Atmospheric Pressure Plasma-Treated Polyurethane Foam as Reusable Absorbent for Removal of Oils and Organic Solvents from Water.

This paper reports the optimization of a two-step atmospheric pressure plasma process to modify the surface properties of a polyurethane (PU) foam and, specifically, to prepare a superhydrophobic/superoleophilic absorbent for the removal of oils and nonpolar organic solvents from water. In particular, in the first step, an oxygen-containing dielectric barrier discharge (DBD) is used to induce the etching/nanotexturing of the foam surfaces; in the second step, an ethylene-containing DBD enables uniform overcoating with a low-surface-energy hydrocarbon polymer film. The combination of surface nanostructuring and low surface energy ultimately leads to simultaneous superhydrophobic and superoleophilic wetting properties. X-ray photoelectron spectroscopy, scanning electron microscopy and water contact angle measurements are used for the characterization of the samples. The plasma-treated PU foam selectively absorbs various kinds of hydrocarbon-based liquids (i.e., hydrocarbon solvents, mineral oils, motor oil, diesel and gasoline) up to 23 times its own weight, while it completely repels water. These absorption performances are maintained even after 50 absorption/desorption cycles and after immersion in hot water as well as acidic, basic and salt aqueous solutions. The plasma-treated foam can remove mineral oil while floating on the surface of mineral oil/water mixtures with a separation efficiency greater than 99%, which remains unaltered after 20 separation cycles.

Transforming colloidal Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr3 perovskite emitters through intermediate heterostructures.

The preparation of strongly emissive CsPbBr3 perovskite nanocrystals with robust surface passivation is a challenge in the field of lead halide perovskite nanomaterials. We report an approach to prepare polymer-capped CsPbBr3 perovskite nanocrystals by reacting oleylammonium/oleate-capped Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) (PMAO). PMAO contains succinic anhydride units that are reactive towards the oleylamine species present on the Cs4PbBr6 nanocrystals' surface and produces polysuccinamic acid, which, in turn, triggers the Cs4PbBr6 to CsPbBr3 conversion. The transformation occurs through the formation of Cs4PbBr6-CsPbBr3 heterostructures as intermediates, which are captured because of the mild reactivity of PMAO and are investigated by high-resolution electron microscopy. The Cs4PbBr6-CsPbBr3 heterostructures demonstrate a dual emission at cryogenic temperature with an indication of the energy transfer from Cs4PbBr6 to CsPbBr3. The fully-transformed CsPbBr3 NCs have high photoluminescence quantum yield and enhanced colloidal stability, which we attribute to the adhesion of polysuccinamic acid to the NC surface through its multiple functional groups in place of oleate and alkylammonium ligands. The PMAO-induced transformation of Cs4PbBr6 NCs opens up a strategy for the chemical modification of metal halide NCs initially passivated with nucleophilic amines.

Correction: Transforming colloidal Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr3 perovskite emitters through intermediate heterostructures.

[This corrects the article DOI: 10.1039/D0SC00738B.].

Poly(furfuryl alcohol)-Polycaprolactone Blends.

Poly(furfuryl alcohol) (PFA) is a bioresin synthesized from furfuryl alcohol (FA) that is derived from renewable saccharide-rich biomass. In this study, we compounded this bioresin with polycaprolactone (PCL) for the first time, introducing new functional polymer blends. Although PCL is biodegradable, its production relies on petroleum precursors such as cyclohexanone oils. With the method proposed herein, this dependence on petroleum-derived precursors/monomers is reduced by using PFA without significantly modifying some important properties of the PCL. Polymer blend films were produced by simple solvent casting. The blends were characterized in terms of surface topography by atomic force microscopy (AFM), chemical interactions between PCL and PFA by attenuated total reflection-Fourier transform infrared (ATR-FTIR), crystallinity by XRD, thermal properties by differential scanning calorimetry (DSC), and mechanical properties by tensile tests and biocompatibility by direct and indirect toxicity tests. PFA was found to improve the gas barrier properties of PCL without compromising its mechanical properties, and it demonstrated sustained antioxidant effect with excellent biocompatibility. Our results indicate that these new blends can be potentially used in diverse applications ranging from food packing to biomedical devices.

