Multifunctional polymer-based nanocomposites for synergistic adsorption and photocatalytic degradation of mixed pollutants in water.

Water pollution is a growing concern for mankind due to its harmful effects on humans, animals and plants. Usually, several pollutants are present in wastewater. For example, dyes and antibiotics are found in wastewater because of their widespread use in factories and hospitals. However, one single technique, e.g. either adsorption or photocatalysis, cannot easily remove more than one kind of pollutant, especially by using one single material in water. For this reason, here multifunctional iron(ii,iii) oxide/poly(N-isopropylacrylamide-co-methacrylic acid)/silver-titanium dioxide (Fe3O4/P(NIPAM-co-MAA)/Ag-TiO2) nanocomposites were used to remove a mixture of pollutants from water. Specifically, three types of experiments were performed to evaluate the adsorption capacity and photodegradation activity of the nanocomposites towards the dye basic fuchsin (BF) and the antibiotic ciprofloxacin (CIP), which were added sequentially to the nanocomposites dispersion or were concurrently present as a mixture. The results demonstrated that the nanocomposites could adsorb BF, and subsequently photodegrade CIP under visible-light irradiation, if BF was the first added pollutant. As well, the nanocomposites could first degrade CIP under visible-light irradiation, and then adsorb BF if they were initially put in contact with CIP. Finally, the ability of adsorbing BF and photodegrading CIP was confirmed in the co-presence of the two pollutants.

Photocatalytic degradation of methylene blue at nanostructured ZnO thin films.

The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l-1MB solution, 540 minUV irradiation), the rate constantkof MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10-9(mol·l-1·min-1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB.

Reusable and Antibacterial Polymer-Based Nanocomposites for the Adsorption of Dyes and the Visible-Light-Driven Photocatalytic Degradation of Antibiotics.

Adsorption and advanced oxidation processes, especially photocatalysis, are amongst the most common water treatment methodologies. Unfortunately, using each of these techniques independently does not fully eliminate the pollutants of diverse nature, which are present in wastewater. Here, an avenue for multifunctional materials for water treatment is opened by reporting for the first time the preparation, characterization, and study of the properties of a novel multifunctional nanocomposite with both adsorption and visible-light-driven photocatalysis abilities. These multifunctional nanocomposites, namely iron (II, III) oxide/poly(N-isopropylacrylamide-co-methacrylic acid)/silver-titanium dioxide (Fe3O4/P(NIPAM-co-MAA)/Ag-TiO2), are prepared by combining magnetic polymeric microspheres (Fe3O4/P(NIPAM-co-MAA)) with silver-decorated titanium dioxide nanoparticles (Ag-TiO2 NPs). Cationic dyes, such as basic fuchsin (BF), can be adsorbed by the nanocomposites thanks to the carboxylic groups of Fe3O4/P(NIPAM-co-MAA) microspheres. Concomitantly, the presence of Ag-TiO2 NPs endows the system with the visible-light-driven photocatalytic degradation ability toward antibiotics such as ciprofloxacin (CIP) and norfloxacin (NFX). Furthermore, the proposed nanocomposites show antibacterial activity toward Escherichia coli (E. coli), thanks to the presence of silver nanoparticles (Ag NPs). Due to the superparamagnetic properties of iron (II, III) oxide nanoparticles (Fe3O4 NPs), the nanocomposites can be also recycled and reused, after the cleaning process, by using an external magnetic field.

Synthesis, characterization and photocatalytic properties of nanostructured lanthanide doped ß-NaYF4/TiO2 composite films.

The photocatalytic approach is known to be one of the most promising advanced oxidation processes for the tertiary treatment of polluted water. In this paper, ß-NaYF4/TiO2 composite films have been synthetized through a novel sol-gel/spin-coating approach using a mixture of ß-diketonate complexes of Na and Y, and Yb3+, Tm3+, Gd3+, Eu3+ as doping ions, together with the TiO2 P25 nanoparticles. The herein pioneering approach represents an easy, straightforward and industrially appealing method for the fabrication of doped ß-NaYF4/TiO2 composites. The effect of the doped ß-NaYF4 phase on the photocatalytic activity of TiO2 for the degradation of methylene blue (MB) has been deeply investigated. In particular, the upconverting TiO2/ß-NaYF4: 20%Yb, 2% Gd, x% Tm (x = 0.5 and 1%) and the downshifting TiO2/ß-NaYF4: 10% Eu composite films have been tested on MB degradation both under UV and visible light irradiation. An improvement up to 42.4% in the degradation of MB has been observed for the TiO2/ß-NaYF4: 10% Eu system after 240 min of UV irradiation.

