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Functionalization of Titanium implants using adequate organic molecules is a proposed method to accelerate the osteointegration process, which relates to topographical, chemical, mechanical, and physical features. This study aimed to assess the potential of a peptide derived from cementum attachment protein (CAP-p15) adsorbed onto aTiO2 surfaces to promote the deposition of calcium phosphate (CaP) minerals and its impact on the adhesion and viability of human periodontal ligament cells (hPDLCs). aTiO2 surfaces were synthesized by magnetron sputtering technique. The CAP-p15 peptide was physically attached to aTiO2 surfaces and characterized by atomic force microscopy, fluorescence microscopy, and water contact angle measurement. We performed in vitro calcium phosphate nucleation assays using an artificial saliva solution (pH 7.4) to simulate the oral environment. morphological and chemical characterization of the deposits were evaluated by scanning electronic microscopy (SEM) and spectroscopy molecular techniques (Raman Spectroscopy, ATR-FTIR). The aTiO2 surfaces biofunctionalized with CAP-p15 were also analyzed for hPDLCs attachment, proliferation, and in vitro scratch-healing assay. The results let us see that the homogeneous amorphous titanium oxide coating was 70 nanometers thick. The CAP-p15 (1 µg/mL) displayed the ability to adsorb onto the aTiO2 surface, increasing the roughness and maintaining the hydrophilicity of the aTiO2 surfaces. The physical adsorption of CAP-p15 onto the aTiO2 surfaces promoted the precipitation of a uniform layer of crystals with a flake-like morphology and a Ca/P ratio of 1.79. According to spectroscopy molecular analysis, these crystalline deposits correspond to carbonated hydroxyapatite. Regarding cell behavior, the biofunctionalized aTiO2 surfaces improved the adhesion of hPDLCs after 24 h of cell culture, achieving 3.4-fold when compared to pristine surfaces. Moreover, there was an increase in cell proliferation and cell migration processes. Physical adsorption of CAP-p15 onto aTiO2 surfaces enhanced the formation of carbonate hydroxyapatite crystals and promoted the proliferation and migration of human periodontal ligament-derived cells in in vitro studies. This experimental model using the novel bioactive peptide CAP-p15 could be used as an alternative to increasing the osseointegration process of implants.

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Silver tungstate (α-Ag2WO4), silver molybdate (ß-Ag2MoO4), and silver vanadate (α-AgVO3) microcrystals have shown interesting antimicrobial properties. However, their biocompatibility is not yet fully understood. Cytotoxicity and the inflammatory response of silver-containing microcrystals were analyzed in THP-1 and THP-1 differentiated as macrophage-like cells, with the alamarBlue™ assay, flow cytometry, confocal microscopy, and ELISA. The present investigation also evaluated redox signaling and the production of cytokines (TNFα, IL-1ß, IL-6, and IL-8) and matrix metalloproteinases (MMP-8 and -9). The results showed that α-AgVO3 (3.9 µg/mL) did not affect cell viability (p > 0.05). α-Ag2WO4 (7.81 µg/mL), ß-Ag2MoO4 (15.62 µg/mL), and α-AgVO3 (15.62 µg/mL) slightly decreased cell viability (p ≤ 0.003). All silver-containing microcrystals induced the production of O2 - and this effect was mitigated by Reactive Oxygen Species (ROS) scavenger and N-acetylcysteine (NAC). TNFα, IL-6 and IL-1ß were not detected in THP-1 cells, while their production was either lower (p ≤ 0.0321) or similar to the control group (p ≥ 0.1048) for macrophage-like cells. The production of IL-8 by both cellular phenotypes was similar to the control group (p ≥ 0.3570). The release of MMP-8 was not detected in any condition in THP-1 cells. Although MMP-9 was released by THP-1 cells exposed to α-AgVO3 (3.9 µg/mL), no significant difference was found with control (p = 0.7). Regarding macrophage-like cells, the release of MMP-8 and -9 decreased in the presence of all microcrystals (p ≤ 0.010). Overall, the present work shows a promising biocompatibility profile of, α-Ag2WO4, ß-Ag2MoO4, and α-AgVO3 microcrystals.

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Perovskite solar cells (PSCs) have rapidly developed into one of the most attractive photovoltaic technologies, exceeding power conversion efficiencies of 25% and as the most promising technology to complement silicon-based solar cells. Among different types of PSCs, carbon-based, hole-conductor-free PSCs (C-PSCs), in particular, are seen as a viable candidate for commercialization due to the high stability, ease of fabrication, and low cost. This review examines strategies to increase charge separation, extraction, and transport properties in C-PSCs to improve the power conversion efficiency. These strategies include the use of new or modified electron transport materials, hole transport layers, and carbon electrodes. Additionally, the working principles of various printing techniques for the fabrication of C-PSCs are presented, as well as the most remarkable results obtained from each technique for small-scale devices. Finally, the manufacture of perovskite solar modules using scalable deposition techniques is discussed.