Combining dietary phenolic antioxidants with polyvinylpyrrolidone: transparent biopolymer films based on p-coumaric acid for controlled release.

Polyvinylpyrrolidone (PVP) has probably been one of the most utilized pharmaceutical polymers with applications ranging from a blood plasma substitute to nanoparticle drug delivery, since its synthesis in 1939. It is a highly biocompatible, non-toxic and transparent film forming polymer. Although high solubility of PVP in aqueous environment is advantageous, it still poses several problems for some applications in which sustained targeting and release are needed or hydrophobic drug inclusion and delivery systems are to be designed. In this study, we demonstrate that a common dietary phenolic antioxidant, p-coumaric acid (PCA), can be combined with PVP covering a wide range of molar ratios by solution blending in ethanol, forming new transparent biomaterial films with antiseptic and antioxidant properties. PCA not only acts as an effective natural plasticizer but also establishes H-bonds with PVP increasing its resistance to water dissolution. PCA could be released in a sustained manner up to a period of 3 days depending on the PVP/PCA molar ratio. Sustained drug delivery potential of the films was studied using methylene blue and carminic acid as model drugs, indicating that the release can be controlled. Antioxidant and remodeling properties of the films were evaluated in vitro by free radical cation scavenging assay and in vivo on a murine model, respectively. Furthermore, the material resorption of films was slower as PCA concentration increased, as observed from the in vivo full-thickness excision model. Finally, the antibacterial activity of the films against common pathogens such as Escherichia coli and Staphylococcus aureus and the effective reduction of inflammatory agents such as matrix metallopeptidases were demonstrated. All these properties suggest that these new transparent PVP/PCA films can find a plethora of applications in pharmaceutical sciences including skin and wound care.

Laser Ablation as a Versatile Tool To Mimic Polyethylene Terephthalate Nanoplastic Pollutants: Characterization and Toxicology Assessment.

The presence of micro- and nanoplastics in the marine environment is raising strong concerns since they can possibly have a negative impact on human health. In particular, the lack of appropriate methodologies to collect the nanoplastics from water systems imposes the use of engineered model nanoparticles to explore their interactions with biological systems, with results not easily correlated with the real case conditions. In this work, we propose a reliable top-down approach based on laser ablation of polymers to form polyethylene terephthalate (PET) nanoplastics, which mimic real environmental nanopollutants, unlike synthetic samples obtained by colloidal chemistry. PET nanoparticles were carefully characterized in terms of chemical/physical properties and stability in different media. The nanoplastics have a ca. 100 nm average dimension, with significant size and shape heterogeneity, and they present weak acid groups on their surface, similarly to photodegraded PET plastics. Despite no toxic effects emerging by in vitro studies on human Caco-2 intestinal epithelial cells, the formed nanoplastics were largely internalized in endolysosomes, showing intracellular biopersistence and long-term stability in a simulated lysosomal environment. Interestingly, when tested on a model of intestinal epithelium, nano-PET showed high propensity to cross the gut barrier, with unpredictable long-term effects on health and potential transport of dispersed chemicals mediated by the nanopollutants.

Photochromic Paper Indicators for Acidic Food Spoilage Detection.

