Adducts of Silicon Tetrafluoride with Aminocyclophosphazenes : Synthesis and Characterization

Stable solid adducts of SiF4 with the following aminocyclophosphazenes have been synthesized : N3P3(NHCH2CH2NH)(NMe2)4(,1 ) ; N3P3(NHCH2CH2NH)C14(,2 ) ; N3P3(NMe2)4C12(,3 ) ; N3P3(NHMe),,(4) ; N3P3(NMe2),, (5) ; N,P,(NHMe),, (6) ; N4P4(NMe2),, (7) ; and N,P,(NHBu'),, (8). They have been characterized by elemental analysis, i.r., and n.m.r. ( H, 31 P, and 19F) spectroscopy. The composition of the adducts varies depending on the ring size and also on the nature of the substituents on the phosphorus. The number of SiF4 molecules accommodated by the ligands is larger when the ring size is large, while it is less when the ligands contain chlorine. Except in the cases of ligands (1) and (2), bonding is through the ring nitrogens. With (I), both exocyclic nitrogen and ring nitrogen atoms, and with (2) only exocyclic nitrogen atoms, participate in co-ordination. In these two cases the silicon is six-co-ordinated, while in the other cases it is five-co-ordinated.

The reaction of sulphur tetrafluoride with pyridine

Abstract is not available.

Silicon tetrafluoride : Preparation and reduction with lithium aluminium hydride

Pure silicon tetrafluoride can be prepared in 66% yield from silicon tetrachloride by refluxing with lead fluoride in acetonitrile. The gas can be reduced to pure silane by lithium aluminum hydride in diethyl ether.

Investigations into electronic stopping regime sputtering of uranium tetrafluoride

Yields were measured for ²³⁵U sputtered from UF₄ by ¹⁶O, ¹⁹F, and ³⁵Cl over the energy range ~.12 to 1.5 MeV/ amu sing a charge equilibrated beam in the stripped beam arrangement for all the incident ions and in the transmission arrangement for ¹⁹F and ³⁵Cl. In addition, yields were measured for ¹⁹F incident in a wide range of discrete charge states. The angular dependence of all the measured yields were consistent with cosʋ. The stripped beam and transmission data were well fit by the form (Az²eqln(BƐ)/Ɛ)⁴ (where Ɛ was the ion energy in MeV/amu and z_eq(Ɛ) was taken from Zeigler(80). The fitted values of B for the various sets of data were consistent with a constant B₀, equal to 36.3 ± 2.7, independent of incident ion. The fitted values of A show no consistent variation with incident ion although a difference can be noted between the stripped beam and transmission values, the transmission values being higher.

The incident charge data were well fit by the assumptions that the sputtering yield depended locally on a power of the incident ion charge and that the sputtering from the surface is exponentially correlated to conditions in the bulk. The equilibrated sputtering yields derived from these data are in agreement with the stripped beam yields.

In addition, to aid in the understanding of these data, the data of Hakansson(80,81a,81b) were examined and contrasted with the UF₄ results. The thermal models of Seiberling(80) and Watson(81) were discussed and compared to the data.

Protection of short-time enamel erosion by different tetrafluoride compounds

objective: This in vitro study aimed to analyse the protective effect of differently concentrated titanium (TiF4), zirconium (ZrF4) and hafnium (HfF4) tetrafluoride on enamel erosion. Methods: Polished enamel surfaces of 36 bovine crowns were covered with tape leaving 4 enamel windows each 3 mm in diameter exposed. The crowns were randomly assigned to six groups (each n = 6) and pretreated with 4% TiF4, 10% TiF4, 4% ZrF4, 10% ZrF4, 4% HfF4 or 10% HfF4 for 4 min (first window), 10 min (second window) or 15 min (third window). The fourth window of each crown was not pretreated and served as control. Erosion was performed stepwise with 1% HCl (pH 2) in five consecutive intervals of each 15 s (total 75 s). Enamel dissolution was quantified by colorimetric determination of phosphate release into the acid. For each tooth, cumulative phosphate loss of enamel pretreated with one of the tetrafluoride compounds was calculated as percentage of the respective control and statistically analysed using two-way ANOVA.Results: Enamel erosion was significantly reduced by TiF4, ZrF4 and HfF4 application. Cumulative phosphate loss (mean % of control, 75 s erosion) after 4-15 min application was significantly lower for 4% ZrF4 (7-11%), 10% ZrF4 (2-6%), 4% HfF4 (11-9%) and 10% HfF4 (12-16%) compared to 4% TiF4 (42-27%) and 10% TiF4 (54-33%). Only for 4% and 10% TiF4, phosphate loss decreased with increasing duration of application, but also increased with increasing acid intervals.Conclusion: TiF4, ZrF4 and HfF4 might protect enamel against short-time erosion, but protection was more enhanced by ZrF4 and HfF4 compared to TiF4 application overtime. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of 4% titanium tetrafluoride solution on the erosion of permanent and deciduous human enamel: an in situ/ex vivo study

