Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel

In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.

Study of the catalytical intermediates of metalloporphyrins supported on imidazole propyl gel

In this work, the catalytic intermediates for Fe(TPP)(+), Fe(TDCPP)(+), Fe(TFPP)(+), Mn(TPP)(+) and Mn(TDCPP)(+) supported on imidazole propyl gel with PhIO were studied by UV-Vis spectrophotometry. For Fe(TPP)+ and Fe(TFPP)+ the study was also monitored by EPR spectroscopy. The active catalytic intermediate observed for FeP-IPG is the ore-iron (IV) porphyrin pi cation radical Fe-IV(O)P.+, which is evidenced by a decrease in the intensity of the Sorer band. The total re-establishment of the initial Soret band intensity for Fe(TDCPP)IPG and Fe(TFPP)IPG at the end of the reaction shows that they were completely recovered, There are advantages in following the reactions of PNO with unsubstituted Fe(TPP)(+) and Mn(TPP)(+) on IPG by UV-Vis, since they were slower and allowed to 'see' the intermediate species without spectral interference from the recovered catalyst, since they are only partially recovered. With Fe(TPP)IPG, a band at 580 nm was detected at the beginning of the reaction, indicating the possible formation of a Fe-OIPh intermediate. Supporting Mn(TPP)(+) on IPG leads to a shift of band V from 478 nm to 488 nm. In the reaction of MnP-IPG with PhIO, we observed the disappearance of the band in 488 nm and the appearance of a band in 412 nm, which corresponds to the active catalytic intermediate Mn-V(O)P as the main component, as is expected for a more efficient system. The recovery of supported catalysts observed in these experiments was further proved with the possibility of their successive recyclings in cyclohexane oxidation reactions by PhIO.

Study of the selectivity of SnO2 supported membranes prepared by a sol-gel route

In this work the sol-gel process was used to prepare SnO2 supported membranes with an average pore size of 2.5 nm. The effects of salt concentration (NaCl or CaCl2) and of the pH of the aqueous solutions used on the flux and selectivity through the SnO2 membrane were analyzed by permeation experiments and the results interpreted taking account of the zeta potential values determined from the electrophoretic mobility of the SnO2 powder aqueous dispersion. The results show that the ion flux (Na+, Ca2+ and Cl-) throughout the membrane is determined by the electrostatic repulsion among these species and the surface charge at the tin oxide-solution interface.

Self-supported bacterial cellulose/boehmite organic-inorganic hybrid films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Early loading of single crowns supported by 6-mm-long implants with a moderately rough surface: a prospective 2-year follow-up cohort study

AimTo evaluate prospectively the clinical and radiographic outcomes after 2 years of loading of 6 mm long moderately rough implants supporting single crowns in the posterior regions.Material and methodsForty SLActive Straumann (R) short (6 mm) implants were placed in 35 consecutively treated patients. Nineteen implants, 4.1 mm in diameter, and 21 implants, 4.8 mm in diameter, were installed. Implants were loaded after 6 weeks of healing. Implant survival rate, marginal bone loss and resonance frequency analysis (RFA) were evaluated at different intervals. The clinical crown/implant ratio was also calculated.ResultsTwo out of 40 implants were lost before loading. Hence, the survival rate before loading was 95%. No further technical or biological complications were encountered during the 2-year follow-up. The mean marginal bone loss before loading was 0.34 +/- 0.38 mm. After loading, the mean marginal bone loss was 0.23 +/- 0.33 and 0.21 +/- 0.39 mm at the 1- and 2-year follow-ups. The RFA values increased between insertion (70.2 +/- 9) and the 6-week evaluation (74.8 +/- 6.1). The clinical crown/implant ratio increased with time from 1.5 at the delivery of the prosthesis to 1.8 after 2 years of loading.ConclusionShort implants (6 mm) with a moderately rough surface loaded early (after 6 weeks) during healing yielded high implant survival rates and moderate loss of bone after 2 years of loading. Longer observation periods are needed to draw more definite conclusions on the reliability of short implants supporting single crowns.To cite this article:Rossi F, Ricci E, Marchetti C, Lang NP, Botticelli D. Early loading of single crowns supported by 6-mm-long implants with a moderately rough surface: a prospective 2-year follow-up cohort study.Clin. Oral Impl. Res. 21, 2010; 937-943.doi: 10.1111/j.1600-0501.2010.01942.x.