A photoresponsive microstructured composite is fabricated through the impregnation of cellulosic filter paper (FP) with a spiropyran-modified acrylic polymer. The polymer enwraps uniformly each individual cellulose fiber, increases the thermal stability of cellulose, and ensures the preservation of the composite functionalities even upon removal of the surface layers through mechanical scratching. The photochromic spiropyran moieties of the polymer, even while embedded in the cellulosic sheet, can reversibly interconvert between the colorless spiropyran and the pink merocyanine isomeric states upon irradiation with UV and visible light, respectively. Moreover, the photochromic polymer presents a faster photochromic response and a higher resistance to photodegradation, with an outstanding reusability for more than 100 switching cycles when it is incorporated in the cellulose network. Most importantly, the acidochromism of the modified FP, attributed to the spiropyran molecules after UV activation, allows the real-time optical and visual detection of acidity changes and spoilage in food products, such as wine and milk. Spoilage due to bacterial degradation and oxidation processes generates acidic vapors that induce the protonation of the merocyanine. This results in a visually detectable chromic transition from pink to white of the treated cellulose fibers, corresponding to a blue shift in the absorption spectrum. The developed photoresponsive cellulose composite can serve as cost-effective robust optical component in integrated functional platforms and consumer-friendly indicators for smart food packaging, as well as portable on demand acidoresponsive interfaces for gas monitoring in industrial and environmental applications.

Titanate Fibroin Nanocomposites: A Novel Approach for the Removal of Heavy-Metal Ions from water.

In this study, we report the fabrication of nanocomposites made of titanate nanosheets immobilized in a solid matrix of regenerated silk fibroin as novel heavy-metal-ion removal systems. The capacity of these nanocomposite films to remove lead, mercury, and copper cations from water was investigated, and as shown by the elemental quantitative analysis performed, their removal capacity is 73 mmol/g for all of the ions tested. We demonstrate that the nanocomposites can efficiently retain the adsorbed ions, with no release of titanate nanosheets occurring even after several exposure cycles to ionic solutions, eliminating the risk of release of potentially hazardous nanosubstances to the environment. We also prove that the introduction of sodium ions in the nanocomposite formulation makes the materials highly selective toward the lead ions. The developed biopolymer nanocomposites can be potentially used for the efficient removal of heavy-metal-ion pollutants from water and, thanks to their physical and optical characteristics, offer the possibility to be used in sensor applications.

Environmentally Benign Production of Stretchable and Robust Superhydrophobic Silicone Monoliths.

Superhydrophobic materials hold an enormous potential in sectors as important as aerospace, food industries, or biomedicine. Despite this great promise, the lack of environmentally friendly production methods and limited robustness remain the two most pertinent barriers to the scalability, large-area production, and widespread use of superhydrophobic materials. In this work, highly robust superhydrophobic silicone monoliths are produced through a scalable and environmentally friendly emulsion technique. It is first found that stable and surfactantless water-in-polydimethylsiloxane (PDMS) emulsions can be formed through mechanical mixing. Increasing the internal phase fraction of the precursor emulsion is found to increase porosity and microtexture of the final monoliths, rendering them superhydrophobic. Silica nanoparticles can also be dispersed in the aqueous internal phase to create micro/nanotextured monoliths, giving further improvements in superhydrophobicity. Due to the elastomeric nature of PDMS, superhydrophobicity can be maintained even while the material is mechanically strained or compressed. In addition, because of their self-similarity, the monoliths show outstanding robustness to knife-scratch, tape-peel, and finger-wipe tests, as well as rigorous sandpaper abrasion. Superhydrophobicity was also unchanged when exposed to adverse environmental conditions including corrosive solutions, UV light, extreme temperatures, and high-energy droplet impact. Finally, important properties for eventual adoption in real-world applications including self-cleaning, stain-repellence, and blood-repellence are demonstrated.

Light Responsive Silk Nanofibers: An Optochemical Platform for Environmental Applications.