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

Effect of a 4% titanium tetrafluoride (TiF4) varnish on demineralisation and remineralisation of bovine enamel in vitro

Objectives: This in vitro study assessed the effect of a 4% TiF4 varnish on demineralisation and remineralisation of sound enamel and artificial carious enamel lesions, respectively.Methods: Bovine sound and carious enamel (n = 110) were randomly allocated to each type of varnish: Duraphat (R))-D (NaF, 2.26%F, pH 4.5, Colgate-Brazil, n = 30), Duofluorid (R)-F (NaF, 2.71%F, pH 8.0, FGM-Brazil, n = 30), TiF4-T (2.45%F, pH 1.0, FGM-Brazil, n = 30) and no-fluoride-P (FGM-Brazil, pH 5.0, n = 20). For the formation of artificial enamel caries, half of the blocks were immersed in 32 mL buffer acetate solution (16 h), whereas the other half was maintained sound. The varnishes were applied onto the enamel surfaces. Thus, the samples were subjected to pH cycles (37 degrees C) for 7 days. The response variables tested were surface and cross-sectional hardness. Data were tested using Kruskal-Wallis test (p < 0.05).Results: All F varnishes significantly reduced demineralisation and increased remineralisation in comparison to placebo. The TiF4 did not significantly reduce the surface enamel softening when compared with the other F varnishes, but it decreased the loss of subsurface hardness to the same extent. In enamel blocks with previous artificial carious lesions, the TiF4 significantly improved the rehardening compared to the other varnishes up to 30 mu m depth.Conclusions: The TiF4 varnish was able to decrease the demineralisation and increase the remineralisation of previously sound and carious enamel, respectively. It was equally effective compared to NaF varnishes on reducing the demineralisation at subsurface, but it was more effective on improving the remineralisation at surface and subsurface. (c) 2007 Elsevier Ltd. All rights reserved.

Effect of 4% titanium tetrafluoride solution on dental erosion by a soft drink: An in situ/ex vivo study

Objective: This in situ/ex vivo study assessed the effect of titanium tetrafluoride (TiF4) on permanent human enamel subjected to erosion.Design: Ten volunteers took part in this study performed in two phases. In the first phase (ERO), they wore acrylic palatal appliances containing two enamel blocks, divided into two rows: TiF4 (F) and no-TiF4 (no-F). During the 1st day, the formation of a salivary pellicle was allowed. In the 2nd day, the TiF4 solution was applied on one row (ERO + F), whereas on the other row no treatment was performed (ERO + no-F). From 3rd until 7th day, the blocks were subjected to erosion, 4x per day. In the 2nd phase (no-ERO), the volunteers wore acrylic palatal appliances containing one enamel block, during 2 days, to assess the effect of TiF4 only (no-ERO + F). Enamel alterations were determined using profilometry (wear), microhardness (%SMHC) tests, scanning electron microscope and microprobe analysis. The %SMHC and wear were tested using ANOVA and Tukey's post hoc tests (p < 0.05).Results: The mean of %SMHC and wear ( mu m) values ( +/- S.D.) were, respectively: ERO + F -73.32 +/- 5.16(A)/2.40 +/- 0.60(a); ERO + no-F -83.49 +/- 4.59B/1.17 +/- 0.48(b) and no-ERO + F -67.92 +/- 6.16(A)/0.21:E 0.09(c). In microscope analysis, the no-F group showed enamel with honeycomb appearance. For F groups, it was observed a surface coating with microcracks. The microprobe analysis revealed the presence of the following elements (%) in groups ERO + F, ERO + no-F and no-ERO + F, respectively: Ca (69.9, 72.5, 66.25); P (25.9, 26.5, 26.06); Ti (3.0, 0, 5.93).Conclusions: The TiF4 was unable to reduce dental erosion. (c) 2007 Elsevier Ltd. All rights reserved.

