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Cement-based products are the synthetic materials most used by humans, with consequent environmental impacts. One strategy that can assist in mitigating the adverse environmental effects of these materials involves the incorporation of multifunctional nanostructured additives. The objective of this work was to demonstrate the efficacy of incorporating mixed oxides (MO) derived from layered double hydroxides (LDH) to control the rheology and porosity of cement-based matrices. Thermal aging of LDH enabled the preparation of MO with different specific surface areas (SSA) for incorporation in different amounts in Portland cement. A low proportion of MO and low SSA increased workability by 22%. In contrast, a high proportion of MO and high SSA led to a 2.4-fold acceleration of cement consolidation and a 36.9% decrease of the porosity of the composite. These features could be attributed to additive-matrix interactions, with the LDH memory effect playing key roles in the cement crystal seed process and in competition for the absorption of free water within the cement paste. Therefore, the unprecedent results obtained suggest that the quantity and SSA of MO are key parameters to fine-tune the paste rheology and structure of hidrated cement. The MO materials showed easy adaptability and excellent potential for use as multifunctional additives in the production of eco-friendly, high-performance cement paste formulations with controllable properties according to the desired application.

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The use of nanotechnology in medicine has important potential applications, including in anticancer strategies. Nanomedicine has made it possible to overcome the limitations of conventional monotherapies, in addition to improving therapeutic results by means of synergistic or cumulative effects. A highlight is the combination of gene therapy (GT) and photodynamic therapy (PDT), which are alternative anticancer approaches that have attracted attention in the last decade. In this review, strategies involving the combination of PDT and GT will be discussed, together with the role of nanocarriers (nonviral vectors) in this synergistic therapeutic approach, including aspects related to the design of nanomaterials, responsiveness, the interaction of the nanomaterial with the biological environment, and anticancer performance in studies in vitro and in vivo.

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Reinforcement steel extensively applied in civil construction is susceptible to corrosion due to the carbonation process in reinforced concrete and chloride ions diffusion. Epoxy-silica-based coatings are a promising option to guarantee the long-term stability of reinforced concrete structures. In this study, the influence of the proportion between the poly (bisphenol-A-co-epichlorhydrin) resin (DGEBA) and the curing agent diethylenetriamine (DETA) on the structural, morphological, and barrier properties of epoxy-silica nanocomposites were evaluated. To simulate different stages of concrete aging, electrochemical impedance spectroscopy (EIS) assays were performed for coated samples in a 3.5 wt.% NaCl solution (pH 7) and in simulated concrete pore solutions (SCPS), which represent the hydration environment in fresh concrete (SCPS2, pH 14) and after carbonation (SCPS1, pH 8). The results showed that coatings with an intermediate DETA to DGEBA ratio of 0.4, presented the best long-term corrosion protection with a low-frequency impedance modulus of up to 3.8 GΩ cm2 in NaCl and SCPS1 solutions. Small-angle X-ray scattering and atomic force microscopy analysis revealed that the best performance observed for the intermediate DETA proportion is associated with the presence of larger silica nanodomains, which act as a filler in the cross-linked epoxy matrix, thus favoring the formation of an efficient diffusion barrier.