Dipyridamole for tracking amyloidogenic proteins aggregation and enhancing polyubiquitination.

Dipyridamole is currently used as a medication that inhibits blood clot formation and it is also investigated in the context of neurodegenerative and other amyloid related diseases. Here, we propose this molecule as a new diagnostic tool to follow the aggregation properties of three different amyloidogenic proteins tested (insulin, amylin and amyloid ß peptide 1-40). Results show that dipyridamole is sensitive to early stage amyloid formation undetected by thioflavin T, giving a different response for the aggregation of the three different proteins. In addition, we show that dipyridamole is also able to enhance ubiquitin chain growth, paving the way to its potential application as therapeutic agent in neurodegenerative diseases.

A Supramolecular Nanoassembly of Lenvatinib and a Green Light-Activatable NO Releaser for Combined Chemo-Phototherapy.

The chemotherapeutic Lenvatinib (LVB) and a nitric oxide (NO) photodonor based on a rhodamine antenna (RD-NO) activatable by the highly compatible green light are supramolecularly assembled by a ß-cyclodextrin branched polymer (PolyCD). The poorly water-soluble LVB and RD-NO solubilize very well within the polymeric host leading to a ternary supramolecular nanoassembly with a diameter of ~55 nm. The efficiency of the NO photorelease and the typical red fluorescence of RD-NO significantly enhance within the polymer due to its active role in the photochemical and photophysical deactivation pathways. The co-presence of LVB within the same host does not affect either the nature or the efficiency of the photoinduced processes of RD-NO. Besides, irradiation of RD-NO does not lead to the decomposition of LVB, ruling out any intermolecular photoinduced process between the two guests despite sharing the same host. Ad-hoc devised Förster Resonance Energy Transfer experiments demonstrate this to be the result of the not close proximity of the two guests, which are confined in different compartments of the same polymeric host. The supramolecular complex is stable in a culture medium, and its biological activity has been evaluated against HEP-G2 hepatocarcinoma cell lines in the dark and under irradiation with visible green light, using LVB at a concentration well below the IC50. Comparative experiments performed using the polymeric host encapsulating the individual LVB and RD-NO components under the same experimental conditions show that the moderate cell mortality induced by the ternary complex in the dark increases significantly upon irradiation with visible green light, more likely as the result of synergism between the NO photogenerated and the chemotherapeutic.

Enhanced visible-light photodegradation of fluoroquinolone-based antibiotics and E. coli growth inhibition using Ag-TiO2 nanoparticles.

Antibiotics in wastewater represent a growing and worrying menace for environmental and human health fostering the spread of antimicrobial resistance. Titanium dioxide (TiO2) is a well-studied and well-performing photocatalyst for wastewater treatment. However, it presents drawbacks linked with the high energy needed for its activation and the fast electron-hole pair recombination. In this work, TiO2 nanoparticles were decorated with Ag nanoparticles by a facile photochemical reduction method to obtain an increased photocatalytic response under visible light. Although similar materials have been reported, we advanced this field by performing a study of the photocatalytic mechanism for Ag-TiO2 nanoparticles (Ag-TiO2 NPs) under visible light taking in consideration also the rutile phase of the TiO2 nanoparticles. Moreover, we examined the Ag-TiO2 NPs photocatalytic performance against two antibiotics from the same family. The obtained Ag-TiO2 NPs were fully characterised. The results showed that Ag NPs (average size: 23.9 ± 18.3 nm) were homogeneously dispersed on the TiO2 surface and the photo-response of the Ag-TiO2 NPs was greatly enhanced in the visible light region when compared to TiO2 P25. Hence, the obtained Ag-TiO2 NPs showed excellent photocatalytic degradation efficiency towards the two fluoroquinolone-based antibiotics ciprofloxacin (92%) and norfloxacin (94%) after 240 min of visible light irradiation, demonstrating a possible application of these particles in wastewater treatment. In addition, it was also proved that, after five Ag-TiO2 NPs re-utilisations in consecutive ciprofloxacin photodegradation reactions, only a photocatalytic efficiency drop of 8% was observed. Scavengers experiments demonstrated that the photocatalytic mechanism of ciprofloxacin degradation in the presence of Ag-TiO2 NPs is mainly driven by holes and ˙OH radicals, and that the rutile phase in the system plays a crucial role. Finally, Ag-TiO2 NPs showed also antibacterial activity towards Escherichia coli (E. coli) opening the avenue for a possible use of this material in hospital wastewater treatment.