Effect of an experimental 4% titanium tetrafluoride varnish on dental erosion by a soft drink

Objectives: This in vitro study assessed the effect of an experimental 4%TiF4 varnish on enamel erosion.Methods: Sixty bovine enamel blocks were randomly allocated to each type of varnish:Duraphat((R)) -D (NaF, 2.26%F), Duofluorid((R))-F(NaF, 2.71% F), TiF4-T(2.45%F) and no-fluoride-P. After application of the varnishes, the blocks were subjected to six sequential pH cycles (cola drink for 10 min and artificial saliva for 50 min, each) per day, during 4 days. After the pH cycles, the blocks were maintained in artificial saliva for 18 h. Enamel alterations were determined in the 2nd and 4th days, using profilometry (wear) and microhardness (%SMHC) tests. Data were tested using ANOVA and Tukey's tests (p < 0.05).Results: the mean %SMHC (+/- S.D.) at the 2nd and 4th day was, respectively, D (-77.26 +/- 5.04(a) and -88.59 +/- 5.11(A)), F (-76.79 +/- 7.82(a) and -88.78 +/- 6.10(A)), T(-88.28 +/- 3.19(b) and -92.04 +/- 2.54(A,B)) and P (-87.96 +/- 2.23(b) and -94.15 +/- 1.14(B)). The mean wear (mu m +/- S.D.) at the 2nd and 4th day was, respectively, D (3.16 +/- 0.32(a) and 7.56 +/- 0.90(A)), F(3.35 +/- 0.78(a,b) and 7.92 +/- 0.98(A)), T (3.81 +/- 0.43(b) and 7.69 +/- 0.76(A)) and P (3.43 +/- 1.13(a,b) and 7.31 +/- 0.53(A)).Conclusions: the NaF varnishes reduced the softening, but had no effect on the reduction of the wear. The TiF4 varnish was not able to reduce the softening and wear. (C) 2007 Elsevier Ltd. All rights reserved.

In situ effect of sodium fluoride or titanium tetrafluoride varnish and solution on carious demineralization of enamel

This study evaluated the effect of titanium tetrafluoride (TiF4) formulations on enamel carious demineralization in situ. Thirteen subjects took part in this cross-over, split-mouth, double-blind study performed in three phases of 14 d each. In each subject, two sound and two predemineralized specimens of bovine enamel were worn intra-orally and plaque accumulation was allowed. One sound and one predemineralized specimen in each subject was treated once with sodium fluoride (NaF) varnish or solution (Treatment A); TiF4 varnish or solution (Treatment B); or placebo varnish or no treatment (Treatment C). The initially sound enamel specimens were exposed to severe cariogenic challenge (20% sucrose, eight times daily for 5 min each time), whereas the predemineralized specimens were not. Eleven subjects were able to finish all experimental phases. The enamel alterations were quantified by surface hardness and transversal microradiography. Demineralization of previously sound enamel was reduced by all test formulations except for the NaF solution, while both TiF4 formulations were as effective as NaF varnish. For the predemineralized specimens, enamel surface hardness was increased only by TiF4 formulations, while subsurface mineral remineralization could not be seen in any group. Within the experimental protocol, TiF4 was able to decrease enamel demineralization to a similar degree as NaF varnish under severe cariogenic challenges, while only TiF4 formulations remineralized the enamel surface.

Preparation of Hexafluorodisilane and Reactions of Hexafluorodisilane and Hexachlorodisilane with Sulfur Trioxide

Hexafluorodisilane has been prepared by the fluorination of hexachlorodisilane or hexabromodisilane by potassium fluoride in boiling acetonitrile, in yields approximating 45 and 60% respectively. Hexafluorodisilane has been characterised by infrared spectral data, vapour density measurements and analytical data. Both hexafluorodisilane and hexachlorodisilane are found to react with sulfur trioxide when heated to 400°C for 12 h. The products of reaction are silicon tetrafluoride, silica and sulfur dioxide with hexafluorodisilane while hexachlorodisilane in addition gives rise to hexachlorodisiloxane.