Resonant X-ray photoelectron spectroscopy: identification of atomic contributions to valence states.

Valence electronic structure is crucial for understanding and predicting reactivity. Valence non-resonant X-ray photoelectron spectroscopy (NRXPS) provides a direct method for probing the overall valence electronic structure. However, it is often difficult to separate the varying contributions to NRXPS; for example, contributions of solutes in solvents or functional groups in complex molecules. In this work we show that valence resonant X-ray photoelectron spectroscopy (RXPS) is a vital tool for obtaining atomic contributions to valence states. We combine RXPS with NRXPS and density functional theory calculations to demonstrate the validity of using RXPS to identify atomic contributions for a range of solutes (both neutral and ionic) and solvents (both molecular solvents and ionic liquids). Furthermore, the one-electron picture of RXPS holds for all of the closed shell molecules/ions studied, although the situation for an open-shell metal complex is more complicated. The factors needed to obtain a strong RXPS signal are investigated in order to predict the types of systems RXPS will work best for; a balance of element electronegativity and bonding type is found to be important. Additionally, the dependence of RXPS spectra on both varying solvation environment and varying local-covalent bonding is probed. We find that RXPS is a promising fingerprint method for identifying species in solution, due to the spectral shape having a strong dependence on local-covalency but a weak dependence on the solvation environment.

Surface science and model catalysis with ionic liquid-modified materials.

Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy.

Density and surface tension of ionic liquids.

We measured the density and surface tension of 9 bis[(trifluoromethyl)sulfonyl]imide ([Tf(2)N](-))-based and 12 1-methyl-3-octylimidazolium ([C(8)C(1)Im](+))-based ionic liquids (ILs) with the vibrating tube and the pendant drop method, respectively. This comprehensive set of ILs was chosen to probe the influence of the cations and anions on density and surface tension. When the alkyl chain length in the [C(n)C(1)Im][Tf(2)N] series (n = 1, 2, 4, 6, 8, 10, 12) is increased, a decrease in density is observed. The surface tension initially also decreases but reaches a plateau for alkyl chain lengths greater than n = 8. Functionalizing the alkyl chains with ethylene glycol groups results in a higher density as well as a higher surface tension. For the dependence of density and surface tension on the chemical nature of the anion, relations are only found for subgroups of the studied ILs. Density and surface tension values are discussed with respect to intermolecular interactions and surface composition as determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). The absence of nonvolatile surface-active contaminants was proven by ARXPS.

Insights into the surface composition and enrichment effects of ionic liquids and ionic liquid mixtures.

A systematic study of ionic liquid surfaces by angle resolved X-ray photoelectron spectroscopy (ARXPS) is presented. By reviewing recent and presenting new results for imidazolium-based ionic liquids (ILs), we discuss the impact of chemical differences on surface composition and on surface enrichment effects. (1) For the hydrophilic ethylene glycol (EG) functionalised ILs [Me(EG)MIm][Tf(2)N], [Et(EG)(2)MIm][Tf(2)N] and [Me(EG)(3)MIm][Tf(2)N], which vary in the number of ethylene glycol units (from 1 to 3), we find that the surface composition of the near-surface region is in excellent agreement with the bulk composition, which is attributed to attractive interactions between the oxygen atoms on the cation to the hydrogen atoms on the imidazolium ring. (2) For [C(n)C(1)Im][Tf(2)N] (where n = 1-16), i.e. ILs with an alkyl chain of increasing length, an enrichment of the aliphatic carbons is observed for longer chains (n > 2), at the expense of the polar cation head groups and the anions in the first molecular layer, both of which are located approximately at the same distance from the outer surface. (3) To study the influence of the anion on the surface enrichment, we investigated ten ILs [C(8)C(1)Im][X] with the same cation, but very different anions [X](-). In all cases, surface enrichment of the cation alkyl chains is found, with the degree of enrichment decreasing with increasing size of the anion, i.e., it is most pronounced for the smallest anions and least pronounced for the largest anions. (4) For the IL mixture [C(2)C(1)Im][Tf(2)N] and [C(12)C(1)Im][Tf(2)N] we find a homogeneous distribution in the outermost surface region with no specific enrichment of the [C(12)C(1)Im](+) cation.

Influence of different substituents on the surface composition of ionic liquids studied using ARXPS.

Angle resolved X-ray photoelectron spectroscopy has been used to study the surface composition of various nonfunctionalized and functionalized 1,3-dialkylimidazolium ionic liquids. For [CnC1Im][Tf2N] (where n = 2-16), an enrichment of the aliphatic carbon was observed for longer chains (n > or = 4). Enrichment of the aliphatic carbon also occurs for alkyl chains attached to the anion, as observed for [C2C1Im][OcOSO3]. Oligo(ethyleneglycol)ether (PEG) functionalities in the cation lead to a surface composition close to bulk stoichiometry and thus a loss in enrichment of the chains. This effect is attributed to attractive interactions between the oxygen atoms on the cation to the hydrogen atoms on the imidazolium ring for [Et(EG)2MIm] [Tf2N] and [Me(EG)3MIm][Tf2N].