Patients' Expectations of and Satisfaction with Implant-Supported Fixed Partial Dentures and Single Crowns

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of viscoelastic characteristics of the colloidal suspensions on the formation of SnO2 supported membranes

SnO2 supported membranes have been prepared by sol-casting on alumina tubular substrate, using aqueous colloidal suspensions prepared by sol-gel route. The viscoelastic behaviour during sol ageing was analyzed by dinamic rheologial measurements. The complex viscosity and the storage and loss moduli have been followed during the sol-gel transition and the results have been correlated with the linear aggregates growth and the scalar percolation models. The scanning electron microscopy has evidenced that the homogeneity and thickness of the membrane depend on the sol ageing time. Crack-free and homogeneous membranes have been obtained for coated layers of 0.5μm thickness. © 1997 Trans Tech Publications.

Prosthetic rehabilitation of a bone defect with a teeth-implant supported, removable partial denture

The use of teeth-implant, mucosa-supported removable dentures for rehabilitation of partially edentulous patients involves highly complex biomechanical aspects. This type of prosthesis associates 3 kinds of support that react differently to the functional and parafunctional forces developed in the oral cavity. Although the construction of removable partial dentures may seem paradoxical when osseointegrated implants are placed, in some cases, this option is an excellent alternative to solve difficulties related to the anatomic, biologic, psychomotor, and financial conditions of the patient. This article reports on a case in which a teeth-implant, mucosa-supported removable partial denture was the option of choice for a patient with financial and anatomic limitations, having a large structural loss of the residual alveolar ridge caused by trauma by a gunshot injury at the mandible. The 5-year follow-up did not reveal any type of biomechanical or functional problem. Copyright © 2006 by Lippincott Williams and Wilkins.

In vitro evaluation of the precision of working casts for implant-supported restoration with multiple abutments

Objective: The purpose of this study was to compare the accuracy of two working cast fabrication techniques using strain-gauge analysis. Methods: Two working cast fabrication methods were evaluated. Based on a master model, 20 working casts were fabricated by means of an indirect impression technique using polyether after splinting the square transfer copings with acrylic resin. Specimens were assigned to 2 groups (n=10): Group A (GA): type IV dental stone was poured around the abutment analogs in the conventional way; Group B (GB), the dental stone was poured in two stages. Spacers were used over the abutment analogs (rubber tubes) and type IV dental stone was poured around the abutment analogs in the conventional way. After the stone had hardened completely, the spacers were removed and more stone was inserted in the spaces created. Six strain-gauges (Excel Ltd.), positioned in a cast bar, which was dimensionally accurate (perfect fit) to the master model, recorded the microstrains generated by each specimen. Data were analyzed statistically by the variance analysis (ANOVA) and Tukey's test (α= 5%). Results: The microstrain values (με) were (mean±SD): GA: 263.7±109.07με, and GB: 193.73±78.83με. Conclusion: There was no statistical difference between the two methods studied.

Effects of mandibular fixed implant-supported prostheses on masticatory and swallowing functions in completely edentulous elderly individuals

Purpose: To evaluate the effect of oral rehabilitation with immediately loaded fixed implant-supported mandibular prostheses on chewing and swallowing in elderly individuals. Materials and Methods: Fifteen completely edentulous patients aged more than 60 years (10 women and rive men), wearing removable dentures in both arches, had a mandibular denture replaced by an implant-supported prosthesis. All individuals were evaluated before surgery and again 3, 6, and 18 months later with regard to mastication and swallowing conditions. Examinations entailed an interview, evaluation of tactile sensitivity of the face, and observation of food intake, masticatory type, formations of bolus, and pain during mastication. The swallowing evaluation comprised observation of clinical signs related to the oral and pharyngeal stages of swallowing, as well as the presence of oral residue. The findings of different evaluations before and 3, 6, and 18 months after the surgical-prosthetic procedure were statistically compared by analysis of variance for repeated measurements at a significance level of 5%. Results: The questionnaire revealed a reduction in complaints of masticatory and swallowing disturbances, a decreased need for liquid ingestion, and reduced choking and coughing. Clinical evaluations showed improved oral function and bolus propulsion for both solid and paste-consistency foods; pain during mastication was also resolved. Conclusion: Treatment with mandibular implant-supported dentures had positive effects on the clinical aspects of mastication and swallowing in elderly individuals.

