Flame Synthesis of Complex Fluoride-Based Nanoparticles as Upconversion Phosphors

Recent improvements in precursor chemistry, reactor geometry and run conditions extend the manufacturing capability of traditional flame aerosol synthesis of oxide nanoparticles to metals, alloys and inorganic complex salts. As an example of a demanding composition, we demonstrate here the one-step flame synthesis of nanoparticles of a 4-element non-oxide phosphor for upconversion applications. The phosphors are characterized in terms of emission capability, phase purity and thermal phase evolution. The preparation of flame-made beta-NaYF4 with dopants of Yb, Tm or Yb, Er furthermore illustrates the now available nanoparticle synthesis tool boxes based on modified flamespray synthesis from our laboratories at ETH Zurich. Since scaling concepts for flame synthesis, including large-scale filtration and powder handling, have become available commercially, the development of industrial applications of complex nanoparticles of metals, alloys or most other thermally stable, inorganic compounds can now be considered a feasible alternative to traditional top-down manufacturing or liquid-intense wet chemistry.

The effect of a tin-containing fluoride mouth rinse on the bond between resin composite and erosively demineralised dentin

OBJECTIVES To evaluate the effect of a tin-containing fluoride (Sn/F) mouth rinse on microtensile bond strength (μTBS) between resin composite and erosively demineralised dentin. MATERIALS AND METHODS Dentin of 120 human molars was erosively demineralised using a 10-day cyclic de- and remineralisation model. For 40 molars, the model comprised erosive demineralisation only; for another 40, the model included treatment with a NaF solution; and for yet another 40, the model included treatment with a Sn/F mouth rinse. In half of these molars (n = 20), the demineralised organic matrix was continuously removed by collagenase. Silicon carbide paper-ground, non-erosively demineralised molars served as control (n = 20). Subsequently, μTBS of Clearfil SE/Filtek Z250 to the dentin was measured, and failure mode was determined. Additionally, surfaces were evaluated using SEM and EDX. RESULTS Compared to the non-erosively demineralised control, erosive demineralisation resulted in significantly lower μTBS regardless of the removal of demineralised organic matrix. Treatment with NaF increased μTBS, but the level of μTBS obtained by the non-erosively demineralised control was only reached when the demineralised organic matrix had been removed. The Sn/F mouth rinse together with removal of demineralised organic matrix led to significantly higher µTBS than did the non-erosively demineralised control. The Sn/F mouth rinse yielded higher μTBS than did the NaF solution. CONCLUSIONS Treatment of erosively demineralised dentin with a NaF solution or a Sn/F mouth rinse increased the bond strength of resin composite. CLINICAL RELEVANCE Bond strength of resin composite to eroded dentin was not negatively influenced by treatment with a tin-containing fluoride mouth rinse.

The effect of monoalkyl phosphates and fluoride on dissolution of hydroxyapatite, and interactions with saliva

The aims were to investigate the effect of monoalkyl phosphates (MAPs) and fluoride on dissolution rate of native and saliva-coated hydroxyapatite (HA). Fluoride at 300 mg/l (as NaF) inhibited dissolution of native HA by 12%, while potassium and sodium dodecyl phosphates (PDP, SDP), at 0.1% or higher, inhibited dissolution by 26-34%. MAPs, but not fluoride, also showed persistence of action. MAPs at 0.5% and fluoride at 300 mg/l were then tested separately against HA pre-treated with human saliva for 2 or 18 h. Agents were applied with brushing to half the specimens, and without brushing to the other half. In control (water-treated) specimens, pre-treatment of HA with human saliva reduced dissolution rate on average by 41% (2 h) and 63% (18 h). Brushing did not have a statistically significant effect on dissolution rate of saliva-coated specimens. In brushed specimens, fluoride significantly increased the inhibition due to 2- or 18-hour saliva pre-treatment. It is hypothesised that brushing partially removes the salivary film and allows KOH-soluble calcium fluoride formation at the surfaces of HA particles. Inhibition was reduced by PDP in 2-hour/non-brushed specimens and in 18-hour/brushed specimens. PDP did not affect dissolution rates in the remaining groups and SDP did not affect dissolution rate in any group. Possible reasons for these variable results are discussed. The experiments show that pre-treatment with saliva can significantly modify results of tests on potential anti-erosive agents and it is recommended that saliva pre-treatment should be a routine part of testing such agents.

Caries-preventive effectiveness of fluoride varnish as adjunct to oral health promotion and supervised tooth brushing in preschool children: a double-blind randomized controlled trial.