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This paper presents the influence of the presence of a modified organoclay, Cloisite® 20A (MMTA) on the structural and drug release properties of ureasil organic-inorganic hybrid. Sol-gel process was used to prepare the hybrid nanocomposites containing sodium diclofenac (DCF) at 5% wt. The effect of the amount of MMTA incorporated into the ureasil hybrid matrix was evaluated and characterized in depth by different techniques such as X-ray diffraction (XRD), small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and swelling properties. The influence of MMTA on ureasil nanocomposites release profile was evaluated by in situ UV-vis. The diffraction patterns of the UPEO-MMTA nanocomposites showed a synergistic contribution effect that led to an intensity increase and narrowed the diffraction peaks, evidencing a crystallite PEO growth as a function of the modified nanoclay content. The interactions between polyether chains and the hydrogenated tallow of MMTA led to an easy intercalation process, as observed in UPEO-MMTA nanocomposites containing low (1% wt) or high (20% wt) nanoclay content. The waterway (channels) created in UPEO-MMTA nanocomposites contributed to a free volume increase in the swollen network compared to UPEO without MMTA. The hypothesis of the channels created after intercalation of the PEO phase in the interlayer of MMTA containing organoammonium ions corroborates with the XRD results, swelling studies by SAXS, and release assays. Furthermore, when these clay particles were dispersed in the polymeric matrix by an intercalation process, water uptake improvement was observed, with an increased amount of DCF release. The design of ureasil-MMTA nanocomposites containing modified nanoclay endows them with tunable properties; for example, swelling degree followed by amount of controlled drug release, opening the way for more versatile biomedical applications.

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In this work, a set of experimental electrophoretic mobility (µe) data was used to show how inappropriate selection of the electrokinetic model used to calculate the zeta potential (ζ-potential) can compromise the interpretation of the results for nanoparticles (NPs). The main consequences of using ζ-potential values as criteria to indicate the colloidal stability of NP dispersions are discussed based on DLVO interaction energy predictions. For this, magnetite (Fe3O4) NPs were synthesized and characterized as a model system for performing electrokinetic experiments. The results showed that the Fe3O4 NPs formed mass fractal aggregates in solution, so the ζ-potential could not be determined under ideal conditions when µe depends on the NP radius. In addition, the Dukhin number (Du) estimated from potentiometric titration results indicated that stagnant layer conduction (SLC) could not be neglected for this system. The electrokinetic models that do not consider SLC grossly underestimated the ζ-potential values for the Fe3O4 NPs. The DLVO interaction energy predictions for the colloidal stability of the Fe3O4 NP dispersions also depended on the electrokinetic model used to calculate the ζ-potential. The results obtained for the Fe3O4 NP dispersions also suggested that, contrary to many reports in the literature, high ζ-potential values do not necessarily reflect high colloidal stability for charge-stabilized NP dispersions.

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Acetaldehyde is an important chemical commodity and a building block for producing several other high-value products in the chemical industry. This has motivated the search for suitable, efficient, stable, and selective catalysts, as well as renewable raw materials such as ethanol. In this work, supported copper catalysts were prepared from CuZnAl layered double hydroxides (LDHs) with different copper contents (5, 10, and 20 wt %) for application in the ethanol dehydrogenation reaction (EDR). The samples were thoroughly characterized by a series of techniques, which allowed for analysis of all of the copper and zinc species involved in the different catalyst preparation steps and during the EDR. The results obtained by in situ quick extended X-ray absorption fine structure (EXAFS) measurements, combined with multivariate data analysis, showed that the copper content in the pristine LDH influenced the phase composition of the mixed oxide support, which consequently affected the dispersion of copper nanoparticles. The higher the copper content, the higher are the ZnAl2O4 and zinc tetrahedral prenuclei (TPN) contents, to the detriment of the ZnO content. All the samples showed high selectivity (>97%) and stability in the catalytic reactions at 300 and 350 °C, with no observed deactivation during 6 h on-stream. Although the samples with lower copper content presented higher copper dispersion and reactivity, the sample containing 20 wt % of copper outperformed the others, with greater conversion and higher activity toward acetaldehyde.

