White Light and Multicolor Emission Tuning in Triply Doped Yb3+/Tm3+/Er3+ Novel Fluoro-phosphate Transparent Glass-ceramics

New Yb3+, Er3+ and Tm3+ doped fluoro-phosphate glasses belonging to the system NaPO3–YF3–BaF2–CaF2 and containing up to 10 wt% of rare-earth ion fluorides were prepared and characterized by differential scanning calorimetry, absorption spectroscopy and up-conversion emission spectroscopy under excitation with a 975 nm laser diode. Transparent and homogeneous glass-ceramics have been reproducibly obtained with a view to manage the red, green and blue emission bands and generate white light. X-ray diffraction as well as electron microscopy techniques have confirmed the formation of fluorite-type cubic nanocrystals at the beginning of the crystallization process while complex nanocrystalline phases are formed after a longer heat-treatment. The prepared glass-ceramics exhibit high optical transparency even after 170 h of thermal treatment. An improvement of up-conversion emission intensity – from 10 to 160 times larger – was measured in the glass-ceramics when compared to the parent glass, suggesting an important incorporation of the rare-earth ions into the crystalline phase(s). The involved mechanisms and lifetime were described in detail as a function of heat-treatment time. Finally, a large range of designable color rendering (from orange to turquoise through white) can be observed in these materials by controlling the laser excitation power and the crystallization rate.

Concentração de flúor e cálcio no fluido do biofilme associada ao uso de dentifrícios fluoretados suplementados com trimetafosfato de sódio ou glicerofosfato de cálcio, sob desafio cariogênico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

In vitro effect of sodium trimetaphosphate additives to conventional toothpastes on enamel demineralization

The aim of this study was to evaluate the ability of conventional toothpastes (1100 ppm F) supplemented with sodium trimetaphosphate (TMP) in demineralization. Blocks of enamel were selected and then divided into seven experimental groups of 12: toothpaste without F and TMP (placebo), toothpaste with 1100 ppm F (1100), and toothpaste with 1100 ppm F supplemented with TMP-1 % (1100 1 % TMP), 3 % (1100 3 % TMP), 4.5 % (1100 4.5 % TMP), 6 % (1100 6 % TMP), and 9 % (1100 9 % TMP). Blocks were subjected to five pH cycles (demineralizing/remineralizing solutions) at 37 °C and treated with toothpaste slurries twice daily, after which the blocks were maintained for 2 days in fresh remineralizing solution. Following treatments, surface hardness (SHf) and cross-sectional hardness were determined for calculating the integrated loss of subsurface hardness (ΔKHN). The fluoride present in the enamel was also measured. The SHf and ΔKHN measurements showed that supplementation with 3 % TMP was the most effective (p < 0.001) and showed greater concentration of F in the enamel (p < 0.001). Addition of 3 % TMP to a conventional toothpaste (1100 ppm F) showed greater efficacy in reducing enamel demineralization. Fluoride toothpastes containing trimetaphosphate possess good anticaries potential required to reduce the prevalence of dental caries in high-risk patients.

Synergistic effect of fluoride and sodium hexametaphosphate in toothpaste on enamel demineralization in situ

To evaluate the effect of a fluoride dentifrice containing sodium hexametaphosphate (HMP) on enamel demineralization in situ. This double-blind and cross-over study consisted of 3 phases (7 days each) in which 12 volunteers wore intraoral appliances containing four enamel bovine blocks. Specimens were treated (3×/day) with placebo (no F or HMP), 1100ppm F (1100F) and 1100F plus HMP1% (1100F-HMP1%) toothpastes, and the cariogenic challenge was performed using a 30% sucrose solution (6×/day). Final surface hardness, the percentage of surface hardness loss (%SH), the integrated loss of subsurface hardness (ΔKHN), as well as enamel calcium (Ca), phosphorus (P) and firmly-bound fluoride (F) were determined. Also, biofilm formed on the blocks were analyzed for F, Ca, P and insoluble extracellular polysaccharide (EPS) concentrations. Data were submitted 1-way ANOVA, followed by Student-Newman-Keuls' test (p<0.05). 1100F-HMP1% promoted the lowest %SH and ΔKHN among all groups (p<0.001). The addition of HMP1% to 1100F did not enhance enamel F uptake, but significantly increased enamel Ca concentrations (p<0.001). Similar EPS concentrations were seen for 1100F-HMP1% and 1100F groups (p>0.05). All the groups were supersaturated with respect to HA. However, only 1100F-HMP1% group was supersaturated with respect to CaF2 (p<0.05). The ionic activities of F(-), CaF(+) and HF(0) for the 1100F-HMP1% group were the highest among all groups (p<0.001). The addition of HMP1% to a conventional toothpaste significantly reduces enamel demineralization in situ when compared to 1100F. This dentifrice could be a viable alternative to patients at high risk of caries.