OBJECTIVES To evaluate the effect of biannual fluoride varnish applications in preschool children as an adjunct to school-based oral health promotion and supervised tooth brushing with 1000ppm fluoride toothpaste. METHODS 424 preschool children, 2-5 year of age, from 10 different pre schools in Athens were invited to this double-blind randomized controlled trial and 328 children completed the 2-year programme. All children received oral health education with hygiene instructions twice yearly and attended supervised tooth brushing once daily. The test group was treated with fluoride varnish (0.9% diflurosilane) biannually while the control group had placebo applications. The primary endpoints were caries prevalence and increment; secondary outcomes were gingival health, mutans streptococci growth and salivary buffer capacity. RESULTS The groups were balanced at baseline and no significant differences in caries prevalence or increment were displayed between the groups after 1 and 2 years, respectively. There was a reduced number of new pre-cavitated enamel lesions during the second year of the study (p=0.05) but the decrease was not statistically significant. The secondary endpoints were unaffected by the varnish treatments. CONCLUSIONS Under the present conditions, biannual fluoride varnish applications in preschool children did not show significant caries-preventive benefits when provided as an adjunct to school-based supervised tooth brushing with 1000ppm fluoride toothpaste. CLINICAL SIGNIFICANCE In community based, caries prevention programmes, for high caries risk preschool children, a fluoride varnish may add little to caries prevention, when 1000ppm fluoride toothpaste is used daily.

Preparation and optimization of calcium fluoride particles for dental applications.

Fluorides are used in dental care due to their beneficial effect in tooth enamel de-/remineralization cycles. To achieve a desired constant supply of soluble fluorides in the oral cavity, different approaches have been followed. Here we present results on the preparation of CaF2 particles and their characterization with respect to a potential application as enamel associated fluoride releasing reservoirs. CaF2 particles were synthesized by precipitation from soluble NaF and CaCl2 salt solutions of defined concentrations and their morphology analyzed by scanning electron microscopy. CaF2 particles with defined sizes and shapes could be synthesized by adjusting the concentrations of the precursor salt solutions. Such particles interacted with enamel surfaces when applied at fluoride concentrations correlating to typical dental care products. Fluoride release from the synthesized CaF2 particles was observed to be largely influenced by the concentration of phosphate in the solution. Physiological solutions with phosphate concentration similar to saliva (3.5 mM) reduced the fluoride release from pure CaF2 particles by a factor of 10-20 × as compared to phosphate free buffer solutions. Fluoride release was even lower in human saliva. The fluoride release could be increased by the addition of phosphate in substoichiometric amounts during CaF2 particle synthesis. The presented results demonstrate that the morphology and fluoride release characteristics of CaF2 particles can be tuned and provide evidence of the suitability of synthetic CaF2 particles as enamel associated fluoride reservoirs.

Fluoride varnishes with calcium glycerophosphate: fluoride release and effect on in vitro enamel demineralization

The aims of this study were (1) to assess the amount of fluoride (F) released from varnishes containing calcium glycerophosphate (CaGP) and (2) to assess the effect of the experimental varnishes on in vitro demineralization. Six test groups using 5 varnishes: base varnish (no active ingredients); Duraphat® (2.26% NaF); Duofluorid® (5.63% NaF/CaF2); experimental varnish 1 (1% CaGP/5.63% NaF/CaF2); experimental varnish 2 (5% CaGP/5.63% NaF/CaF2); and no varnish were set up. In stage 1, 60 acrylic blocks were randomly distributed into 6 groups (n = 10). Then 300 µg of each varnish was applied to each block. The blocks were immersed in deionized water, which was changed after 1, 8, 12, 24, 48 and 72 hours. Fluoride concentration in the water was analyzed using a fluoride electrode. In stage 2, 60 bovine enamel samples were distributed into 6 groups (n = 10), and treated with 300 µg of the respective varnish. After 6 h the varnish was removed and the samples were subjected to a 7-day in vitro pH cycle (6 h demineralization/18 h remineralization per day). The demineralization was measured using surface hardness. The results showed that both experimental varnishes released more fluoride than Duofluorid® and Duraphat® (p < 0.05), but Duraphat® showed the best preventive effect by decreasing enamel hardness loss (p < 0.05). Therefore, we conclude that even though (1) the experimental varnishes containing CaGP released greater amounts of F, (2) they did not increase in the preventive effect against enamel demineralization.