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A chromate of copper and cobalt (Φy) was synthesized and characterized. Φy activated peroxymonosulfate (PMS) to degrade ciprofloxacin (CIP) in water. The Φy/PMS combination showed a high degrading capability toward CIP (~100% elimination in 15 min). However, Φy leached cobalt (1.6 mg L-1), limiting its use for water treatment. To avoid leaching, Φy was calcinated, forming a mixed metal oxide (MMO). In the combination of MMO/PMS, no metals leached, the CIP adsorption was low (<20%), and the action of SO4•- dominated, leading to a synergistic effect on pollutant elimination (>95% after 15 min of treatment). MMO/PMS promoted the opening and oxidation of the piperazyl ring, plus the hydroxylation of the quinolone moiety on CIP, which potentially decreased the biological activity. After three reuse cycles, the MMO still presented with a high activation of PMS toward CIP degradation (90% in 15 min of action). Additionally, the CIP degradation by the MMO/PMS system in simulated hospital wastewater was close to that obtained in distilled water. This work provides relevant information on the stability of Co-, Cu-, and Cr-based materials under interaction with PMS and the strategies to obtain a proper catalyst to degrade CIP.

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One of the main causes of food spoilage is the lipid oxidation of its components, which generates the loss of nutrients and color, together with the invasion of pathogenic microorganisms. In order to minimize these effects, active packaging has played an important role in preservation in recent years. Therefore, in the present study, an active packaging film was developed using polylactic acid (PLA) and silicon dioxide (SiO2) nanoparticles (NPs) (0.1% w/w) chemically modified with cinnamon essential oil (CEO). For the modification of the NPs, two methods (M1 and M2) were tested, and their effects on the chemical, mechanical, and physical properties of the polymer matrix were evaluated. The results showed that CEO conferred to SiO2 NPs had a high percentage of 2,2-diphenyl-l-picrylhydrazyl (DPPH) free radical inhibition (>70%), cell viability (>80%), and strong inhibition to E. coli, at 45 and 11 µg/mL for M1 and M2, respectively, and thermal stability. Films were prepared with these NPs, and characterizations and evaluations on apple storage were performed for 21 days. The results show that the films with pristine SiO2 improved tensile strength (28.06 MPa), as well as Young's modulus (0.368 MPa) since PLA films only presented values of 27.06 MPa and 0.324 MPa, respectively; however, films with modified NPs decreased tensile strength values (26.22 and 25.13 MPa), but increased elongation at break (from 5.05% to 10.32-8.32%). The water solubility decreased from 15% to 6-8% for the films with NPs, as well as the contact angle, from 90.21° to 73° for the M2 film. The water vapor permeability increased for the M2 film, presenting a value of 9.50 × 10-8 g Pa-1 h-1 m-2. FTIR analysis indicated that the addition of NPs with and without CEO did not modify the molecular structure of pure PLA; however, DSC analysis indicated that the crystallinity of the films was improved. The packaging prepared with M1 (without Tween 80) showed good results at the end of storage: lower values in color difference (5.59), organic acid degradation (0.042), weight loss (24.24%), and pH (4.02), making CEO-SiO2 a good component to produce active packaging.

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In this work, the structural, vibrational, morphological, and colloidal properties of commercial 15.1 nm TiO2 nanoparticles (NPs) and nanowires (NWs, 5.6 thickness, 74.6 nm length) were studied with the purpose of determining their ecotoxicological properties. This was achieved by evaluating acute ecotoxicity experiments carried out in the environmental bioindicator Daphnia magna, where their 24-h lethal concentration (LC50) and morphological changes were evaluated using a TiO2 suspension (pH = 7) with point of zero charge at 6.5 for TiO2 NPs (hydrodynamic diameter of 130 nm) and 5.3 for TiO2 NWs (hydrodynamic diameter of 118 nm). Their LC50 values were 157 and 166 mg L-1 for TiO2 NWs and TiO2 NPs, respectively. The reproduction rate of D. magna after fifteen days of exposure to TiO2 nanomorphologies was delayed (0 pups for TiO2 NWs and 45 neonates for TiO2 NPs) in comparison with the negative control (104 pups). From the morphological experiments, we may conclude that the harmful effects of TiO2 NWs are more severe than those of 100% anatase TiO2 NPs, likely associated with brookite (36.5 wt. %) and protonic trititanate (63.5 wt. %) presented in TiO2 NWs according to Rietveld quantitative phase analysis. Specifically, significant change in the heart morphological parameter was observed. In addition, the structural and morphological properties of TiO2 nanomorphologies were investigated using X-ray diffraction and electron microscopy techniques to confirm the physicochemical properties after the ecotoxicological experiments. The results reveal that no alteration in the chemical structure, size (16.5 nm for TiO2 NPs and 6.6 thickness and 79.2 nm length for NWs), and composition occurred. Hence, both TiO2 samples can be stored and reused for future environmental purposes, e.g., water nanoremediation.