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Organic-inorganic hybrid coatings deposited on different types of metallic alloys have shown outstanding anticorrosive performance. The incorporation of osteoconductive additives such as hydroxyapatite (HA) and ß-tricalcium phosphate (ß-TCP) into organic-inorganic hybrid coatings is promising to improve the osseointegration and corrosion resistance of Ti6Al4V alloys, which are the most widely used metallic orthopedic and dental implant materials today. Therefore, this study evaluated the capability of poly(methyl methacrylate) (PMMA)-TiO2 and PMMA-ZrO2 hybrid coatings modified with HA and ß-TCP to act as bioactive and corrosion protection coatings for Ti6Al4V alloys. In terms of cell growth and mineralization, osteoblast viability, Ca+2 deposition and alkaline phosphatase assays revealed a significant improvement for the HA and ß-TCP modified coatings, compared to the bare alloy. This can be explained by an increase in nanoscale roughness and associated higher surface free energy, which lead to enhanced protein adsorption to promote osteoblast attachment and functions on the coatings. The effect of HA and ß-TCP additives on the anticorrosive efficiency was studied by electrochemical impedance spectroscopy (EIS) in a simulated body fluid (SBF) solution. The coatings presented a low-frequency impedance modulus of up to 430 GΩ cm2, 5 decades higher than the bare Ti6Al4V alloy. These findings provide clear evidence of the beneficial role of HA and ß-TCP modified hybrid coatings, improving both the biocompatibility and corrosion resistance of the Ti6Al4V alloy.

Assuntos

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In this work, we describe the synthesis and characterization of the SPIONP-CUR conjugate between curcumin (CUR) and superparamagnetic iron oxide nanoparticles (SPIONPs), in addition to its application in photodynamic therapy (PDT) using a protocol free of organic solvents as a dispersant. The SPIONP-CUR conjugate was characterized by X-ray diffraction, transmission electron microscopy, zeta potential measurements, Fourier transform infrared spectroscopy, thermogravimetry, magnetometry and magnetic hyperthermia assays. The SPIONP-CUR conjugation occurred by bonding between the keto-enol moiety of CUR and the iron atoms present on the surfaces of the SPIONPs. The conjugate showed heating power under an alternating magnetic field (AMF) and photodynamic action when irradiated with blue LED light. In experiments using PDT against Staphylococcus aureus in the planktonic phase, it was demonstrated that with application of blue light at 3.12 J cm-2, the conjugate (dispersed in water) caused a total reduction of the bacterial load. In the absence of light, the reduction was insignificant, even after 24 h of contact with the bacteria.

Assuntos

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In this work, structural and active corrosion inhibition effects induced by lithium ion addition in organic-inorganic coatings based on poly(methyl methacrylate) (PMMA)-silica sol-gel coatings have been investigated. The addition of increasing amounts of lithium carbonate (0, 500, 1000, and 2000 ppm), yielded homogeneous hybrid coatings with increased connectivity of nanometric silica cross-link nodes, covalently linked to the PMMA matrix, and improved adhesion to the aluminum substrate (AA7075). Electrochemical impedance spectroscopy (EIS), performed in 3.5% NaCl aqueous solution, showed that the improved structural properties of coatings with higher lithium loadings result in an increased corrosion resistance, with an impedance modulus up to 50 GΩ cm2, and revealed that the lithium induced self-healing ability significantly improves their durability. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) suggest that the regeneration process occurs by means of lithium ions leaching from the adjacent coating toward the corrosion spot, which is restored by a protective layer of precipitated Li rich aluminum hydroxide species. An analogue mechanism has been proposed for artificially scratched coatings presenting an increase of the impedance modulus after salt spray test compared to the lithium free coating. These results evidence the active role of lithium ions in improving the passive barrier of the PMMA-silica coating and in providing through the self-restoring ability a significantly extended service life of AA7075 alloy exposed to saline environment.