Nanosensor-Based Real-Time Monitoring of Stress Biomarkers in Human Saliva Using a Portable Measurement System.

Small molecules with no or little charge are considered to have minimal impact on signals measured by field effect transistor (FET) sensors. This fact typically excludes steroids from the family of analytes, detected by FETs. We present a portable multiplexed platform based on an array of nanowire sensors for label-free monitoring of daytime levels of the stress hormone cortisol in saliva samples, obtained from multiple donors. To achieve an effective quantification of the cortisol with FETs, we rely on the specific DNA aptamer sequences as receptors, bringing the complex "target-receptor" closer to the nanowire surface. Upon binding, cortisol induces conformational changes of negatively charged aptamers, wrapping it into a close proximity to the silicon nanowires, to efficiently modulate their surface potential. Thus, the sensors allow for a real-time assessment of the steroid biomarkers at low nanomolar concentration. The measurement platform is designed in a building-block concept, consisting of a modular measuring unit and a customizable biochip board, and operates using a complementary metal-oxide-semiconductor-integrated multiplexer. The platform is capable of continuous and simultaneous measurement of samples from multiple patients. Cortisol levels detected with the presented platform agreed well with the results obtained with a commercial high-sensitivity immunoassay.

Design and Performance of Novel Self-Cleaning g-C3N4/PMMA/PUR Membranes.

In the majority of photocatalytic applications, the photocatalyst is dispersed as a suspension of nanoparticles. The suspension provides a higher surface for the photocatalytic reaction in respect to immobilized photocatalysts. However, this implies that recovery of the particles by filtration or centrifugation is needed to collect and regenerate the photocatalyst. This complicates the regeneration process and, at the same time, leads to material loss and potential toxicity. In this work, a new nanofibrous membrane, g-C3N4/PMMA/PUR, was prepared by the fixation of exfoliated g-C3N4 to polyurethane nanofibers using thin layers of poly(methyl methacrylate) (PMMA). The optimal amount of PMMA was determined by measuring the adsorption and photocatalytic properties of g-C3N4/PMMA/PUR membranes (with a different PMMA content) in an aqueous solution of methylene blue. It was found that the prepared membranes were able to effectively adsorb and decompose methylene blue. On top of that, the membranes evinced a self-cleaning behavior, showing no coloration on their surfaces after contact with methylene blue, unlike in the case of unmodified fabric. After further treatment with H2O2, no decrease in photocatalytic activity was observed, indicating that the prepared membrane can also be easily regenerated. This study promises possibilities for the production of photocatalytic membranes and fabrics for both chemical and biological contaminant control.

Ultrasmall silicon nanoparticles as a promising platform for multimodal imaging.

