Synthesis of Au Nanoparticles Assisted by Linker-Modified TiO2 Nanoparticles.

Plasmonic nanoparticles, especially gold ones, have been widely employed as photosensitizers in photoelectrovoltaic or photocatalytic systems. To improve the system's performance, a greater interaction of the nanoparticles with the semiconductor, generally TiO2, is desired. Moreover, this performance is enhanced when an efficient covering of TiO2 surface by the sensitizer is achieved. The Brust-Schiffrin-like methods are of the most employed approaches for nanoparticles synthesis. In a traditional approach, the reduction of the gold precursor is performed in the presence of a stabilizer (typically a thiol molecule) free in solution. A second step in which the obtained nanoparticles are anchored to the semiconductor surface is necessary in the case of photosensitive applications. Drawbacks like steric hindrance turn more difficult the covering of the semiconductor's surface by nanoparticles. In this paper, we report a variation of this methodology, where the linker is previously anchored to the TiO2 nanoparticles surface. The resulting system is employed as the stabilizer in the gold reduction step. This strategy is carried out in aqueous media in two simple steps. A great covering of the titania surface by gold nanoparticles is achieved in all cases and the gold nanoparticles in the resulting nanoaggregate might be useful for photoelectrovoltaic or photocatalytic applications.

Spraying Fluorinated Silicon Oxide Nanoparticles on CuONPs@CF-PVDF Membrane: A Simple Method to Achieve Superhydrophobic Surfaces and High Flux in Direct Contact Membrane Distillation.

Desalinization of seawater can be achieved by membrane distillation techniques (MD). In MD, the membranes should be resistant to fouling, robust for extended operating time, and preferably provide a superhydrophobic surface. In this work, we report the preparation and characterization of a robust and superhydrophobic polyvinylidene fluoride membrane containing fluoroalkyl-capped CuONPs (CuONPs@CF) in the inner and fluorinated capped silicon oxide nanoparticles (SiO2NPs@CF) on its surface. SiO2NPs@CF with a mean diameter of 225 ± 20 nm were prepared by the sol method using 1H,1H,2H,2H-perfluorodecyltriethoxysilane as a capping agent. Surface modification of the membrane was carried out by spraying SiO2NPs@CF (5% wt.) dispersed in a mixture of dimethyl formamide (DMF) and ethanol (EtOH) at different DMF/EtOH % v/v ratios (0, 5, 10, 20, and 50). While ethanol dispersed the nanoparticles in the spraying solution, DMF dissolved the PVDF on the surface and retained the sprayed nanoparticles. According to SEM micrographs and water contact angle measurements, the best results were achieved by depositing the nanoparticles at 10% v/v of DMF/EtOH. Under these conditions, a SiO2NPs covered surface was observed with a water contact angle of 168.5°. The water contact angle was retained after the sonication of the membrane, indicating that the modification was successfully achieved. The membrane with SiO2NPs@CF showed a flux of 14.3 kg(m2·h)-1, 3.4 times higher than the unmodified version. The method presented herein avoids the complicated modification procedure offered by chemical step modification and, due to its simplicity, could be scalable to a commercial membrane.

Design and Study of a Photo-Switchable Polymeric System in the Presence of ZnS Nanoparticles under the Influence of UV Light Irradiation.

Recent progress in the field of photosensitive materials has prompted a need to develop efficient methods to synthesize materials with basic intermolecular architectural designs and novel properties. Accordingly, in this work we design and study a photoactive polymer as a photo-switchable polymeric system in the presence and absence of ZnS nanoparticles (average size < 10 nm) at 5 wt.%. The influence of UV light irradiation on its properties were also studied. The photoactive block copolymer was obtained from styrene (S) and methyl methacrylate (MMA) as monomers and 1-(2-hydroxyethyl)-3,3-dimethylindoline-6-nitrobenzopyran (SP) was grafted to the block copolymer backbone as a photochromic agent. Furthermore, the incorporation of ZnS (NPs) as photo-optical switch component into the system enhances the purple colored photo-emission, with the open form of the spiropyran derivative (merocyanine, MC). The ZnS stabilize the isomeric equilibrium in the MC interconversion of the photochromic agent. The photo-switchable properties of the PS-b-PMMA-SP in the presence of ZnS (NPs) were examined using UV-VIS spectroscopy, Photoluminescence (PL) spectroscopy, optical fluorescence and scanning electronic microscopy (SEM-EDX.). The observed changes in the absorbance, fluorescence and morphology of the system were associated to the reversible interconversion of the two states of the photochromic agent which regulates the radiative deactivation of the luminescent ZnS NPs component. After UV irradiation the photoactive polymer becomes purple in color. Therefore, these basic studies can lead to the development of innovative functional and nanostructured materials with photosensitive character as photosensitive molecular switches.