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In this article, we demonstrate that each functional group of ureasil organic-inorganic hybrid (OIH) materials can act as a specific coordination site for a given active guest species, hence allowing the possibility of combining different functional properties. To illustrate this concept, the sol-gel process was used to produce diurea cross-linked siloxane-polyethylene oxide (U-PEO) and siloxane-polypropylene oxide (U-PPO) hybrid host frameworks with similar molecular weights (1900 and 2000 g mol-1 for PEO and PPO, respectively), with Li+ and Eu3+ as active guest ions providing ionic conduction and photoluminescence (PL) properties, respectively. Comparison of Fourier transform infrared spectra and small-angle X-ray scattering results for single-doped (using Li+ or Eu3+) and co-doped (using Li+ and Eu3+) U-PEO and U-PPO hosts showed that in every case, there was specific coordination of Eu3+ by the carbonyl group of the urea bridge and of Li+ by ether-type oxygen of the PEO and PPO chains. Optical analyses demonstrated that loading with Li+ did not affect the luminescence properties of the Eu3+-loaded OIH. Although loading with Eu3+ had a small effect on ionic transport, co-doping with Li+ ions ensured macroscopic ion-conduction of the transparent and luminescent hybrid material. The results suggested that the combination of both properties in a transparent elastomeric material could be useful for the development of multifunctional devices. The results suggested that the combination of both properties in a transparent elastomeric material could be useful for the development of multifunctional polyelectrolytes applied in the field of dual luminescent devices such as photoelectrochromic smart windows.

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In this work, we report the effects of incorporation of variable amounts (1-20 wt %) of sodium montmorillonite (MMT) into a siloxane-poly(ethylene oxide) hybrid hydrogel prepared by the sol-gel route. The aim was to control the nanostructural features of the nanocomposite, improve the release profile of the sodium diclofenac (SDCF) drug, and optimize the swelling behavior of the hydrophilic matrix. The nanoscopic characteristics of the siloxane-cross-linked poly(ethylene oxide) network, the semicrystallinity of the hybrid, and the intercalated or exfoliated structure of the clay were investigated by X-ray diffraction, small-angle X-ray scattering, and differential scanning calorimetry. The correlation between the nanoscopic features of nanocomposites containing different amounts of MMT and the swelling behavior revealed the key role of exfoliated silicate in controlling the water uptake by means of a flow barrier effect. The release of the drug from the nanocomposite displayed a stepped pattern kinetically controlled by the diffusion of SDCF molecules through the mass transport barrier created by the exfoliated silicate. The sustained SDCF release provided by the hybrid hydrogel nanocomposite could be useful for the prolonged treatment of painful conditions, such as arthritis, sprains and strains, gout, migraine, and pain after surgical procedures.

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ZnO/ZnS heterostructures have emerged as an attractive approach for tailoring the properties of particles comprising these semiconductors. They can be synthesized using low temperature sol-gel routes. The present work yields insight into the mechanisms involved in the formation of ZnO/ZnS nanostructures. ZnO colloidal suspensions, prepared by hydrolysis and condensation of a Zn acetate precursor solution, were allowed to react with an ethanolic thioacetamide solution (TAA) as sulfur source. The reactions were monitored in situ by Small Angle X-ray Scattering (SAXS) and UV-vis spectroscopy, and the final colloidal suspensions were characterized by High Resolution Transmission Electron Microscopy (HRTEM). The powders extracted at the end of the reactions were analyzed by X-ray Absorption spectroscopy (XAS) and X-ray diffraction (XRD). Depending on TAA concentration, different nanostructures were revealed. ZnO and ZnS phases were mainly obtained at low and high TAA concentrations, respectively. At intermediate TAA concentrations, we evidenced the formation of ZnO/ZnS heterostructures. ZnS formation could take place via direct crystal growth involving Zn ions remaining in solution and S ions provided by TAA and/or chemical conversion of ZnO to ZnS. The combination of all the characterization techniques was crucial to elucidate the reaction steps and the nature of the final products.