Fluoride gel supplemented with sodium hexametaphosphate reduces enamel erosive wear in situ

This study evaluated the effect of fluoride gels, supplemented or not with sodium hexametaphosphate (HMP), on enamel erosive wear in situ. Twelve healthy volunteers wore palatal appliances containing four bovine enamel discs. Subjects were randomly allocated into four experimental phases (double-blind, crossover protocol) according to the gels: Placebo (no fluoride or HMP), 1% NaF, 2% NaF, and 1% NaF+9% HMP. Enamel discs were selected after polishing and surface hardness analysis, and treated only once with the respective gels prior to each experimental phase. Erosion (ERO) was performed by extra-oral immersion of the appliance in 0.05M citric acid, pH 3.2 (four times/day, five minutes each, 5 days). Additional abrasion (ERO+ABR) was produced on only two discs by toothbrushing with fluoridated dentifrice after ERO (four times/day, 30s, 5 days). The specimens were submitted to profilometry and hardness analysis. The results were analyzed by two-way ANOVA and the Student-Newman-Keuls test (p<0.05). The 1% NaF+9% HMP gel promoted significantly lower enamel wear for ERO compared to the other groups, being statistically lower than 1% NaF and Placebo for ERO+ABR. Similarly, the lowest values of integrated lesion area were found for 1% NaF+9% HMP and 2% NaF, respectively, for ERO and ERO+ABR. The addition of HMP to the 1% NaF gel promoted greater protective effect against ERO and ERO+ABR compared to the 1% NaF gel, achieving similar protective levels to those seen for the 2% NaF gel. Gel containing 1% NaF+9% HMP showed a high anti-erosive potential, being a safer alternative when compared to a conventional 2% NaF gel.

Effect of Er:YAG laser on CaF2 formation and its anticariogenic action on human enamel: An in vitro study

Objective: The objective of this study was to evaluate the effect of Er: YAG laser on the formation of CaF2, after the application of acidulated phosphate fluoride (APF), and its influence on the anti-cariogenic action in human dental enamel. Background Data: Er:YAG laser was designed to promote ablation of the enamel. However, the possibility of using this energy to increase the enamel's resistance to caries has hardly been explored, and neither has its interaction with the use of fluorides. Materials and Methods: One hundred and twenty blocks of enamel were allocated to four groups of 30 blocks each: (1) C, control group; (2) Er:YAG, laser; (3) APF; and (4) Er:YAG+APF. Of these, 80 blocks were submitted to pH cycling for 14 days. In the other 40 blocks, fluoride (CaF2) was measured before cycling. After pH cycling, surface microhardness (SMH), microhardness in cross-section (converted to mineral contents % vol. min.), and fluoride after cycling (40 blocks) were also determined. Results: SMH decreased in all groups. The control group showed the highest decrease, and Er:YAG+APF showed the lowest decrease (p < 0.05). Groups APF and Er:YAG showed the same results (p > 0.05). Mineral content at depths 10, 20, and 40 μm was lower in the control and Er:YAG groups, and higher in groups APF and Er:YAG+APF. CaF2 (μgF/cm2) deposited before pH cycling was higher in the APF group when compared to the Er:YAG+APF group. Control and Er:YAG groups showed the lowest values (p > 0.05). Conclusion: It was concluded that Er:YAG laser influenced the deposition of CaF2 on the enamel and showed a superficial anti-cariogenic action, but not in depth.