Preparation of photoactive ZnS-composite porous polymer films: Fluorescent and morphological properties.

This work describes the use of the breath figure (BF) method for the fabrication of photoactive porous polymer films and the characterization of their responsive to photo stimulus. The films incorporate self-assembled photoactive polymers and ZnS nanoparticles (NPs). The effect of both components on the optical and morphological properties of the films were analyzed. Films with a hexagonally ordered pattern were obtained. The photoactive polymer was prepared by grafting the photochromic component 1-(2-hydroxyethyl)-3,3-dimethylindoline-6-nitrobenzopyran (SP) to polystyrene-block-polymethacrylic acid (PS-b-PMMA). ZnS NPs were incorporated into the polymer solution, and the films were prepared using spin-coating on glass substrates before subjecting them to the BF method. The hollow footprints were obtained before introducing the ZnS NPs in order to maintain the necessary conditions for hexagonal film growth. Accordingly, the SEM micrographs of the films prepared in the presence of ZnS NPs displayed a loss in the pore arrangement as a consequence of the interaction between SP moiety and NPs. The light-emitting properties of films were characterized by blue and violet colors when exposed to UV light under fluorescence. Progress in the field of breath-figure formation and its application, such as exemplified in this work, leads to functional structures with suitable applications in chemistry and materials science. It is expected that such microstructured polymeric films will have interesting applications in photonic and optoelectronic devices.

PVDF Composite Membranes with Hydrophobically-Capped CuONPs for Direct-Contact Membrane Distillation.

Water scarcity is an imminent problem that humanity is beginning to attempt to solve. Among the several technologies that have been developed to mitigate water scarcity, membrane distillation is of particular note. In the present work, CuO nanoparticles capped with 1-octanethiol (CuONPs@CH) or 1H,1H,2H,2H-perfluorodecanethiol (CuONPs@CF) are prepared. The nanoparticles are characterized by FT-IR and TGA methods. Two weight losses are observed in both cases, with the decomposition of the organic fragments beginning at 158 °C and 230 °C for CuONPs@CF and CuONPs@CH, respectively. Flat sheet PVDF composite membranes containing nanoparticles are prepared by the casting solution method using nanoparticle concentrations that ranged between 2-20% with a non-woven polyester fabric as support. The obtained membranes showed a thickness of 240 ± 40 µm. According to water contact angle (87° for CuONPs@CH and 95° for CuONPs@CF, both at 10% w.t) and roughness (12 pixel for CuONPs@CH and 14 pixels for CuONPs@CF, both at 10% w.t) determinations, the hydrophobicity of membranes changed due to a decrease in surface energy, while, for naked CuONPs, the roughness factor represents the main role. Membranes prepared with capped nanoparticles showed similar porosity (60-64%). SEM micrographs show asymmetric porous membranes with a 200-nm surface pore diameter. The largest finger-like pores in the membranes prepared with CuONPs, CuONPs@CH and CuONPs@CF had values of 63 ± 10 µm, 32 ± 8 µm, and 45 ± 10 µm, respectively. These membranes were submitted to a direct contact membrane distillation module and flux values of 1.8, 2.7, and 3.9 kg(m2·h)-1 at ΔT = 30 °C were obtained for the CuONPs, CuONPs@CH, and CuONPs@CF, respectively. The membranes showed 100% salt rejection during the testing time (240 min).

Exploration of Copper Oxide Nanoneedle Electrosynthesis Applied in the Degradation of Methylene Blue.

In this study, we report a low cost, fast and unexplored electrochemical synthesis strategy of copper oxide nanoneedles films as well as their morphological and chemical characterization. The nanostructured films were prepared using electrochemical anodization in alkaline electrolyte solutions of ethylene glycol, water and fluoride ions. The film morphology shows nanoneedle-shaped structures, with lengths up to 1-2 µm; meanwhile, high-resolution X-ray photoelectron spectroscopy (HRXPS) and spectroscopy Raman analyses indicate that a mixture of Cu(II) and Cu(I) oxides, or only Cu(I) oxide, is obtained as the percentage of water in the electrolyte solution decreases. A preliminary study was also carried out for the photocatalytic degradation of the methylene blue (MB) dye under irradiation with simulated sunlight in the presence of the nanoneedles obtained, presenting a maximum degradation value of 88% of MB and, thus, demonstrating the potential characteristics of the material investigated in the degradation of organic dyes.