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Carbon nanotubes (CNTs) and graphene oxide (GO) have been used to reinforce PMMA-siloxane-silica nanocomposites considered to be promising candidates for environmentally compliant anticorrosive coatings. The organic-inorganic hybrids were prepared by benzoyl peroxide (BPO)-induced polymerization of methyl methacrylate (MMA) covalently bonded through 3-(trimethoxysilyl)propyl methacrylate (MPTS) to silica domains formed by hydrolytic condensation of tetraethoxysilane (TEOS). Single-walled carbon nanotubes and graphene oxide nanosheets were dispersed by surfactant addition and in a water/ethanol solution, respectively. These were added to PMMA-siloxane-silica hybrids at a carbon (CNT or GO) to silicon (TEOS and MPTS) molar ratio of 0.05% in two different matrices, both prepared at BPO/MMA molar ratios of 0.01 and 0.05. Atomic force microscopy and scanning electron microscopy showed very smooth, homogeneous, and defect-free surfaces of approximately 3-7 µm thick coatings deposited onto A1020 carbon steel by dip coating. Mechanical testing and thermogravimetric analysis confirmed that both additives CNT and GO improved the scratch resistance, adhesion, wear resistance, and thermal stability of PMMA-siloxane-silica coatings. Results of electrochemical impedance spectroscopy in 3.5% NaCl solution, discussed in terms of equivalent circuits, showed that the reinforced hybrid coatings act as a very efficient anticorrosive barrier with an impedance modulus up to 1 GΩ cm(2), approximately 5 orders of magnitude higher than that of bare carbon steel. In the case of GO addition, the high corrosion resistance was maintained for more than 6 months in saline medium. These results suggest that both carbon nanostructures can be used as structural reinforcement agents, improving the thermal and mechanical resistance of high performance anticorrosive PMMA-siloxane-silica coatings and thus extending their application range to abrasive environments.

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The unique properties of ceramic foams enable their use in a variety of applications. This work investigated the effects of different parameters on the production of zirconia ceramic foam using the sol-gel process associated with liquid foam templates. Evaluation was made of the influence of the thermal treatment temperature on the porous and crystalline characteristics of foams manufactured using different amounts of sodium dodecylsulfate (SDS) surfactant. A maximum pore volume, with high porosity (94%) and a bimodal pore size distribution, was observed for the ceramic foam produced with 10% SDS. Macropores, with an average size of around 30 µm, were obtained irrespective of the SDS amount, while the average size of the supermesopores increased systematically as the SDS amount was increased up to 10%, after which it decreased. X-ray diffraction analyses showed that the sample treated at 500 °C was amorphous, while crystallization into a tetragonal metastable phase occurred at 600 °C due to the presence of sulfate groups in the zirconia structure. At 800 and 1000 °C the monoclinic phase was observed, which is thermodynamically stable at these temperatures.

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Efficient incorporation of (PtCl3EtOH)(-) anion derived from CisPt moiety into ureasil-PPO (poly(propylene oxide)) network was achieved from one-pot sol-gel synthesis carried out in the presence of water, HCl, and ethanol. Reactant proportion was adequately chosen to lead the sol-gel formation of siloxane nodes at the end of short PPO chains, to prevent the CisPt hydrolysis, and to induce platinum ligand exchange. The efficient dissolution of Pt species and the formation of a homogeneous liquid-like solution on the transparent and elastomeric ureasil-PPO hybrid were evidenced by differential scanning calorimetry and small-angle X-ray scattering. The CisPt ligand exchange and the formation of a Zeise-type salt Y(+)(PtCl3R)(-) were demonstrated by Raman spectroscopy and Pt L3-edge EXAFS analysis. In light of these results and in agreement with the proportion of reactants introduced in the media for synthesis and those self-produced by hydrolysis and condensation processes, we proposed for R the ethanol moiety and for Y the ammonium cation. The Raman spectroscopy studies indicated also that the ammonium cations are coordinated by the ether-type oxygen atoms of the PPO chains backbone, whereas the amine groups of the urea linkage participate in the (PtCl3EtOH)(-) anion coordination. In situ Raman monitoring of Pt species decomplexation induced by immersion of hybrid matrix in water highlighted the specific participation of Pt ligands in interaction with the urea group and of NH4(+) cations coordinated by ether-type oxygen atoms in the formation of supramolecular interactions between the PPO chains. The electrospray mass spectrometry analysis of the Pt species released in water from the ureasil-PPO hybrid evidenced that the structure of the complex, NH4 (PtCl3 EtOH), incorporated in the matrix is totally preserved after delivery. Due to both well-known antitumoral and catalytic activities of Pt species, the results reported herein are of prime importance for further applications as drug delivery systems with optimized release pattern or as potential materials for new conceptual development of in situ catalyst delivery in homogeneous catalysis.