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Clusters are physical entities composed of a few to thousands of atoms with capabilities to develop novel materials, like cluster-assembled materials. In this sense, knowing the electronic structure and physicochemical properties of the isolated clusters can be useful to understand how they interact with other chemical species by intermolecular forces, as free, embedded, and saturated clusters, and by intramolecular forces, acting as support clusters. In this way, in the present work, the electronic structure and physicochemical properties of metal oxide nanoclusters (MgO, Al2O3, SiO2, and TiO2) were studied by highly correlated molecular quantum chemistry methods. Through the electronic state's characterization, a semiconductor aspect was found for the titania oxide nanocluster (Te < 0.8 eV) while the other agglomerates showed a characteristic of insulating material (Te > 3.3 eV). From the stability index, the following stability order can be characterized: (SiO2)4 > (Al2O3)4 > (MgO)4 > (TiO2)3. Initial information of intermolecular and intramolecular forces caused by the studied clusters was calculated through the relative electrophilicity index, which classified the (MgO)4 and (TiO2)3 clusters as the more reactive ones, in which the (MgO)4 cluster was identified as a nucleophilic species, while the (TiO2)3 cluster as an electrophilic molecule.

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Global energy demand is increasing; thus, emerging renewable energy sources, such as organic solar cells (OSCs), are fundamental to mitigate the negative effects of fuel consumption. Within OSC's advancements, the development of efficient and stable interface materials is essential to achieve high performance, long-term stability, low costs, and broader applicability. Inorganic and nanocarbon-based materials show a suitable work function, tunable optical/electronic properties, stability to the presence of moisture, and facile solution processing, while organic conducting polymers and small molecules have some advantages such as fast and low-cost production, solution process, low energy payback time, light weight, and less adverse environmental impact, making them attractive as hole transporting layers (HTLs) for OSCs. This review looked at the recent progress in metal oxides, metal sulfides, nanocarbon materials, conducting polymers, and small organic molecules as HTLs in OSCs over the past five years. The endeavors in research and technology have optimized the preparation and deposition methods of HTLs. Strategies of doping, composite/hybrid formation, and modifications have also tuned the optical/electrical properties of these materials as HTLs to obtain efficient and stable OSCs. We highlighted the impact of structure, composition, and processing conditions of inorganic and organic materials as HTLs in conventional and inverted OSCs.

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Nanomaterials have attracted much attention over the last decades due to their very different properties compared to those of bulk equivalents, such as a large surface-to-volume ratio, the size-dependent optical, physical, and magnetic properties. A number of solution fabrication methods have been developed for the synthesis of metal and metal oxides nanoparticles, but few solid-state methods have been reported. The application of nanostructured materials to electronic solid-state devices or to high-temperature technology requires, however, adequate solid-state methods for obtaining nanostructured materials. In this review, we discuss some of the main current methods of obtaining nanomaterials in solid state, and also we summarize the obtaining of nanomaterials using a new general method in solid state. This new solid-state method to prepare metals and metallic oxides nanostructures start with the preparation of the macromolecular complexes chitosan·Xn and PS-co-4-PVP·MXn as precursors (X = anion accompanying the cationic metal, n = is the subscript, which indicates the number of anions in the formula of the metal salt and PS-co-4-PVP = poly(styrene-co-4-vinylpyridine)). Then, the solid-state pyrolysis under air and at 800 °C affords nanoparticles of M°, MxOy depending on the nature of the metal. Metallic nanoparticles are obtained for noble metals such as Au, while the respective metal oxide is obtained for transition, representative, and lanthanide metals. Size and morphology depend on the nature of the polymer as well as on the spacing of the metals within the polymeric chain. Noticeably in the case of TiO2, anatase or rutile phases can be tuned by the nature of the Ti salts coordinated in the macromolecular polymer. A mechanism for the formation of nanoparticles is outlined on the basis of TG/DSC data. Some applications such as photocatalytic degradation of methylene by different metal oxides obtained by the presented solid-state method are also described. A brief review of the main solid-state methods to prepare nanoparticles is also outlined in the introduction. Some challenges to further development of these materials and methods are finally discussed.

