RESUMO
The sol-gel process enables the preparation of silica-based matrices with tailored composition and properties that can be used in a variety of applications, including catalysis, controlled release, sensors, separation, etc. Commonly, it is assumed that silica matrices prepared via the sol-gel synthesis route are "inert" and, therefore, do not affect the properties of the substrate or the catalyst. This short review points out that porous silica affects the properties of adsorbed/entrapped species and, in some cases, takes an active part in the reactions. The charged matrix affects the diffusion of ions, thus affecting catalytic and adsorption processes. Furthermore, recent results point out that ≡Si-O. radicals are long-lived and participate in redox processes. Thus, clearly, porous silica is not an inert matrix as commonly considered.
RESUMO
BACKGROUND: Condylar hyperplasia is a non-neoplastic overgrowth of the mandibular condyle. The disorder is progressive and causes gradual jaw deviation, facial asymmetry, and dental malocclusion. The only treatment capable of stopping hyperplastic growth is surgical condylectomy to remove the upper portion of the condyle containing the deranged growth center. When this procedure is conducted in proportion to the length of the healthy side it may also correct the jaw deviation and facial asymmetry. OBJECTIVES: To assess the degree to which condylectomy corrects the asymmetry and to determine the proportion of patients after condylectomy who were satisfied with the esthetic result and did not desire further corrective surgery. METHODS: We conducted a retrospective analysis of medical records of patients who underwent condylectomy that was not followed by corrective orthognathic surgery for at least 1 year to determine the degree of correction of chin deviation and lip cant. Patient satisfaction from treatment or desire and undergo further corrective surgery was reported. RESULTS: Chin deviation decreased after condylectomy from a mean of 4.8° to a mean of 1.8° (P < 0.001). Lip cant decreased after condylectomy from a mean of 3.5° to a mean of 1.5° (P < 0.001). Most patients (72%) were satisfied with the results and did not consider further corrective orthognathic surgery. CONCLUSIONS: Proportional condylectomy could be a viable treatment to both arrest the condylar overgrowth and achieve some correction of the facial asymmetry.
Assuntos
Assimetria Facial , Hiperplasia , Côndilo Mandibular , Satisfação do Paciente , Humanos , Assimetria Facial/etiologia , Assimetria Facial/cirurgia , Hiperplasia/cirurgia , Estudos Retrospectivos , Côndilo Mandibular/cirurgia , Côndilo Mandibular/patologia , Feminino , Masculino , Adulto , Resultado do Tratamento , Adolescente , Adulto Jovem , Procedimentos Cirúrgicos Ortognáticos/métodos , Queixo/cirurgiaRESUMO
Polyoxometalates (POMs) have been well studied and explored in electro/photochemical water oxidation catalysis for over a decade. The high solubility of POMs in water has limited its use in homogeneous conditions. Over the last decade, different approaches have been used for the heterogenization of POMs to exploit their catalytic properties. This study focused on a Keggin POM, K6[CoW12O40], which was entrapped in a sol-gel matrix for heterogeneous electrochemical water oxidation. Its entrapment in the sol-gel matrix enables it to catalyze the oxygen evolution reaction at acidic pH, pH 2.0. Heterogenization of POMs using the sol-gel method aids in POM's recyclability and structural stability under electrochemical conditions. The prepared sol-gel electrode is robust and stable. It achieved electrochemical water oxidation at a current density of 2 mA/cm2 at a low overpotential of 300 mV with a high turnover frequency (TOF) of 1.76 [mol O2 (mol Co)-1s-1]. A plausible mechanism of the electrocatalytic process is presented.
RESUMO
Dip-pen nanolithography (DPN) is a powerful and unique technique for precisely depositing tiny nano-spherical cap shapes (nanoclusters) onto a desired surface. In this study, a meta-chemical surface (MCS; a pattern with advanced features) is developed by DPN and applied to electrochemical lead sensing, yielding a calibration curve in the ppb range. An ink mixture of PMMA and NTPH (which binds to Pb (II), as supported by DFT calculations) is patterned over a Pt surface. The average height of the nanoclusters is ≈13 nm with a high surface area-to-volume ratio, which depends on the ink composition and the MCS surface. This ratio affected the sensitivity of the MCS as a detecting tool. The results indicate that the sensor's features can be controlled by the ability to control the size of the nanoclusters, attributed to the unique properties of the DPN production method. These results are significant for the water-source purification industry.