Concentração de flúor em águas envasadas: análise laboratorial e da legislação relacionada

Fluoridation of water for human consumption is a method of caries prevention that brings great social benefit, if kept at optimal levels. The increase in the production of bottled water emphasizes the need to verify whether fluoride presence in these waters occurs in sufficient quantity to prevent decay, or if it represents a significant risk of fluorosis. Objective: to compare the concentrations of fluoride present in bottled water to those declared on the labels, and to make a critical analysis of legal norms on the subject. Materials and method: this was a cross-sectional study, through which 22 samples of bottled water sold in state of Ceará, Brazil, were analyzed. Analyses were performed in duplicate by the electrometric method, and results were compared to those printed on the labels. Detailed searches by laws, resolutions, ordinances, and other official documents in force, related to the topic were performed. Results: the fluoride concentrations found ranged from 0.01 to 0.36 mgF/l. Although 72.7% of the samples were classified as fluoridated, the fluoride concentrations observed were shown to be insufficient for caries prevention. As for the rules, situations where they are not clear or even divergent were found. Conclusion: the current legislation on the subject requires updates to become more objective and to create new criteria on the use of the term “fluoridated water”.

Caries formation around restorative composite and glass ionomer cement

This in vitro study evaluated the demineralization around restorations class V made on the buccal and lingual surfaces of teeth when using different restorative materials. Thirty extracted teeth were randomly divided into 3 groups (n=10) according to the restorative material: Group I - Fuji II LC (GC America Inc., Alsip, Illinois, USA), Group II - Tetric (Ivoclar Vivadent AG, Schaan, Liechtenstein) and Group III - Chelon Fil (3M/ESPE., Seefeld, Germany). The teeth were submitted to a pH-cycling model associated to a thermocycling model. Sections were made and the specimens were analyzed under a polarized light microscopy as for the presence of demineralization. Measurements were performed and the results were subjected to statistical analysis using Anova and Tukey´s Test (α=0.05). Mean values of demineralization depth (µm) according to each positions showed that the demineralization was significantly reduced when Chelon Fil (Group III) was used for all depths, when compared to fluoridated resin materials. Also, it was verified that non-fluoridated resin material, composite resin Tetric, had the lowest inhibitory effect on the development of demineralization.

Caracterização mineralógica e química das fontes de poeira e sua influência na atmosfera da região do polo cerâmico de Santa Gertrudes (SP)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Hydroxythiazole-Based Fluorescent Probes for Fluoride Ion Detection

This work describes the synthesis of five O-silyloxy-1,3-thiazoles and their use as fast-response turn-on probes for fluoride ion detection in polar aprotic solvents and in aqueous cetyltrimethylammonium bromide micellar medium. The fluoride-triggered deprotection of these silyl ethers results in ca. 180-nm shifts in the fluorescence emission wavelengths. All compounds are suitable for the detection of fluoride ions with a detection limit in DMSO of 107 mol?L1; derivatives containing a 2-pyridyl moiety in the thiazole system are more efficient than those with a 3- or 4-pyridyl moiety. Typical anionic interferents, such as acetate or chloride, are not detected by O-silyloxy-1,3-thiazoles, making these compounds very specific for fluoride.

Titanium surface topography after brushing with fluoride and fluoride-free toothpaste simulating 10 years of use