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Sol-Gel is a low cost, well-established and flexible synthetic route to produce a wide range of micro- and nanostructures. Small variations in pH, temperature, precursors, time, pressure, atmosphere, among others, can lead to a wide family of compounds that share the same molecular structures. In this work, we present a general review of the synthesis of LaMnO3, SrTiO3, BaTiO3 perovskites and zinc vanadium oxides nanostructures based on Sol-Gel method. We discuss how small changes in the parameters of the synthesis can modify the morphology, shape, size, homogeneity, aggregation, among others, of the products. We also discuss the different precursors, solvents, working temperature, reaction times used throughout the synthesis. In the last section, we present novel uses of Sol-Gel with organic materials with emphasis on carbon-based compounds. All with a perspective to improve the method for future applications in different technological fields.

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To date, the formation mechanisms of TiO2, as well as its heterostructures, have not been clarified. Moreover, detailed research on the transition from a tetragonal anatase phase to the monoclinic phase of the TiO2(B) phase and their interface structure has been quite limited until now. In the present study, we report on the sonochemical synthesis of TiO2-anatase with a crystallite size of 5.2 ± 1.5 nm under different NaOH concentrations via the hydrothermal method. The use of alkaline solution and the effect of the temperature and reaction time on the formation and structural properties of TiO2-anatase nanopowders were studied. The effects of NaOH concentration on the formation and transformation of titanate structures are subject to thermal effects that stem from the redistribution of energy in the system. These mechanisms could be attributed to three phenomena: (1) the self-assembly of nanofibers and nanosheets, (2) the Ostwald ripening process, and (3) the self-development of hollow TiO2 mesostructures.

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The focus of this paper is centered on the thermal reduction of KMnO4 at controlled temperatures of 400 and 800 °C. The materials under study were characterized by atomic absorption spectroscopy, thermogravimetric analysis, average oxidation state of manganese, nitrogen adsorption-desorption, and impedance spectroscopy. The structural formulas, found as a result of these analyses, were K 0.29 + ( M n 0.84 4 + M n 0.16 3 + ) O 2.07 · 0.61 H 2 O and K 0.48 + ( M n 0.64 4 + M n 0.36 3 + ) O 2.06 · 0.50 H 2 O . The N2 adsorption-desorption isotherms show the microporous and mesoporous nature of the structure. Structural analysis showed that synthesis temperature affects the crystal size and symmetry, varying their electrical properties. Impedance spectroscopy (IS) was used to measure the electrical properties of these materials. The measurements attained, as a result of IS, show that these materials have both electronic and ionic conductivity. The conductivity values obtained at 10 Hz were 4.1250 × 10-6 and 1.6870 × 10-4 Ω-1cm-1 for Mn4 at 298 and 423 K respectively. For Mn8, the conductivity values at this frequency were 3.7074 × 10-7 (298) and 3.9866 × 10-5 Ω-1cm-1 (423 K). The electrical behavior was associated with electron hopping at high frequencies, and protonic conduction and ionic movement of the K+ species, in the interlayer region at low frequencies.

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Active food packaging systems promote better food quality and/or stability, such as by releasing antimicrobial agents into food. Advantages of adding antimicrobials to the packaging material instead of into the bulk food include controlled diffusion, reduced antimicrobial contents, and improved cost effectiveness. Nanostructured antimicrobials are especially effective due to their high specific surface area. The present review is focused on recent advances and findings on the main nanostructured antimicrobial packaging systems for food packaging purposes. Several kinds of nanostructures, including both inorganic particles and organic structures, have been proven effective antimicrobials by different mechanisms of action and with different application scopes. Moreover, there are systems containing nanocarriers to protect antimicrobials and deliver them in a controlled fashion. On the other hand, scientific data about migration of nanostructures onto food and their toxicity are still limited, requiring special attention from researchers and regulation sectors.

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This paper describes a thermal method to obtain metal oxides on a titanium substrate surface. This adapted Pechini method is a versatile, easy to handle and scalable technique to obtain electrodes for industrial uses, such as Dimensionally Stable Anodes (DSA). This method has advantages over other thermal methods like dip coating or sputtering, as it needs a smaller amount of polymeric mixture than dip coating method to cover the same area and is less expensive than sputtering method. The thermal method described herein to prepare DSA type electrodes of RuO2-ZrO2 doped with Sb2O5 over titanium plates needs no sophisticated equipment as spray pyrolysis technique does; a muffle, ultrasonic equipment, and a hot plate magnetic stirrer are the principal apparatus necessary to carry out the adapted Pechini method. On the other hand, this method allows metal oxides to disperse homogeneously. The cyclic voltammograms showed the stability of DSA, and the accelerated life test allowed establishing its useful life (18.18 years) at a current density of 10 mA cm-2.