RESUMO
The Na3 [Ru2 (µ-CO3 )4 ] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na3 [Ru2 (µ-CO3 )4 ] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and kcat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO3 has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO3 , the diffusing species is probably OH- , which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na3 [Ru2 (µ-CO3 )4 ] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source.
RESUMO
Para chloro aniline (PCA) is a common toxic pollutant found in pharmaceutical wastewater. Our study suggests a novel PCA treatment method based on a heterogeneous advanced oxidation process (AOP) that proceeds in an electron exchange matrix (EEM) prepared by the incorporation of redox-active specie in silica matrices using the sol-gel synthesis route. The results, which are supported by DFT calculations, show that the silicon skeleton of the EEM has two important roles, both as a porous matrix that hosts the redox species and as an oxidant species involved in the AOP. The calculations indicate that the formation of a radical on the nitrogen is favored. The suggested mechanism could shed light on the AOP, which proceeds in a heterogenous system, and on its application inside the understudied EEMs that, until now, have been a virtual black box. A better understanding of the mechanism could lead to improved control over the heterogeneous processes that can play a critical role in industries with the need to treat small amounts of toxic compounds at low concentrations, such as in the pharmaceutical industry.
RESUMO
The purpose of the present study was to evaluate the 3-dimensional orofacial changes occurring after proportional condylectomy in patients with unilateral condylar hyperplasia type 2 (hemimandibular hyperplasia). Eight patients underwent proportional condylectomy that was not followed by orthognathic surgery or orthodontic treatment for at least 1 year. The precondylectomy and postcondylectomy photographs and radiographs were analyzed cephalometrically and compared. The average length of the condylar segment removed was 13 mm and this resulted in almost equal heights of the ramus-condyle units of both sides. Evaluations in the vertical plane improved after surgery; however, when the preoperative asymmetry was significant, the residual asymmetry continued to be notable after condylectomy. Transverse plane evaluations improved after condylectomy, and chin position was satisfactorily centralized in all patients. In the horizontal plane, mandibular setback occurred, and this was considered favorable when the preoperative skeletal profile was class III, whereas the opposite was when the patient was class I before surgery. The occlusion improved gradually over the postoperative months by the intrusion on the affected side and extrusion on the unaffected side into a bilaterally balanced posterior contacts with residual anterior open bite. In conclusion, condylar hyperplasia type 2 patients with mild asymmetry and low esthetic demands can benefit from proportional condylectomy as the sole treatment to both stop the hyperplastic condylar growth and improve the asymmetry to some extent. Surgeons should be able to predict the change that is expected to occur after proportional condylectomy and discuss this with the patient before surgery.
Assuntos
Assimetria Facial , Côndilo Mandibular , Humanos , Côndilo Mandibular/diagnóstico por imagem , Côndilo Mandibular/cirurgia , Côndilo Mandibular/patologia , Hiperplasia/cirurgia , Hiperplasia/patologia , Assimetria Facial/diagnóstico por imagem , Assimetria Facial/cirurgia , Assimetria Facial/patologia , Estética Dentária , OsteotomiaRESUMO
Vast efforts are directed today toward the development of efficient, green methods for the degradation of toxic compounds, especially those that are water-soluble. Though Fenton reactions are commonly used in wastewater treatment, their mechanisms and the active species involved remain obscure due to their mechanistic complexity. In this work, the mechanism of an electro-Fenton reaction, in which a FeLaO3 catalyst was entrapped in a sol-gel matrix, was studied in the presence of azo dyes as the model for toxic compounds. Increased knowledge about this important mechanism will confer greater control over related processes and enable a more efficient and green degradation method. DFT calculations showed that in the presence of Fe(IV), OH are formed under acidic conditions and that both the iron and hydroxyl species function as oxidation reagents in the degradation process. The structure of the formed Fe(IV) embedded in the solid matrix was not the typical tetravalent structure. Entrapment in the sol-gel matrix stabilized the catalyst, enhanced its efficiency and enabled it to be recycled. Sol-gel matrices constitute a simple method for the degradation of stable and toxic compounds under extreme pH conditions. The findings of this study are highly significant for the treatment of typically acidic wastewaters.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Compostos Azo , Catálise , Peróxido de Hidrogênio , Oxirredução , Poluentes Químicos da Água/análiseRESUMO