Bimodal systems for nuclear and optical imaging are currently being intensively investigated due to their comparable detection sensitivity and the complementary information they provide. In this perspective, we have implemented both modalities on biocompatible ultrasmall silicon nanoparticles (Si NPs). Such nanoparticles are particularly interesting since they are highly biocompatible, have covalent surface functionalization and demonstrate very fast body clearance. We prepared monodisperse citrate-stabilized Si NPs (2.4 ± 0.5 nm) with more than 40 accessible terminal amino groups per particle and, for the first time, simultaneously, a near-infrared dye (IR800-CW) and a radiolabel (64Cu-NOTA = 1,4,7-triazacyclononane-1,4,7-triacetic acid) have been covalently linked to the surface of such Si NPs. The obtained nanomaterials have been fully characterized using HR-TEM, XPS, UV-Vis and FT-IR spectroscopy. These dual-labelled particles do not exhibit any cytotoxicity in vitro. In vivo studies employing both positron emission tomography (PET) and optical imaging (OI) techniques revealed rapid renal clearance of dual-labelled Si NPs from mice.

Biodistribution studies of ultrasmall silicon nanoparticles and carbon dots in experimental rats and tumor mice.

Ultrasmall clearable nanoparticles possess enormous potential as cancer imaging agents. In particular, biocompatible silicon nanoparticles (Si NPs) and carbon quantum dots (CQDs) hold great potential in this regard. Their facile surface functionalization easily allows the introduction of different labels for in vivo imaging. However, to date, a thorough biodistribution study by in vivo positron emission tomography (PET) and a comparative study of Si vs. C particles of similar size are missing. In this contribution, ultrasmall (size <5 nm) Si NPs and CQDs were synthesized and characterized by high-resolution transmission electron microscopy (HR-TEM), Fourier-transform infrared (FTIR), absorption and steady-state emission spectroscopy. Subsequent functionalization of NPs with a near-infrared dye (Kodak-XS-670) or a radiolabel (64Cu) enabled a detailed in vitro and in vivo study of the particles. For radiolabeling experiments, the bifunctional chelating agent S-2-(4-isothiocyanatobenzyl)-1,4,7-triazacyclononane-1,4,7-triacetic acid (p-SCN-Bn-NOTA) was conjugated to the amino surface groups of the respective NPs. Efficient radiolabeling of NOTA-functionalized NPs with the positron emitter 64Cu was found. The biodistribution and PET studies showed a rapid renal clearance from the in vivo systems for both variants of the nanoparticles. Interestingly, the different derivatives investigated exhibited significant differences in the biodistribution and pharmacokinetic properties. This can mostly be attributed to different surface charge and hydrophilicity of the NPs, arising from the synthetic strategy used to prepare the particles.

Ultrasmall inorganic nanoparticles: State-of-the-art and perspectives for biomedical applications.

Ultrasmall nanoparticulate materials with core sizes in the 1-3nm range bridge the gap between single molecules and classical, larger-sized nanomaterials, not only in terms of spatial dimension, but also as regards physicochemical and pharmacokinetic properties. Due to these unique properties, ultrasmall nanoparticles appear to be promising materials for nanomedicinal applications. This review overviews the different synthetic methods of inorganic ultrasmall nanoparticles as well as their properties, characterization, surface modification and toxicity. We moreover summarize the current state of knowledge regarding pharmacokinetics, biodistribution and targeting of nanoscale materials. Aside from addressing the issue of biomolecular corona formation and elaborating on the interactions of ultrasmall nanoparticles with individual cells, we discuss the potential diagnostic, therapeutic and theranostic applications of ultrasmall nanoparticles in the emerging field of nanomedicine in the final part of this review.

BiFeO3 films doped in the A or B sites: effects on the structural and morphological properties.

Metal-Organic Chemical Vapor Deposition (MOCVD) has been applied to the fabrication of BiFeO3 films undoped and doped with Ba or Ti on SrTiO3 (100) and YSZ (100) substrates. The films have been deposited using a multi-metal source, consisting of the Bi(phenyl)3, Fe(tmhd)3 and Ba(hfa)2 tetraglyme or Ti(tmhd)2(O-iPr)2 (phenyl = -C6H5, H-tmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = iso-propoxide; H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = CH3O(CH2CH2O)4CH3) precursor mixture. The structural and morphological characterization of films has been carried out using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Chemical compositional studies have been performed by energy dispersive X-ray (EDX) analysis. Structural and morphological characterizations point to the formation of homogeneous and flat surfaces for both undoped and doped BiFeO3 films.