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X-ray Absorption Fine Structure (XAFS) spectroscopy has been widely used to characterize the short-range order of glassy materials since the theoretical basis was established 45 years ago. Soon after the technique became accessible, mainly due to the existence of Synchrotron laboratories, a wide range of glassy materials was characterized. Silicate glasses have been the most studied because they are easy to prepare, they have commercial value and are similar to natural glasses, but borate, germanate, phosphate, tellurite and other less frequent oxide glasses have also been studied. In this manuscript, we review reported advances in the structural characterization of oxide-based glasses using this technique. A focus is on structural characterization of transition metal ions, especially Ti, Fe, and Ni, and their role in different properties of synthetic oxide-based glasses, as well as their important function in the formation of natural glasses and magmas, and in nucleation and crystallization. We also give some examples of XAFS applications for structural characterization of glasses submitted to high pressure, glasses used to store radioactive waste and medieval glasses. This updated, comprehensive review will likely serve as a useful guide to clarify the details of the short-range structure of oxide glasses.

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This mini review is limited to very recent studies (last 5-10 years) on two major issues, concerning: the production and physical/chemical modification of bacterial cellulose (BC), and its transformation into carbon and integrated synthesis of metal oxides (TiO2, ZnO, Fe3O4, etc.), metal sulfide (ZnS, CdS, etc.) and metal nanoparticles (Au, Ag, Pt, Pd, etc.) within bacterial cellulose nanoribbons network. We believe that the crossover of these two domains could be of considerable interest in the view of improving the performance of materials prepared with bacterial cellulose. The diversity of these nanomaterials allows targeting of many very different properties/applications: electrochemical devices, catalysis and photocatalysis, sensors, etc. After an introduction to the most important chemical and physical characteristics of BC, production parameters, and its physical and chemical modifications, we review the use of BC as a precursor of inorganic materials like carbon and composites with metal or inorganic nanoparticles.

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The development of sensors and biosensors based on copper enzymes and/or copper oxides for phenol sensing is disclosed in this work. The electrochemical properties were studied by cyclic and differential pulse voltammetry using standard solutions of potassium ferrocyanide, phosphate/acetate buffers and representative natural phenols in a wide pH range (3.0 to 9.0). Among the natural phenols herein investigated, the highest sensitivity was observed for rutin, a powerful antioxidant widespread in functional foods and ubiquitous in the plant kingdom. The calibration curve for rutin performed at optimum pH (7.0) was linear in a broad concentration range, 1 to 120 µM (r = 0.99), showing detection limits of 0.4 µM. The optimized biomimetic sensor was also applied in total phenol determination in natural samples, exhibiting higher stability and sensitivity as well as distinct selectivity for antioxidant compounds.

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Well-defined mixed-metal [CoMn3 O4 ] and [NiMn3 O4 ] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts' heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni-Mn oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3 O4 cubane-like geometry was maintained in the absence of thermal treatment (2-Ni). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in Photosystem II, including the MMn3 O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides.

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Hydrated ferric oxide (HFeO), hydrated zirconium oxide (HZrO) and hydrated copper oxide (HCuO) were immobilized within a microporous anion exchange resin (IRA-400), forming hybrid media for enhanced phosphate removal from aqueous systems. Empirical data from batch kinetic trials fitted the pseudo second order mechanism for chemical adsorption and each media was rate limited by intraparticle diffusion overall. These models were also used to predict the adsorption rate constants and the equilibrium adsorption capacities, which ranged from 26.51 to 30.44 mgP g(-1), and from 24.15 to 27.90 mgP g(-1) of media for the calculated and experimental capacities, respectively. The phosphate adsorption behavior by the hybrid materials fit both the Langmuir and Freundlich adsorption isotherms (R(2)>0.94), and the maximum adsorption capacities were 111.1 mgP g(-1) for HFeO, 91.74 mgP g(-1) for HZrO and 74.07 mgP g(-1) for HCuO. The effect of competing ions such as sulfate reduced these capacities to 18.52 mgP g(-1) for HFeO and 18.97 mgP g(-1) for HZrO. Despite this decrease, HFeO was capable of reducing the phosphate in a real wastewater matrix by 83%, and the HZrO media was able to reduce it by 86%, suggesting that such hybrid media have the potential for application at full scale.

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