Photochromic spiropyran-doped silk fibroin poly(ethylene oxide) nanofibers which combine the attractive properties and biocompatibility of silk with the photocontrollable and reversible optical, mechanical, and chemical response of the spiropyran dopants are herein presented. As proved, the reversible variation of the absorption and emission signals of the mats and of their Young's modulus upon alternate UV and visible light irradiation is ascribed to the reversible photoconversion of the spiropyran form to its polar merocyanine counterpart. Most importantly, the interactions of the merocyanine molecules with acidic vapors as well as with heavy metal ions dispersed in solution produce analyte-specific spectral changes in the emission profile of the composite, accompanied by a characteristic chromic variation. Because of the high surface-to-volume ratio of the nanofibrous network, such interactions are fast, thus enabling both an optical and a visual detection in a 30-60 s time scale. The sensing platform can be easily regenerated for more than 20 and 3 cycles upon acid or ion depletion, respectively. Overall, the photocontrolled properties of the silk composites combined with a straightforward preparation method render them suitable as porous materials and scaffolds with tunable compliance and reusable nanoprobes for real time optical detection in biomedical, environmental, and industrial applications.

One-Pot Hybrid SnO2 /Poly(methyl methacrylate) Nanocomposite Formation through Pulsed Laser Irradiation.

The localized in situ formation of tin dioxide (SnO2 ) nanoparticles embedded in poly(methyl methacrylate) (PMMA) films is presented. This is achieved by the photoinduced conversion of the tin acetate precursor included in polymeric films, through controlled UV or visible pulsed laser irradiation at λ=355 and 532 nm, respectively. The evolution of the formation of nanoparticles is followed by UV/Vis spectroscopy and shows that their growth is affected in different ways by the laser pulses at the two applied wavelengths. This, in combination with electron microscopy analysis, reveals that, depending on the irradiation wavelength, the size of the nanoparticles in the final nanocomposites differs. This difference is attributed to distinct mechanistic pathways that lead to the synthesis of small nanoparticles (from 1.5 to 4.5 nm) at λ=355 nm, whereas bigger ones (from 5 to 16 nm) are formed at λ=532 nm. At the same time, structural studies with both X-ray and electron diffraction measurements demonstrate the crystallinity of SnO2 nanoparticles in both cases, whereas XPS analysis confirms the light-induced oxidation of tin acetate into SnO2 . Taken all together, it is demonstrated that the pulsed laser irradiation at λ=355 and 532 nm leads to the formation of SnO2 nanoparticles with defined features highly dispersed in PMMA solid matrices.

USPIO size control through microwave nonaqueous sol-gel method for neoangiogenesis T2 MRI contrast agent.

AIM: Tunable size ultrasmall superparamagnetic iron oxide (USPIO) nanoparticles from 3 to 9 nm coated with polyethylene glycol phosphonate moieties have been designed for neovascularization MRI. MATERIALS & METHODS: USPIO were synthesized using a nonaqueous sol-gel method. An ischemia-reperfusion rat model has been chosen for neo-angiogenesis and scanned on MRI after injection of different sized USPIO. Histological studies have been performed for USPIO localization within the tissue. RESULTS: The magnetic properties and consequently their MRI relaxivities are drastically dependent on the crystalline core size. In vivo MRI spots were observed specifically in the ischemic area. The best MRI contrast within neovascularization is generated by 6 nm nanoparticles proving that compromise between T2 relaxivity and physico-chemical properties is essential for the design of effective MRI contrast agent.

Chemical Modification of Graphene Oxide through Diazonium Chemistry and Its Influence on the Structure-Property Relationships of Graphene Oxide-Iron Oxide Nanocomposites.

4-Carboxyphenyl groups are covalently grafted onto graphene oxide via diazonium chemistry for studying their role on the adsorption of iron oxide nanoparticles. The nanoparticles are deposited via a novel phase-transfer approach involving specific interactions at the interface between two immiscible solvents. The increased density and the homogeneous distribution of surface carboxyl moieties enable the preparation of a nanocomposite with improved iron oxide distribution and loading. Structure-properties relationships are investigated by analysing the electrochemical properties of the nanocomposites, which are regarded as promising active materials for application in supercapacitors. It is demonstrated that the nature of the interactions between the components similarly affects the overall electrochemical performances of the nanocomposites and the structure of the materials.

Effect of 10 different TiO2 and ZrO2 (nano)materials on the soil invertebrate Enchytraeus crypticus.