Influence of different anions on the surface composition of ionic liquids studied using ARXPS.

Angle-resolved X-ray photoelectron spectroscopy has been used to study the influence of different types of anions on the surface composition of ionic liquids (ILs). We have investigated nine ILs with the same cation, 1-octyl-3-methylimidazolium [C(8)C(1)Im](+), but very different anions. In all cases, an enrichment of the cation alkyl chains is found at the expense of the polar cation head groups and the anions in the first molecular layer. This enhancement effect decreases with increasing size of the anion, which means it is most pronounced for the smallest anions and least pronounced for the largest anions. A simple model is proposed to explain the experimental observations.

Concepts for the treatment of adolescent patients with missing permanent teeth.

INTRODUCTION: Missing permanent teeth is observed with syndromes or is frequently hereditarily propagated in families. The treatment of these patients is a multi-task of specialists of oral surgery, orthodontics and prosthodontics. DISCUSSION: Despite functional and aesthetic considerations, the main problem of all treatment is that it had to be performed in a growing child. This article discusses the conventional and implant-driven concepts to treat patients from childhood to adolescence with selective or multiple missing permanent teeth.

In vitro study of fracture strength and marginal adaptation of polyethylene-fibre-reinforced-composite versus glass-fibre-reinforced-composite fixed partial dentures.

This in vitro study was carried out in order to estimate the clinical usability of adhesively luted three-unit posterior fixed partial dentures (FPD) made of a polyethylene-fibre-reinforced-composite system (PFRC) in comparison with a glass-fibre-reinforced-composite system (GFRC). Therefore the fracture strength and marginal adaptation were examined. A total of 16 FPDs of each material combination were manufactured and adhesively luted to human molars. Before and after an artificial ageing process by thermal cycling and mechanical loading (TCML) the quality of the marginal adaptation was examined by evaluating epoxy replicas in a scanning electron microscope (SEM). After TCML the fracture strength of eight FPDs of each series was tested by mechanical loading them to failure. With the remaining eight FPDs the quality of deeper layers of the luting was examined with a dye penetration technique. The calculated median fracture strength values (25/75% percentiles) were 830 N (643/982) for the PFRC and 884 N (684/1,113) for the GFRC. The SEM analysis showed at least 80% of perfect marginal areas for both material combinations in dentine as well as in enamel before and after TCML. Looking at the cement-tooth interfaces the dye penetration technique showed statistically significant better results for the enamel finishing lines than for those in dentine. With finishing lines in dentine the two material combinations showed statistically significant differences for this interface. Fracture force results as well as marginal quality encourage further clinical investigations on both systems although the GFRC performed slightly better than the PFRC.

In vitro repair of three-unit fiber-reinforced composite FPDs.

PURPOSE: Clinical damage, such as the fracture or abrasion of composite veneers, may cause the loss of a fixed partial denture (FPD). Intraoral methods may help in repairing and therefore lengthening the life span of the restoration. The aim of this in vitro study was to evaluate an intraoral method of repairing fractured FPDs made of two different fiber-reinforced composite framework systems. MATERIALS AND METHODS: Shear bond strengths of a composite between two different fiber-reinforced composite frameworks were determined after five different mechanical surface treatments. A silicate-silane coating intraoral air-abrading system provided the most reliable bond strength values and was therefore used for treatment for the following veneer repair. The repair of 24 three-unit posterior FPDs was performed using a restorative composite resin. All FPDs were examined after simulating clinical service using thermocycling and mechanical loading. Fracture forces were determined for original FPDs and for FPDs after simulated intraoral repair. RESULTS: The fracture strength of all original FPDs was about 900 N. After repair, a maximum decrease in strength of about 15% was determined. FPDs that were extremely damaged by cutting the framework showed the lowest results, with values of about 450 N. CONCLUSION: The repair of the fractured veneer of fiber-reinforced composite FPDs provided good results and therefore may lengthen the life span of damaged FPDs. The repair of the fractured frameworks showed good results but can only be recommended for limited temporary use.

In vitro repair of all-ceramic and fibre-reinforced composite crowns.

