Accelerated Cr (VI) removal by a three-dimensional electro-Fenton system using green iron nanoparticles.

Green-synthesized iron nanoparticles (GAP-FeNP) were used as particle electrodes in a three-dimensional electro-Fenton (3DEF) process to accelerate the removal of hexavalent chromium [Cr (VI)]. Removal was evaluated by varying the pH (3.0, 6.0, and 9.0) and initial Cr (VI) concentrations (10, 30, and 50 mg/L) at 5 and 25 min. These results demonstrated that GAP-FeNP/3DEF treatment achieved more than 94% Cr (VI) removal under all tested conditions. Furthermore, it was observed that Cr (VI) removal exceeded 98% under pH 9.0 in all experimental parameters tested. The results of the response surface methodology (RSM) determined two optimal conditions: the first, characterized by a pH of 3.0, Cr (VI) concentration at 50 mg/L, and 25 min, yielded a Cr (VI) removal of 99.7%. The second optimal condition emerged at pH 9.0, with Cr (VI) concentrations of 10 mg/L and 5 min, achieving a Cr (VI) removal of 99.5%. This study highlights the potential of the GAP-FeNP to synergistically accelerate Cr (VI) removal by the 3DEF process, allowing faster elimination and expansion of the alkaline (pH 9.0) applicability. PRACTITIONER POINTS: The required time for >99% of Cr (VI) removal by the GAP-FeNP/3DEF process was shortened from 25 to 5 min. EF process with GAP-FeNP reduces the time necessary for Cr (VI) removal, which is 67% faster than conventional methods. EF process using GAP-FeNP removed >94% of Cr (VI) after 25 min for all initial Cr (VI) concentrations and pH treatments. Cr (VI) removal by the GAP-FeNP/3DEF process was >98% at a pH of 9.0, widening the solution pH applicability.

Novel pathway for the sonochemical synthesis of silver nanoparticles with near-spherical shape and high stability in aqueous media.

The present study shows the development of a novel sonochemical synthesis pathway of sub-15 nm silver nanoparticles (AgNPs) with quasi-spherical shape and high stability in aqueous suspension. Different analytical techniques such as on-line UV-Vis spectroscopy, Atomic Force Microscopy (AFM), and Transmission Electron Microscopy (TEM) were complementarily used to characterize the evolution of the properties of AgNPs synthesized with this new route. Furthermore, different centrifugation conditions were studied to establish a practical, simple and straightforward purification method. Particle size was determined by TEM employing two different deposition methods, showing that purified AgNPs have a size of 8.1 nm ± 2.4 nm with a narrow dispersion of the size distribution (95% coverage interval from 3.4 to 13 nm). Critical information of the shape and crystalline structure of these sub-15 nm AgNPs, provided by shape descriptors (circularity and roundness) using TEM and high resolution (HR)-TEM measurements, confirmed the generation of AgNPs with quasi-spherical shapes with certain twin-fault particles promoted by the high energy of the ultrasonic treatment. Elemental analysis by TEM-EDS confirmed the high purity of the sub-15 nm AgNPs, consisting solely of Ag. At the optical level, these AgNPs showed a bandgap energy of (2.795 ± 0.002) eV. Finally, the evaluation of the effects of ultraviolet radiation (UVC: 254 nm and UVA: 365 nm) and storage temperature on the spectral stability revealed high stability of the optical properties and subsequently dimensional properties of sub-15 nm AgNPs in the short-term (600 min) and long-term (24 weeks).

Sonotherapy in the reduction of anxiety and postoperative pain in patients with regional anesthesia as a sole technique: randomized, controlled clinical trial.

OBJECTIVE: To determine if sonotherapy reduces the anxiety level and postoperative pain in adults undergoing outpatient orthopedic surgery under regional anesthesia. METHOD: A randomized, double-blind, placebo-controlled study in 80 adult patients undergoing orthopedic surgery, 40 received intervention with sonotherapy and 40 did not receive it. Pain, anxiety in the preoperative period, immediate postoperative, high, 24 and 48 hours later were measured. Hemodynamic parameters were measured in four moments. RESULTS: No significant differences were found between the two groups in the pain scales neither anxiety. A significant reduction of the systolic blood pressure was observed after the application of sonotherapy and in recovery. There was no difference in other hemodynamic variables such as heart rate, respiratory rate, arterial oxygen saturation or diastolic blood pressure between groups, however, the observed changes in some of them occurred faster in the intervention group. CONCLUSIONS: In adult patients undergoing outpatient orthopaedic surgery under regional anaesthesia, sound therapy is a novel strategy that significantly reduces systolic blood pressure, considered as an indicator of decreased anxiety. However, in our study, no difference could be demonstrated in terms of pain control or the need for additional sedation or analgesia.

OBJETIVO: Evaluar la eficacia de la sonoterapia en la diminución de la ansiedad y el dolor posoperatorio en adultos llevados a cirugía ambulatoria de ortopedia bajo anestesia regional. MÉTODO: estudio aleatorizado, doble ciego, controlado con placebo, en 80 pacientes adultos sometidos a cirugía ortopédica; 40 recibieron intervención con sonoterapia y 40 no la recibieron. Se midieron el dolor y la ansiedad en el preoperatorio, en el posoperatorio inmediato, al alta, y 24 y 48 horas después. Se midieron parámetros hemodinámicos en cuatro momentos. RESULTADOS: No se encontraron diferencias significativas entre ambos grupos en las escalas de dolor ni ansiedad. Se observó una reducción significativa de la presión arterial sistólica luego de la aplicación de la intervención y en recuperación. No se observaron diferencias en otras variables hemodinámicas entre los grupos, pero la reducción de algunas ocurre de forma más rápida en el grupo de intervención. CONCLUSIONES: En pacientes adultos llevados a cirugía ambulatoria de ortopedia bajo anestesia regional, la sonoterapia es una estrategia novedosa que reduce la presión arterial sistólica, y esto puede considerarse como un indicador de disminución de la ansiedad. En nuestro estudio no se pudo demostrar diferencia en términos de control del dolor ni de requerimiento de sedación o analgesia adicional.

Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides.

Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface-the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology-significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared.

Surface-initiated polymerization from barium titanate nanoparticles for hybrid dielectric capacitors.

A phosphonic acid is used as a surface initiator for the growth of polystyrene and polymethylmethacrylate (PMMA) from barium titanate (BTO) nanoparticles through atom transfer radical polymerization with activators regenerated by electron transfer. This results in the barium titanate cores embedded in the grafted polymer. The one-component system, PMMA-grafted-BTO, achieves a maximum extractable energy density of 2 J/cm(3) at a field strength of ∼220 V/µm, which exhibits a 2-fold increase compared to that of the composite without covalent attachment or the neat polymer. Such materials have potential applications in hybrid capacitors due to the high permittivity of the nanoparticles and the high breakdown strength, mechanical flexibility, and ease of processability due to the organic polymer. The synthesis, processing, characterization, and testing of the materials in capacitors are discussed.

Efficient modification of metal oxide surfaces with phosphonic acids by spray coating.

We report a rapid method of depositing phosphonic acid molecular groups onto conductive metal oxide surfaces. Solutions of pentafluorobenzyl phosphonic acid (PFBPA) were deposited on indium tin oxide, indium zinc oxide, nickel oxide, and zinc oxide by spray coating substrates heated to temperatures between 25 and 150 °C using a 60 s exposure time. Comparisons of coverage and changes in work function were made to the more conventional dip-coating method utilizing a 1 h exposure time. The data show that the work function shifts and surface coverage by the phosphonic acid were similar to or greater than those obtained by the dip-coating method. When the deposition temperature was increased, the magnitude of the surface coverage and work function shift was also found to increase. The rapid exposure of the spray coating was found to result in less etching of zinc-containing oxides than the dip-coating method. Bulk heterojunction solar cells made of polyhexylthiophene (P3HT) and bis-indene-C60 (ICBA) were tested with PFBPA dip and spray-modified ITO substrates as well as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)-modified ITO. The spray-modified ITO solar cells showed a similar open circuit voltage (VOC) and fill factor (FF) and a less than 5% lower short circuit current density (JSC) and power conversion efficiency (PCE) than the dip- and PEDOT:PSS-modified ITO. These results demonstrate a potential path to a scalable method to deposit phosphonic acid surface modifiers on metal oxides while overcoming the limitations of other techniques that require long exposure and post-processing times.

The modification of indium tin oxide with phosphonic acids: mechanism of binding, tuning of surface properties, and potential for use in organic electronic applications.

Transparent metal oxides, in particular, indium tin oxide (ITO), are critical transparent contact materials for applications in next-generation organic electronics, including organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs). Understanding and controlling the surface properties of ITO allows for the molecular engineering of the ITO-organic interface, resulting in fine control of the interfacial chemistries and electronics. In particular, both surface energy matching and work function compatibility at material interfaces can result in marked improvement in OLED and OPV performance. Although there are numerous ways to change the surface properties of ITO, one of the more successful surface modifications is the use of monolayers based on organic molecules with widely variable end functional groups. Phosphonic acids (PAs) are known to bind strongly to metal oxides and form robust monolayers on many different metal oxide materials. They also demonstrate several advantages over other functionalizing moieties such as silanes or carboxylic acids. Most notably, PAs can be stored in ambient conditions without degradation, and the surface modification procedures are typically robust and easy to employ. This Account focuses on our research studying PA binding to ITO, the tunable properties of the resulting surfaces, and subsequent effects on the performance of organic electronic devices. We have used surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and infrared reflection adsorption spectroscopy (IRRAS) to determine that PAs bind to ITO in a predominantly bidentate fashion (where two of three oxygen atoms from the PA are involved in surface binding). Modification of the functional R-groups on PAs allows us to control and tune the surface energy and work function of the ITO surface. In one study using fluorinated benzyl PAs, we can keep the surface energy of ITO relatively low and constant but tune the surface work function. PA modification of ITO has resulted in materials that are more stable and more compatible with subsequently deposited organic materials, an effective work function that can be tuned by over 1 eV, and energy barriers to hole injection (OLED) or hole-harvesting (OPV) that can be well matched to the frontier orbital energies of the organic active layers, leading to better overall device properties.

Surface-initiated synthesis of poly(3-methylthiophene) from indium tin oxide and its electrochemical properties.

Poly(3-methylthiophene) (P3MT) was synthesized directly from indium tin oxide (ITO) electrodes modified with a phosphonic acid initiator, using Kumada catalyst transfer polymerization (KCTP). This work represents the first time that polymer thickness has been controlled in a surface initiated KCTP reaction, highlighting the utility of KCTP in achieving controlled polymerizations. Polymer film thicknesses were regulated by the variation of the solution monomer concentration and ranged from 30 to 265 nm. Electrochemical oxidative doping of these films was used to manipulate their near surface composition and effective work function. Doped states of the P3MT film are maintained even after the sample is removed from solution and potential control confirming the robustness of the films. Such materials with controllable thicknesses and electronic properties have the potential to be useful as interlayer materials for organic electronic applications.