Fluoride varnishes containing calcium glycerophosphate: fluoride uptake and the effect on in vitro enamel erosion

OBJECTIVES Calcium glycerophosphate (CaGP) was added to fluoride varnishes to analyze their preventive effect on initial enamel erosion and fluoride uptake: potassium hydroxide (KOH)-soluble and KOH-insoluble fluoride bound to enamel. MATERIALS AND METHODS This study was carried out in two parts. Part 1: 108 enamel samples were randomly distributed into six varnish groups: base varnish (no active ingredients); Duraphat® (2.26 %NaF); Duofluorid® (5.63 %NaF/CaF2); experimental varnish 1 (1 %CaGP/5.63 %NaF/CaF2); experimental varnish 2 (5 %CaGP/5.63 %NaF/CaF2); and no varnish. Cyclic demineralization (90 s; citric acid, pH = 3.6) and remineralization (4 h) was made once a day, for 3 days. Change in surface microhardness (SMH) was measured. Part 2: 60 enamel samples were cut in half and received no varnish (control) or a layer of varnish: Duraphat®, Duofluorid®, experimental varnishes 1 and 2. Then, KOH-soluble and KOH-insoluble fluoride were analyzed using an electrode. RESULTS After cyclic demineralization, SMH decreased in all samples, but Duraphat® caused less hardness loss. No difference was observed between varnishes containing CaGP and the other varnishes. Similar amounts of KOH-soluble and insoluble fluoride was found in experimental varnish 1 and Duofluorid®, while lower values were found for experimental varnish 2 and Duraphat®. CONCLUSION The addition of CaGP to fluoride varnishes did not increase fluoride bound to enamel and did not enhance their protection against initial enamel erosion. CLINICAL RELEVANCE We observe that the fluoride varnishes containing CaGP do not promote greater amounts of fluoride bound to enamel and that fluoride bound to enamel may not be closely related to erosion prevention.

The relationship between calcium and fluoride intake, pregnancy and lactation and the risk of height loss in white women

This study was designed to investigate the effect of calcium and fluoride intake, and parity and lactation on the risk of spinal osteoporosis. Height loss was used as a surrogate measure for spinal fractures by taking advantage of documented changes in height found during the 25-year follow-up of the Charleston Heart Study cohort. Women who had lost 2-4" in height or who had no change in height during the follow-up period were defined as case and comparison subjects respectively. Calcium intake when the subjects were "about 25" and in the recent past, average intake of fluoride over 25 years, and parity and history of breastfeeding were ascertained by questionnaire from 54 case and 77 comparison subjects. Low calcium intake in the past decreased the risk of height loss (age-adjusted OR = 0.3, 95%CI: 0.1-0.96) although several potentially important confounding variables could not be adjusted for. There was no association between risk of height loss and present calcium intake (OR = 0.8, 95%CI: 0.3-2.6 for low versus high intake) after adjustment for past calcium intake. High fluoride intake decreased the risk of height loss (adjusted OR = 0.4, 95%CI: 0.1-1.2). The effect of fluoride or calcium intake in the present was modified by the level of the other nutrient. Compared to a low intake of both calcium and fluoride, a high intake of one increased the risk of height loss (crude OR = 3.3 for high fluoride/low calcium, crude OR = 6.0 for high calcium/low fluoride) although a high intake of both was slightly protective (crude OR = 0.7). It is estimated that a "high" nutrient intake in this population was greater than 850mg/day for calcium and 2mg/day for fluoride. After adjustment for age, increasing parity decreased the risk of height loss in women who had never breastfed (OR = 0.2, 95%CI: 0.01-1.7 for 4 or more children). Women who had breastfed were also at lower risk of height loss than nulliparous women (OR = 0.3, 95%CI: 0.1-1.2 for 4 or more children) although at any level of parity, breastfeeding women had a greater risk of height loss than did non-breastfeeding women. ^

(Supplement) Groundwater quality in Lahore Pakistan: emphasis on Arsenic and Fluoride levels

The dataset provides detailed information on the study that was conducted in Lahore's 7 major towns. The sample was taken from 472 tubewells and analyzed for major cations and anions using APHA 2012 techniques as explained herein. Besides, E.coli determination was done to check for microbial contamination. The data includes results from PHREEQC modeling of As(III)/ As(V) species and saturation indices as well as Aquachem's computed hydrochemical water facies. The WHO (2011) and EPA standards included in Aquachem identified the parameters that where in violation. Bicarbonates dominated the groundwater types with 50.21% of the samples exceeding the EPA maximum permissible limit of 250 mg/L in drinking water. Similarly, 30.51% of the samples had TDS values greater than 500 mg/L while 85.38 % of the samples exceed 10 µg/L threshold limit value of arsenic. Also, instances of high magnesium hazard values were observed which requires constant assessment if the groundwater is used for irrigation. Higher than 50% MH values are detrimental to crops which may reduce the expected yields. The membrane filtration technique using m-Endo Agar indicated that 3.59% samples had TNC (too numerous to count) values for E.coli while 5.06% showed values higher than 0 cfu/ 100 ml acceptable value in drinking water. Any traces of E-coli in a groundwater sample indicate recent fecal contamination. Such outcomes signify presence of enteric pathogens. If the groundwater is not properly dosed with disinfectants it may cause harm to human health. It is concluded that more studies are needed and proper groundwater management implement to safeguard the lives of communities that depend solely on groundwater in the city.