OBJECTIVES: To evaluate the effect of a novel radiofrequency (RF)-utilizing toothbrush on reduction of stains and improvement of teeth shade. MATERIALS AND METHODS: This was an open label, prospective study, including six clinical visits that were conducted over a period of 8 weeks. Subjects performed twice daily brushing using a novel RF-utilizing toothbrush, used manually with no mechanical vibration. Teeth shade and stains were assessed using Vita Easyshade advanced 4.0 device and a visual assessment of standardized digital photographs, before, and following 4 and 8 weeks of treatment. RESULTS: Twelve subjects completed the study with fully evaluable data. A notable shade improvement (whitening) was observed between the visits according to the average scores of teeth whitening index per subject. Statistical analysis conducted by the unstructured mix model confirmed a significant reduction in the average score of whitening index between baseline and visit 5 (p < 0.001) as well as between baseline and visit 6 (p < 0.001). No significant difference was found between the average teeth shade in visit 5 as compared to visit 6 (p = 0.918). No significant difference was found in teeth shade between females and males; however, subjects age was significantly correlated with teeth shade (p < 0.001). Digital photographs indicated a notable reduction in visible dark stains. The toothbrush was well tolerated and no device-related adverse events were reported during the study. CONCLUSIONS: The novel RF-utilizing toothbrush produced significant benefits relating to teeth whitening and stains reduction, following one and 8 weeks of brushing.
Assuntos
Clareamento Dental , Descoloração de Dente , Feminino , Humanos , Masculino , Projetos Piloto , Estudos Prospectivos , Descoloração de Dente/terapia , Escovação DentáriaRESUMO
Olefin metathesis, a powerful synthetic method with numerous practical applications, can be improved by developing heterogeneous catalysts that can be recycled. In this study, a single-stage process for the entrapment of ruthenium-based catalysts was developed by the sol-gel process. System effectiveness was quantified by measuring the conversion of the ring-closing metathesis reaction of the substrate diethyl diallylmalonate and the leakage of the catalysts from the matrix. The results indicate that the nature of the precursor affects pore size and catalyst activity. Moreover, matrices prepared with tetraethoxysilane at an alkaline pH exhibit a better reaction rate than in the homogenous system under certain reaction conditions. To the best of our knowledge, this is the first study to present a one-step process that is simpler and faster than the methods reported in the literature for catalyst entrapment by the sol-gel process under standard conditions.
RESUMO
Isotopic composition analysis of natural and depleted uranium by inductively coupled plasma optical emission spectrometry (ICP-OES) requires the use of a high-resolution instrument due to the very slight isotopic shifts between the atomic emission spectra of the 238U and 235U isotopes. In this work, we show that conventional ICP-OES (without high-resolution optics) can be used for highly accurate uranium isotopic analysis, on par with the results obtained by ICP-MS. Such accurate measurements are achieved by applying a preparatory mathematical procedure termed the optimal sensitivity position (OSP) procedure. In the OSP procedure, a theoretical spectrum for 238U is constructed and subtracted from the measured spectra of calibration solutions encompassing various isotopic ratios. The resultant spectra are used to locate the optimal measurement positions for both major uranium isotopes (238U and 235U) and the background measurement position. Herein, the optimal measurement positions are revealed to be located not at each isotope's peak maximum but at 424.427, 424.409, and 424.390 nm for 238U, 235U, and the background position, respectively. These locations remained stationary during the period of this work, implying that the use of a routine mathematical procedure is not required before every analysis. The OSP procedure offers a direct and highly accurate approach for determining the isotopic ratio of uranium in a relatively cheap and simple fashion. Furthermore, this work also demonstrates the possibility of greatly enhancing ICP-OES capabilities using mathematical analysis of spectra.
RESUMO
We use dip-pen nanolithography to accurately pattern Ni(OH)2 nanoclusters on a metachemical surface with an exceptionally large surface area. The distance between the nanoclusters can be manipulated to control the oxygen-evolution reaction current and overpotential, thereby improving the efficiency of the water-splitting process while using minute amounts of the catalyst.