Nearly 80% of all the nano-powders produced worldwide are metal oxides, and among these materials titanium dioxide (TiO2 ) is one of the most produced. Titanium dioxide's toxicity is estimated as low to soil organisms, but some studies have shown that TiO2 nanoparticles can cause oxidative stress. Additionally, it is known that TiO2 is activated by ultraviolet (UV) radiation, which can promote photocatalytic generation of reactive oxygen species, which is seldom taken into account in toxicity testing. In the present study, the authors investigated the effects of different TiO2 and zirconium materials on the soil oligochaete Enchytraeus crypticus, using exposure via soil, water, and soil:water extracts, and studied the effects combined with UV radiation. The results showed that zirconium dioxide (bulk and nano) was not toxic, whereas zirconium tetrachloride reduced enchytraeid reproduction in soil (50% effect concentration = 502 mg/kg). The TiO2 materials were also not toxic via soil exposure or under UV radiation. However, pre-exposure to TiO2 and UV radiation via aqueous media caused a lower reproductive output post-exposure in clean soil (20-50% less but only observed at the lowest concentration tested, 1 mg/L); that is, the effect of TiO2 in water was potentiated by the UV radiation and measurable as a decrease in reproduction in soil media.

Efficient and tuneable photoluminescent boehmite hybrid nanoplates lacking metal activator centres for single-phase white LEDs.

White light-emitting diodes (WLEDs) are candidates to revolutionize the lighting industry towards energy efficient and environmental friendly lighting and displays. The current challenges in WLEDs encompass high luminous efficiency, chromatic stability, high colour-rending index and price competitiveness. Recently, the development of efficient and low-cost downconverting photoluminescent phosphors for ultraviolet/blue to white light conversion was highly investigated. Here we report a simple route to design high-efficient WLEDs by combining a commercial ultraviolet LED chip (InGaAsN, 390 nm) and boehmite (γ-AlOOH) hybrid nanoplates. Unusually high quantum yields (ηyield=38-58%) result from a synergic energy transfer between the boehmite-related states and the triplet states of the benzoate ligands bound to the surface of the nanoplates. The nanoplates with ηyield=38% are able to emit white light with Commission International de l'Eclairage coordinates, colour-rendering index and correlated colour temperature values of (0.32, 0.33), 85.5 and 6,111 K, respectively; overwhelming state-of-the-art single-phase ultraviolet-pumped WLEDs phosphors.

Organic photovoltaic devices with colloidal TiO2 nanorods as key functional components.

We report on a novel approach to integrate colloidal anatase TiO(2) nanorods as key functional components into polymer bulk heterojunction (BHJ) photovoltaic devices by means of mild, all-solution-based processing techniques. The successful integration of colloidal nanoparticles in organic solar cells relies on the ability to remove the long chain insulating ligands, which indeed severely reduces the charge transport. To this aim we have exploited the concomitant mechanisms of UV-light-driven photocatalytic removal of adsorbed capping ligands and hydrophilicization of TiO(2) surfaces in both solid-state and liquid-phase conditions. We have demonstrated the successful integration of the UV-irradiated films and colloidal solutions of TiO(2) nanorods in inverted and conventional solar cell geometries, respectively. The inverted devices show a power conversion efficiency of 2.3% that is a ca. three times improvement over their corresponding cell counterparts incorporating untreated TiO(2), demonstrating the excellent electron-collecting property of the UV-irradiated TiO(2) films. The integration of UV-treated TiO(2) solutions in conventional devices results in doubled power conversion efficiency for the thinner active layer and in maximum power conversion efficiency of 2.8% for 110 nm thick devices. In addition, we have demonstrated, with the support of device characterizations and optical simulations, that the TiO(2) nanocrystal buffer layer acts both as electron-transporting/hole-blocking material and optical spacer.

Controlled swapping of nanocomposite surface wettability by multilayer photopolymerization.

