctional platform for removing several pollutants, which may allow their incorporation in more efficient and less energy-consuming water treatment processes favouring its application, even in low energy resources countries.

Photocatalytic and antimicrobial multifunctional nanocomposite membranes for emerging pollutants water treatment applications.

Emerging pollutants represent a new global problem for water quality. As these compounds get into the environment, they cause severe threats to aquatic environments and human health and are typically resistant to conventional wastewater treatments. In this work, TiO2 nanoparticles surface was functionalized with silver (Ag) nanoparticles, and solvent cast and electrospun membranes of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) were prepared with different concentrations of TiO2 and Ag-TiO2 to produce a multifunctional material. The photocatalytic activity of the nanocomposites was evaluated through the degradation of norfloxacin under ultraviolet (UV) and visible radiation. It is shown that nanocomposites with Ag-TiO2 show the highest degradation efficiencies: 64.2% under UV and 80.7% under visible radiation, for 90 and 300 min, respectively. Furthermore, the recyclability of the membranes has also been demonstrated. Finally, it is shown the antimicrobial activity of the nanocomposite membranes, demonstrating the suitability of the Ag-TiO2/PVDF-HFP nanocomposites as multifunctional photocatalytic and antimicrobial membranes for water remediation applications.