Objectives: To conduct a controlled study contrasting titanium surface topography after procedures that simulated 10 years of brushing using toothpastes with or without fluoride. Methods: Commercially pure titanium (cp Ti) and Ti-6Al-4V disks (6 mm circle divide x 4 mm) were mirror-polished and treated according to 6 groups (n = 6) as a function of immersion (I) or brushing (B) using deionised water (W), fluoride-free toothpaste (T) and fluoride toothpaste (FT). Surface topography was evaluated at baseline (pretreatment) and post-treatment, using atomic force microscope in order to obtain three-dimensional images and mean roughness. Specimens submitted to immersion were submerged in the vehicles without brushing. For brushed specimens, procedures were conducted using a linear brushing machine with a soft-bristled toothbrush. Immersion and brushing were performed for 244 h. IFT and BFT samples were analysed under scanning electron microscope with Energy-Dispersive X-ray Spectroscopy (EDS). Pre and post-treatment values were compared using the paired Student T-test (alpha = .05). Intergroup comparisons were conducted using one-way ANOVA with Tukey post-test (alpha = .05). Results: cp Ti mean roughness (in nanometers) comparing pre and post-treatment were: IW, 2.29 +/- 0.55/2.33 +/- 0.17; IT, 2.24 +/- 0.46/2.02 +/- 0.38; IFT, 2.22 +/- 0.53/1.95 +/- 0.36; BW, 2.22 +/- 0.42/3.76 +/- 0.45; BT, 2.27 +/- 0.55/16.05 +/- 3.25; BFT, 2.27 +/- 0.51/22.39 +/- 5.07. Mean roughness (in nanometers) measured in Ti-6Al-4V disks (pre/post-treatment) were: IW, 1.79 +/- 0.25/2.01 +/- 0.25; IT, 1.61 +/- 0.13/1.74 +/- 0.19; IFT, 1.92 +/- 0.39/2.29 +/- 0.51; BW, 2.00 +/- 0.71/2.05 +/- 0.43; BT, 2.37 +/- 0.86/11.17 +/- 2.29; BFT, 1.83 +/- 0.50/15.73 +/- 1.78. No significant differences were seen after immersions (p > .05). Brushing increased the roughness of cp Ti and of Ti-6Al-4V (p < .01); cp Ti had topographic changes after BW, BT and BFT treatments whilst Ti-6Al-4V was significantly different only after BT and BTF. EDS has not detected fluoride or sodium ions on metal surfaces. Conclusions: Exposure to toothpastes (immersion) does not affect titanium per se; their use during brushing affects titanium topography and roughness. The associated effects of toothpaste abrasives and fluorides seem to increase roughness on titanium brushed surfaces. (C) 2012 Elsevier Ltd. All rights reserved.

Seven years of external control of fluoride levels in the public water supply in Bauru, São Paulo, Brazil

Fluoridation of the public water supplies is recognized as among the top ten public health achievements of the twentieth century. However, the positive aspects of this measure depend on the maintenance of fluoride concentrations within adequate levels. To report the results of seven years of external control of the fluoride (F) concentrations in the public water supply in Bauru, SP, Brazil in an attempt to verify, on the basis of risk/benefit balance, whether the levels are appropriate. From March 2004 to February 2011, 60 samples were collected every month from the 19 supply sectors of the city, totaling 4,641 samples. F concentrations in water samples were determined in duplicate, using an ion-specific electrode (Orion 9609) coupled to a potentiometer after buffering with TISAB II. After the analysis, the samples were classified according to the best risk-benefit adjustment. Means (±standard deviation) of F concentrations ranged between 0.73±0.06 and 0.81±0.10 mg/L for the different sectors during the seven years. The individual values ranged between 0.03 and 2.63 mg/L. The percentages of the samples considered “low risk” for dental fluorosis development and of “maximum benefit” for dental caries prevention (0.55-0.84 mg F/L) in the first, second, third, fourth, fifth, sixth, and seventh years of the study were 82.0, 58.5, 37.4, 61.0, 89.9, 77.3, and 72.4%, respectively, and 69.0% for the entire period. Fluctuations of F levels were found in the public water supply in Bauru during the seven years of evaluation. These results suggest that external monitoring of water fluoridation by an independent assessor should be implemented in cities where there is adjusted fluoridation. This measure should be continued in order to verify that fluoride levels are suitable and, if not, to provide support for the appropriate adjustments

Effect of fluoride sodium mouthwash solutions on cpTI: evaluation of physicochemical properties

The effects of fluoride, which is present in different oral hygiene products, deserve more investigation because little is known about their impact on the surface of titanium, which is largely used in Implantology. This study evaluated the surface of commercially pure titanium (cpTi) after exposure to different concentrations of sodium fluoride (NaF). The hypothesis tested in this study was that different concentrations of NaF applied at different time intervals can affect the titanium surface in different ways. The treatments resulted in the following groups: GA (control): immersion in distilled water; GB: immersion in 0.05% NaF for 3 min daily; GC: immersion in 0.2% NaF for 3 min daily; GD: immersion in 0.05% NaF for 3 min every 2 weeks; and GE: immersion in 0.2% NaF for 3 min every 2 weeks. The experiment lasted 60 days. Roughness was measured initially and every 15 days subsequently up to 60 days. After 60 days, corrosion analysis and anodic polarization were done. The samples were examined by scanning electron microscopy (SEM). The roughness data were analyzed by ANOVA and there was no significant difference among groups and among time intervals. The corrosion data (i corr) were analyzed by the Mann-Whitney test, and significant differences were found between GA and GC, GB and GC, GC and GD, GC and GE. SEM micrographs showed that the titanium surface exposed to NaF presented corrosion that varied with the different concentrations. This study suggests that the use of 0.05% NaF solution on cpTi is safe, whereas the 0.2% NaF solution should be carefully evaluated with regard to its daily use.