Assuntos

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The ability of assembling inorganic, organic, and even bioactive components in a single material unfolds an exciting direction in the development of novel multifunctional hybrid materials. Recently, we have observed that the hydrophilic/hydrophobic character of the organic polymeric moieties determines the swelling/diffusion control of the drug release. In this work, the antitumor cisplatin (CisPt) molecules incorporated into the ureasil-PEO (poly(ethylene oxide)) hybrid material was used as a probe for the in situ and simultaneous UV-vis and Raman spectroscopies monitoring of the kinetics of both the water uptake as well as the CisPt release by the hybrid matrix. Drug molecules were incorporated during the hydrolysis and polycondensation steps. The monolithic xerogel were analyzed by X-ray absorption spectroscopy and differential scanning calorimetry, while the drug release properties were monitored by Raman as well as UV-vis spectroscopies. The results show that the molecular structure of the CisPt is preserved in the one pot sol-gel route used in synthesizing the CisPt-loaded PEO1900 hybrid. The in situ monitoring of water uptake clearly points out the key contribution of the osmotic flow on the stepped profile of the CisPt delivered from the PEO1900 hybrid matrix.

Assuntos

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Recent advances have accelerated the development of biosensors for the analysis of specific gene sequences. In this kind of biosensor, a DNA probe is immobilized on a transducer and the hybridization with the target DNA is monitored by suitable methodology. In the present work, the streptavidin (STA) was encapsulated in thin films siloxane-poly(propylene oxide) hybrids prepared by sol-gel method and deposited on the graphite electrode surface by dip-coating process. Biotinylated 18-mer probes were immobilized through STA and a novel amperometric DNA biosensor for the detection and genotyping of the hepatitis C virus (genotypes 1, 2A/C, 2B and 3) is described. The HCV RNA from serum was submitted to reverse transcriptase-linked polymerase chain reaction (RT-PCR) and biotin-labeled cDNA was obtained. Thus, the cDNA was hybridized to the target-specific oligonucleotide probe immobilized on the graphite electrode surface and following the avidin-peroxidase conjugate was added. The enzymatic response was investigated by constant potential amperometry at -0.45V versus Ag/AgCl using H(2)O(2) and KI solutions. HCV RNA negative and positive controls and positive samples of sera patients were analyzed and the results were compared to commercial kit. The proposed methodology appeared to be suitable and convenient tool for streptavidin immobilization and diagnose of HCV disease.

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This paper surveys the topology of macroporous silica prepared using latex templates covering the submicrometric range (0.1-0.7 mum). The behavior of latex spheres in aqueous dispersion has been analyzed by dynamic light scattering (DLS) measurement indicating the most appropriate conditions to form well-defined cubic arrays. The optical behavior of latex spheres has been analyzed by transmittance and reflectance measurements in order to determine their diameter and filling factor when they were assembled in bidimensional arrays. Macroscopic templates have been obtained by a centrifugation process and their crystalline ordering has been confirmed by porosimetry and scanning electron microscopy. These self-assembled structures have been used to produce macroporous silica, whose final topology depends on the pore size distribution of the original template. It has been seen that latex spheres are ordered in a predominant fcc arrangement with slipping of tetragonal pores due to the action of attractive electrostatic interactions. The main effect is to change the spherical shape of voids in macroporous silica into a hexagonal configuration with possible applications to fabricate photonic devices with novel optical properties.