Evaluation of a two-step pouring technique for implant-supported prostheses impression

The aim of this study was to evaluate the efficacy of a pouring technique for implant-supported prostheses impressions. A metallic matrix (control group) with two implants positioned at 90 and 65 degrees was fabricated. The matrix was submitted to the direct transfer impression technique. In group CP (conventional pouring - n = 10), casts were obtained by the conventional pouring technique. In group EP (experimental pouring - n = 10), the analogs were embraced with latex tubes before the first pouring and then submitted to a second pouring. Vertical misfit and implants/analogs inclinations were evaluated. Data were analyzed by analysis of variance and Tukey's test (p < .05). Results demonstrated significant difference (p < .05) between control and experimental groups for misfit measurement in perpendicular implant/analog and between control group and group EP in leaning implant/analog. Considering inclination, there were significant differences (p < .05) between control and experimental groups for leaning analogs. Independently of the pouring technique, perpendicular implants produced more accurate casts.

Effect of unilateral misfit on preload of retention screws of implant-supported prostheses submitted to mechanical cycling

Purpose: The aim of this study was to evaluate the effect of different levels of unilateral angular misfit on preload maintenance of retention screws of single implant-supported prostheses submitted to mechanical cycling. Materials and methods: Premachined UCLA abutments were cast with cobalt-chromium alloy to obtain 48 crowns divided into four groups (n=12). The crowns presented no misfit in Group A (control group) and unilateral misfits of 50μm, 100μm and 200μm in the groups B, C and D, respectively. The crowns were attached to external hexagon implants with a titanium retention screw with torque of 30N/cm. Oblique loading of 130N at 2Hz was applied on each replica, totalizing 5×104 and 1×106cycles. Detorque values were measured initially and after each cycling period. Data were evaluated by analysis of variance and Tukey's HSD test (p<0.05). Results: All groups presented reduced initial detorque values (p< 0.05) in comparison to the insertion torque (30. ± 0.5. N/cm) and Group A (25.18. N/cm) exhibited the lowest reduction. After mechanical cycling, all groups presented detorque values from 19.5. N/cm to 22.38. N/cm and the mechanical cycling did not statistically influence the detorque values regardless the misfit level of the replicas. Conclusion: The unilateral misfit influenced the preload maintenance only before mechanical cycling. The mechanical cycling did not influence the torque reduction. © 2010 Japan Prosthodontic Society.

Effect of axial loads on implant-supported partial fixed prostheses by strain gauge analysis

Objectives: The present study used strain gauge analysis to perform an in vitro evaluation of the effect of axial loading on 3 elements of implant-supported partial fixed prostheses, varying the type of prosthetic cylinder and the loading points. Material and methods: Three internal hexagon implants were linearly embedded in a polyurethane block. Microunit abutments were connected to the implants applying a torque of 20 Ncm, and prefabricated Co-Cr cylinders and plastic prosthetic cylinders were screwed onto the abutments, which received standard patterns cast in Co-Cr alloy (n = 5). Four strain gauges (SG) were bonded onto the surface of the block tangentially to the implants, SG 01 mesially to implant 1, SG 02 and SG 03 mesially and distally to implant 2, respectively, and SG 04 distally to implant 3. Each metallic structure was screwed onto the abutments with a 10 Ncm torque and an axial load of 30 kg was applied at five predetermined points (A, B, C, D, E). The data obtained from the strain gauge analyses were analyzed statistically by RM ANOVA and Tukey's test, with a level of significance of p<0.05. Results: There was a significant difference for the loading point (p=0.0001), with point B generating the smallest microdeformation (239.49 με) and point D the highest (442.77 με). No significant difference was found for the cylinder type (p=0.748). Conclusions: It was concluded that the type of cylinder did not affect in the magnitude of microdeformation, but the axial loading location influenced this magnitude.

Optimization of query results in peer-to-peer database supported by semantics

The development of new technologies that use peer-to-peer networks grows every day, with the object to supply the need of sharing information, resources and services of databases around the world. Among them are the peer-to-peer databases that take advantage of peer-to-peer networks to manage distributed knowledge bases, allowing the sharing of information semantically related but syntactically heterogeneous. However, it is a challenge to ensure the efficient search for information without compromising the autonomy of each node and network flexibility, given the structural characteristics of these networks. On the other hand, some studies propose the use of ontology semantics by assigning standardized categorization of information. The main original contribution of this work is the approach of this problem with a proposal for optimization of queries supported by the Ant Colony algorithm and classification though ontologies. The results show that this strategy enables the semantic support to the searches in peer-to-peer databases, aiming to expand the results without compromising network performance. © 2011 IEEE.