Assuntos
Hidróxidos/química , Níquel/química , Água/química , Nanopartículas/ultraestrutura , Oxirredução , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Rare-earth (RE) oxides are important in myriad fields, including metallurgy, catalysis, and ceramics. However, the phase diagram of RE oxides in the nanoscale might differ from the phase diagrams for bulk, thus attracting attention nowadays. We suggest that grain size in the nanoscale also determines the obtained crystallographic phase along with temperature and pressure. For this purpose, nanoparticles of Sm2O3 and Eu2O3 were mixed in an inert MgO matrix via the sol-gel method. This preparation method allowed better isolation of the oxide particles, thus hindering the grain growth process associated with increasing the temperature. The mixed oxides were compared to pure oxides, which were heat-treated using two methods: gradual heating versus direct heating to the phase transition temperature. The cubic phase in pure oxides was preserved to a higher extent in the gradual heating treatment compared to the direct heating treatment. Additionally, in MgO, even a higher extent of the cubic phase was preserved at higher temperatures compared to the pure oxide, which transformed into the monoclinic phase at the same temperature in accordance with the phase diagram for bulk. This indicates that the cubic phase is the equilibrium phase for nanosized particles and is determined also by size.
RESUMO
Porous yttria-stabilised zirconia ceramics have been gaining popularity throughout the years in various fields, such as energy, environment, medicine, etc. Although yttria-stabilised zirconia is a well-studied material, voided yttria-stabilised zirconia powder particles have not been demonstrated yet, and might play an important role in future technology developments. A sol-gel synthesis accompanied by a freeze-drying process is currently being proposed as a method of obtaining sponge-like nano morphology of embedded faceted voids inside yttria-stabilised zirconia particles. The results rely on a freeze-drying stage as an effective and simple method for generating nano-voided yttria-stabilised zirconia particles without the use of template-assisted additives.
RESUMO
Kinetic and DFT results for the carbonate catalysed Co(H2O)6(2+) + H2O2 Fenton-like reaction suggest a mechanism involving the formation of a cyclic transient, cyclic-(CO4)Co(II)(OOH)(H2O)2(-) that decomposes into Co(II)(H2O)(OOH)(OH)2 + CO3Ë(-), i.e. no OHË radicals are involved. Plausible biological implications are pointed out.
Assuntos
Carbonatos/química , Peróxido de Hidrogênio/química , Ferro/química , Catálise , Cobalto/química , Complexos de Coordenação/química , Radical Hidroxila/química , OxirreduçãoRESUMO
PURPOSE: The present retrospective analysis was performed to assess the effectiveness of sialoendoscopic treatment of chronic obstructive parotitis. MATERIALS AND METHODS: The study group included 87 parotid glands with stricture as the only cause of gland obstruction. After sialographic and sialoendoscopic evaluation, sialoendoscopic 4-step surgical treatments were performed. The treatment protocol was designed. RESULTS: Sialoendoscopy proved to be a successful procedure in 94.7% of the affected parotid glands we treated. CONCLUSION: The minimally invasive technique of sialoendoscopy for treatment of strictures of the salivary glands could be a welcome innovation, helping to avoid radical surgical treatment of salivary gland disease.
Assuntos
Endoscopia , Parotidite/etiologia , Ductos Salivares/patologia , Doença Crônica , Constrição Patológica/complicações , Humanos , Procedimentos Cirúrgicos Minimamente Invasivos , Parotidite/diagnóstico por imagem , SialografiaRESUMO
The antioxidant properties of Bucillamine (BUC), a di-thiol compound used for treatment of rheumatoid arthritis (RA) and its possible mode of action, were investigated. BUC exhibits potent antioxidant activity similar to those of trolox and ascorbic acid. It reduces the stable free radical diphenyl-2-picrylhydrazyl (DPPH) with IC(50) of 18.5+/-0.1 micromol, its relative antioxidant activity by the ferric reducing ability (FRAP) is 2.07+/-0.01 mM and by the trolox equivalent antioxidant capacity (TEAC), 1.46+/-0.05 mM. However, its superoxide and apparent hydroxyl radical scavenging activities are low (IC(50) at millimolar concentrations). We found that BUC is a strong iron (II) and copper (II) chelator. This finding is very important since these metal ions are significantly higher in RA patients and may be involved in oxidative stress-induced damage. Our study suggests that BUC is a potent antioxidant which exerts its beneficial therapeutic activities in RA patients by metal chelation rather than by scavenging free radical species.