Single-layered photopolymerized nanocomposite films of polystyrene and TiO(2) nanorods change their wetting characteristics from hydrophobic to hydrophilic when deposited on substrates with decreasing hydrophilicity. Interestingly, the addition of a second photopolymerized layer causes a swapping in the wettability, so that the final samples result converted from hydrophobic to hydrophilic or vice versa. The wettability characteristics continue to be swapped as the number of photopolymerized layers increases. In fact, odd-layered samples show the same wetting behavior as single-layered ones, while even-layered samples have the same surface characteristics as double-layered ones. Analytical surface studies demonstrate that all samples, independently of the number of layers, have similar low roughness, and that the wettability swap is due to the different concentration of the nanocomposites constituents on the samples surface. Particularly, the different interactions between the hydrophilic TiO(2) nanorods and the underlying layer lead to different amounts of nanorods exposed on the nanocomposites surface. Moreover, due to the unique property of TiO(2) to reversibly increase its wettability upon UV irradiation and subsequent storage, the wetting characteristics of the multilayered nanocomposites can be tuned in a reversible manner. In this way, a combination of substrate, number of photopolymerized layers, and external UV light stimulus can be used in order to precisely control the surface wettability properties of nanocomposite films, opening the way to a vast number of potential applications in microfluidics, protein assays, and cell growth.

Light-controlled directional liquid drop movement on TiO2 nanorods-based nanocomposite photopatterns.

Patterned polymeric coatings enriched with colloidal TiO(2) nanorods and prepared by photopolymerization are found to exhibit a remarkable increase in their water wettability when irradiated with UV laser light. The effect can be completely reversed using successive storage in vacuum and dark ambient environment. By exploiting the enhancement of the nanocomposites hydrophilicity upon UV irradiation, we prepare wettability gradients along the surfaces by irradiating adjacent surface areas with increasing time. The gradients are carefully designed to achieve directional movement of water drops along them, taking into account the hysteresis effect that opposes the movement as well as the change in the shape of the drop during its motion. The accomplishment of surface paths for liquid flow, along which the hydrophilicity gradually increases, opens the way to a vast number of potential applications in microfluidics.

Electron diffractive imaging of oxygen atoms in nanocrystals at sub-ångström resolution.

High-resolution imaging of low-atomic-number chemical elements using electron microscopy is challenging and may require the use of high doses of electrons. Electron diffractive imaging, which creates real-space images using diffraction intensities and phase retrieval methods, could overcome such issues, although it is also subject to limitations. Here, we show that a combination of electron diffractive imaging and high-resolution transmission electron microscopy can image individual TiO(2) nanocrystals with a resolution of 70 pm while exposing the specimen to a low dose of electrons. Our approach, which does not require spherical and chromatic aberration correction, can reveal the location of light atoms (oxygen) in the crystal lattice. We find that the unit cell in nanoscale TiO(2) is subtly different to that in the corresponding bulk.

The effect of polymer matrices in the in-situ CdS formation under UV irradiation of precursor-polymer films.

Polymer films embedding cadmium thiolate precursors have been irradiated with ultraviolet laser pulses resulting in the formation of cadmium sulfide crystalline nanoparticles through a macroscopically non-destructive procedure for the host matrix. Controlling the number of the incident laser pulses, the gradual increase of the size of the nanoparticles is accomplished, and consequently the progressive change of the emission characteristics of the formed nanocomposites. The X-ray diffraction and transmission electron microscopy measurements were used for the full characterization of the nanoparticles. This study compares two polymer matrices, poly(methyl methacrylate) and a cyclic olefin copolymer, and reveals the importance of each one for the emission characteristics of the formed cadmium sulfide nanocrystals. It is found that the poly(methyl methacrylate) matrix contributes to the increase of the trap states on the surface of the formed nanocrystals, causing the broadening of their emission. On the other hand the cadmium sulfide nanoparticles, grown into the cyclic olefin copolymer matrix, exhibit narrower emission spectra.