Synthese von optisch aktiven 2-Vinyl-piperidinen - Schlüsselbausteine für die Clavepictin-Totalsynthese

Im Rahmen der vorliegenden Arbeit wurden eine Vielzahl optisch aktiver 1,2,6-trisubstituierte Piperidine stereoselekiv dargestellt. Bei der anschließenden Aza-Claisen-Umlagerunge wurden daraus chirale Azecinone (zyklische, ungesättigte, zehngliedrige Lactame) gebildet, die sich für die Totalsynthese u. a. von Clavepictin A eignen.rnrnDazu wurde zunächst über eine weitere zwitterionische Aza-Claisen-Umlagerung ein Dien aufgebaut, welches durch intramolekulare Grubbs-Metathese zum Piperidin geschlossen werden konnte. Daraus wurde ein Baikiain- sowie ein Pipecolinsäure-Derivat hergestellt.rnrnAuf einem weiteren Weg zu hochsubstituierten Piperidinen wurde eine von Katritzky et al. erarbeitete Synthese eines Bisaminals auf ihre Flexibilität bezüglich des Substitutionsmusters in 2- und 6-Position am Piperidinring durch eine Kaskade an Reduktionen und Grignard-Reaktionen zu stereoselektiv trisubstituierten 2-Vinyl-Piperidinen untersucht. rnrnDie anschließende zwitterionische Aza-Claisen-Umlagerung an diesen Vinyl-Piperidinen mit verschiedenen Säurefluoriden diente jeweils zur Überprüfung der Tauglichkeit der ausgewählten Reaktionswege zur Totalsynthese von Clavepictin. Durch Strukturbestimmung der gebildeten Azecinone mittels NOESY wurde der erwartete Chiralitätstransfer bei der Umlagerungsreaktion untersucht bzw. bestätigt.rnrnNebenbei wurde dabei ein Chinolizidin-Derivat gefunden, dessen Darstellung durch eine neuartige Dominoreaktion erklärt wurde und dessen Grundstruktur einen weiteren und ggf. kürzeren Syntheseweg zu Clavepictin A und seinen Derivaten zulassen sollte. rn

Fluoride in dental erosion

Dental erosion develops through chronic exposure to extrinsic/intrinsic acids with a low pH. Enamel erosion is characterized by a centripetal dissolution leaving a small demineralized zone behind. In contrast, erosive demineralization in dentin is more complex as the acid-induced mineral dissolution leads to the exposure of collagenous organic matrix, which hampers ion diffusion and, thus, reduces further progression of the lesion. Topical fluoridation inducing the formation of a protective layer on dental hard tissue, which is composed of CaF(2) (in case of conventional fluorides like amine fluoride or sodium fluoride) or of metal-rich surface precipitates (in case of titanium tetrafluoride or tin-containing fluoride products), appears to be most effective on enamel. In dentin, the preventive effect of fluorides is highly dependent on the presence of the organic matrix. In situ studies have shown a higher protective potential of fluoride in enamel compared to dentin, probably as the organic matrix is affected by enzymatical and chemical degradation as well as by abrasive influences in the clinical situation. There is convincing evidence that fluoride, in general, can strengthen teeth against erosive acid damage, and high-concentration fluoride agents and/or frequent applications are considered potentially effective approaches in preventing dental erosion. The use of tin-containing fluoride products might provide the best approach for effective prevention of dental erosion. Further properly designed in situ or clinical studies are recommended in order to better understand the relative differences in performance of the various fluoride agents and formulations.