New Poly(imide)s Bearing Alkyl Side-Chains: A Study on the Impact of Size and Shape of Lateral Groups on Thermal, Mechanical, and Gas Transport Properties.

A set of five new aromatic poly(imide)s (PIs) incorporating pendant acyclic alkyl moieties were synthesized. The difference among them was the length and bulkiness of the pendant group, which comprises of linear alkyl chains from three to six carbon atoms, and a tert-butyl moiety. The effect of the side group length on the physical, thermal, mechanical, and gas transport properties was analyzed. All PIs exhibited low to moderate molecular weights (Mn ranged between 27.930-58.970 Da, and Mw ranged between 41.760-81.310 Da), good solubility in aprotic polar solvents, except for PI-t-4, which had a tert-butyl moiety and was soluble even in chloroform. This behaviour was probably due to the most significant bulkiness of the side group that increased the interchain distance, which was corroborated by the X-ray technique (PI-t-4 showed two d-spacing values: 5.1 and 14.3 Å). Pure gas permeabilities for several gases were reported (PI-3 (Barrer): He(52); H2(46); O2(5.4); N2(1.2); CH4(1.1); CO2(23); PI-t-4 (Barrer): He(139); H2(136); O2(16.7); N2(3.3); CH4(2.3); CO2(75); PI-5 (Barrer): He(44); H2(42); O2(5.9); N2(1.4); CH4(1.2); CO2(27); PI-6 (Barrer): He(45); H2(43); O2(6.7); N2(1.7); CH4(1.7); CO2(32)). Consistent higher volume in the side group was shown to yield the highest gas permeability. All poly(imide)s exhibited high thermal stability with 10% weight loss degradation temperature between 448-468 °C and glass transition temperature between 240-270 °C. The values associated to the tensile strength (45-87 MPa), elongation at break (3.2-11.98%), and tensile modulus (1.43-2.19 GPa) were those expected for aromatic poly(imide)s.

Porous Surface Films With Tunable Morphologies and Hydrophobic Properties Based on Block Copolymer Under the Effects of Thermal Annealing.

The fabrication of porous-structured polymer films with patterned surface structures has recently attracted increased interest within the material science field. In this work, a series of microstructure scale patterned polymer films were obtained via breath figure methods (BF) with hydrophobic surface films based on self-assembled diblock copolymers by atom-transfer radical polymerization (ATRP). The surface characteristics and morphological properties, pore size, roughness, thickness, and wettability of the block copolymer films was studied in response to variation of the hydrophilic co-monomer structures. A significant improvement of the quality and order of the hydrophobic films was observed in response to thermal annealing and a consequent optimization of the assembly process.

Preparation of CuONPs@PVDF/Non-Woven Polyester Composite Membrane: Structural Influence of Nanoparticle Addition.

Membrane distillation techniques have appeared as promising options for guaranteeing the availability of potable water in times of scarcity of this essential resource. For membrane preparation, polyvinylidene fluoride (PVDF) is preferred due to the easier synthesis procedures, with respect to other fluorine-based polymers. In this work, copper oxide nanoparticles (CuONPs) of different weight percent (wt %) embedded in PVDF membranes supported on non-woven polyester fabric (NWPET) were prepared by the phase inversion method, and characterized by spectroscopy (ATR-FTIR, Raman) and electron microscopy techniques (SEM). The PVDF deposited onto the NWPET was mostly composed of its polar ß-phase (F(ß) = 53%), which was determined from the ATR-FTIR spectrum. The F(ß) value remained constant throughout the whole range of added CuONP concentrations (2⁻10 wt %), as was determined from the ATR-FTIR spectrum. The absence of signals corresponding to CuONPs in the ATR-FTIR spectra and the appearance of peaks at 297, 360, and 630 cm-1 in the Raman spectra of the membranes suggest that the CuONPs are preferably located in the inner PVDF membrane, but not on its surface. The membrane morphologies were characterized by SEM. From the obtained SEM micrographs, a decrease and increase in the amount of micropores and nanopores, respectively, near the surface and intercalated in the finger-like layer were observed. As a result of the CuONP addition, the nanopores in the sponge-like layer decreased in size. The values of water contact angle (WCA) measurements showed a decreasing trend, from 94° to 80°, upon the addition of CuONPs (2⁻10 wt %), indicating a diminishment in the hydrophobicity degree of the membranes. Apparently, the increase in the amount of nanopores near the surface decreased the membrane roughness, so it became less hydrophobic.

In-Situ Preparation of CdTe Quantum Dots Capped with a ß-Cyclodextrin-Epichlorohydrin Polymer: Polymer Influence on the Nanocrystal's Optical Properties.