Shear bond strength between fibre reinforced composite and all-ceramic frameworks and veneering/repair composites was investigated after different surface treatments for evaluating the possibility of a repair. Then, 24 crowns were adhesively luted on human teeth and artificially aged. Repair quality was characterized by a loading to fracture test, where undamaged crowns were compared to repaired crowns. To simulate repeated damage, aging and repair, the procedure was performed three times for each crown. A combined silicate-silane treatment of the fibre-reinforced composite frameworks and the hydrofluoric acid etching of the ceramic showed good repair qualities and a sufficient fracture strength for clinical application.

In vitro fracture force and marginal adaptation of ceramic crowns fixed on natural and artificial teeth.

PURPOSE: Artificial teeth made of acrylic resin or alloy are considered substitutes for rare caries-free human teeth in in vitro examinations. The purpose of this study was to compare the fracture strength and marginal adaptation of all-ceramic single crowns fixed to natural teeth with crowns fixed to artificial teeth after artificial aging. MATERIALS AND METHODS: The fracture force and marginal adaptation were investigated in 28 adhesively luted all-ceramic crowns on human molars of different sizes, as well as on alloy and liquid crystal polymer (LCP) artificial teeth. The fracture force was determined using a universal testing machine, and the semiquantitative marginal adaptation was examined using a scanning electron microscope, in both instances after simulating 5 years of clinical service. RESULTS: Fracture force was found to be significantly higher for crowns fixed on substitute materials (alloy = 1,838 N; LCP = 1,392 N) than for crowns on human teeth (888 N). No significant differences in marginal quality could be determined between the groups. All crowns showed marginal gaps of about 10% and perfect margins at about 90%. CONCLUSION: The high in vitro fracture values of all-ceramic crowns on artificial materials may lead to a misinterpretation of the tested restorative materials, overvaluing the material properties in a first preclinical estimation. Human teeth or materials with a comparable modulus of elasticity are therefore preferred in in vitro fracture tests.

Accuracy of quantitative digital subtraction radiography for determining changes in calcium mass in mandibular bone: an in vitro study.

The aim of this in vitro study was to determine the accuracy of digital subtraction radiography (DSR) to detect small changes in calcium mass in alveolar bone adjacent to tooth roots. In each of 4 dried porcine mandible segments, one interproximal and one buccal "defect" region was defined adjacent to a premolar root. A series of cortical and cancellous bone slices with a 50 microns--stepwise increasing thickness (0-5000 microns) were attached to the mandible segments covering the respective "defect" region. Standardized radiographs were quantitatively assessed for density changes using DSR. After dissolving each bone slice in hydrochloric acid, its calcium concentration was photometrically determined. For each bone slice, the mean calcium mass covering a single pixel of the subtraction image was calculated. The Wilcoxon signed-rank test and the Mann-Whitney U-test were used for statistical analysis (alpha = 0.05). A strong linear correlation (r2 = 0.86-1.00; p < or = 0.001) was found between the thickness of the bone slices and their calcium mass. Cortical bone showed a 3.5 times higher mean calcium mass/pixel than cancellous bone. Furthermore, a strong linear correlation (r2 = 0.63-1.00; p < or = 0.001) was found between the mean calcium mass per image pixel and the radiographic density changes. Neither the bone type nor the "defect" localization had a significant influence on radiographic density changes caused by changes in calcium mass. A change in mean calcium mass per image pixel of 0.1-0.15 mg was necessary to be detected by DSR. In conclusion, this study revealed a high accuracy of DSR to detect small changes in calcium mass in alveolar cortical and cancellous bone.

Quantitative digital subtraction radiography for the determination of small changes in bone thickness: an in vitro study.

OBJECTIVE: The objective of this study was to determine the ability of quantitative digital subtraction radiography to detect small changes in bone thickness adjacent to tooth roots. STUDY DESIGN: A series of cortical or cancellous bone slices with a 50 microm-stepwise increasing thickness were attached to 4 porcine mandible sections covering buccal and interproximal "defect" regions. Standardized radiographs were quantitatively evaluated for radiographic density changes with the use of digital subtraction radiography. Furthermore, all radiographs were conventionally evaluated by 10 clinicians. The Wilcoxon signed-rank test and the Mann-Whitney U test were used for statistical analysis (alpha = 0.05). RESULTS: A high linear correlation was found between the actual thickness of bone slices and radiographic density changes (cortical bone: r2 = 0.89 to 0.99; cancellous bone r2 = 0.61 to 0.86, p < or = 0.001). A certain increase in bone thickness caused a 3 times higher increase in radiographic density for cortical bone than for cancellous bone (p < or = 0.05). The detection limits of digital subtraction radiography were 200 microm for cortical and 500 microm for cancellous bone, whereas the detection limits of conventional radiography were 600 microm and 2850 microm, respectively. CONCLUSIONS: This in vitro study demonstrated a very high correlation between the objective, quantitative assessment of subtle changes in alveolar bone by digital subtraction radiography and the true changes in bone thickness.