ß-Cyclodextrin (ßCD), the less water soluble of the cyclodextrins, has been used as a capping agent in the preparation of semiconductor nanocrystals or quantum dots (QDs). Nevertheless, no reports have been found in the use of the highly water-soluble polymer of this, prepared by the crosslinking of the ßCD units with epichlorohydrin in basic medium (ßCDP). This polymer, besides to overcome the low solubility of the ßCD, increases the inclusion constant of the guest; two parameters that deserve its use as capping agent, instead of the native cyclodextrin. In the present manuscript, we afforded the in-situ aqueous preparation of cadmium telluride (CdTe) QDs capped with ßCDP. The polymer influence on the photoluminescent properties of the nanocrystals was analyzed. The ßCDP controls the nanocrystals growth during the Oswald ripening stage. Consequently, the CdTe capped ßCDP QDs showed lower Stokes-shift values, higher photoluminescent efficiency, and narrower size distribution than for nanocrystals obtained in the absence of polymer. Transmission electron microscopy (TEM) micrographs and energy dispersive X-ray spectroscopy (EDS) analysis revealed the composition and crystallinity of the CdTe QDs. This ßCDP capped CdTe QDs is a potential scaffold for the supramolecular modification of QDs surface.

Two New Fluorinated Phenol Derivatives Pyridine Schiff Bases: Synthesis, Spectral, Theoretical Characterization, Inclusion in Epichlorohydrin-ß-Cyclodextrin Polymer, and Antifungal Effect.

It has been reported that the structure of the Schiff bases is fundamental for their function in biomedical applications. Pyridine Schiff bases are characterized by the presence of a pyridine and a phenolic ring, connected by an azomethine group. In this case, the nitrogen present in the pyridine is responsible for antifungal effects, where the phenolic ring may be also participating in this bioactivity. In this study, we synthesized two new pyridine Schiff Bases: (E)-2-[(3-Amino-pyridin-4-ylimino)-methyl]-4,6-difluoro-phenol (F1) and (E)- 2-[(3-Amino-pyridin-4-ylimino)-methyl]-6-fluoro-phenol (F2), which only differ in the fluorine substitutions in the phenolic ring. We fully characterized both F1 and F2 by FTIR, UV-vis, 1H; 13C; 19F-NMR, DEPT, HHCOSY, TOCSY, and cyclic voltammetry, as well as by computational studies (DFT), and NBO analysis. In addition, we assessed the antifungal activity of both F1 (two fluorine substitution at positions 4 and 6 in the phenolic ring) and F2 (one fluorine substitution at position 6 in the phenolic ring) against yeasts. We found that only F1 exerted a clear antifungal activity, showing that, for these kind of Schiff bases, the phenolic ring substitutions can modulate biological properties. In addition, we included F1 and F2 into in epichlorohydrin-ß-cyclodextrin polymer (ßCD), where the Schiff bases remained inside the ßCD as determined by the ki , TGA, DSC, and SBET. We found that the inclusion in ßCD improved the solubility in aqueous media and the antifungal activity of both F1 and F2, revealing antimicrobial effects normally hidden by the presence of common solvents (e.g., DMSO) with some cellular inhibitory activity. The study of structural prerequisites for antimicrobial activity, and the inclusion in polymers to improve solubility, is important for the design of new drugs.

Reduction of Au(III) by a ß-cyclodextrin polymer in acid medium. A stated unattainable reaction.

Gold nanoparticles (AuNPs) can be prepared from the reduction of Au(III) with cyclodextrins acting as both, reducing and capping agent. It has been stated that a basic medium (pH=9-12) is a mandatory condition to achieve such reduction. We demonstrated, for the first time, the reduction of Au(III) by a crosslinked ß-cyclodextrin-epichlorohydrin polymer (ßCDP) in acid medium (pH ∼3). The coordination of Au(III) to the ßCD in ßCDP polymer required a ßCD:[AuCl4]- ratio of 4:1. The same ratio was necessary to achieve a 50% of the reduction of Au(III) to Au0 within the first 24h of reaction. During this initial time, the reaction showed a concentration-dependent reduction rate while for longer times the reduction rate was diffusion-dependent. An overall mechanism to explain this dependency has been proposed. The 13C NMR spectrum identified the oxidation of the COH groups to carboxylic ones by recording a signal at 175.6ppm. Gold nanoparticles cores (AuNPs) with a diameter of 34.2±7.7nm, determined by Transmission Electron Microscopy (TEM), was prepared by refluxing HAuCl4 in an aqueous solution of ßCDP. The AuNPs core was capped by dimers of the ßCDP polymer as determined by Dynamic Light Scattering measurements.