Dentin Bond Strength of Two Recent CAD/CAM-Materials after Storage

Purpose: To investigate the bond strength to dentin of two recent resin-ceramic materials for computer-aided design/computer-aided manufacturing (CAD/CAM) after 24 hours and after six months storage. Methods and Materials: Ninety cylinders were milled out of Lava Ultimate (3M ESPE) and 90 cylinders out of VITA ENAMIC (VITA Zahnfabrik) (dimension of cylinders: ∅=3.6 mm, h=2 mm). All Lava Ultimate cylinders were sandblasted (aluminium oxide, grain size: 27 μm) and cleaned with ethanol, whereas all VITA ENAMIC cylinders were acid-etched (5% hydrofluoric acid) and cleaned with water-spray. According to the three groups of cements used, the cylinders (n=30/resin-ceramic material) were further pretreated with 1) Scotchbond Universal for RelyX Ultimate (3M ESPE), 2) CLEARFIL Ceramic Primer for PANAVIA F2.0 (Kuraray), or 3) no further pretreatment for Ketac Cem Plus (3M ESPE). The cylinders were then bonded to ground human dentin specimens with 1) Scotchbond Universal and RelyX Ultimate (light-cured), 2) ED PRIMER II and PANAVIA F2.0 (light-cured), or 3) no adhesive system; Ketac Cem Plus (self-cured). Shear bond strength (SBS) was measured after 24 hours for 15 specimens/group and after six months (37°C, 100% humidity) for the other 15 specimens/group. SBS-values were statistically analysed with nonparametric ANOVA followed by exact Wilcoxon rank sum tests (α=0.05). Results: SBS of the two resin-ceramic materials and the three cements after 24 hours and after six months storage are shown in Figure 1. The statistical analysis showed that the duration of storage had a significant effect on SBS of Lava Ultimate for all three cements but had no significant effect on SBS of VITA ENAMIC. For Lava Ultimate SBS-values were (MPa; medians after 24 hours/six months): 13.5/22.5 (p=0.04) for RelyX Ultimate, 11.4/5.8 (p=0.0006) for PANAVIA F2.0, and 0.34/0.09 (p=0.04) for Ketac Cem Plus (Fig. 1). For VITA ENAMIC SBS-values were (MPa; medians after 24 hours/six months): 16.0/21.2 (p=0.10) for RelyX Ultimate, 11.4/14.4 (p=0.06) for PANAVIA F2.0, and 0.43/0.41 (p=0.32) for Ketac Cem Plus (Fig. 1). After 24 hours, there was no significant difference in SBS between Lava Ultimate and VITA ENAMIC for all three cements (p≥0.37). After six months, there was no significant difference in SBS between Lava Ultimate and VITA ENAMIC for RelyX Ultimate and Ketac Cem Plus (p≥0.07) whereas for PANAVIA F2.0, SBS was significantly lower for Lava Ultimate than for VITA ENAMIC (p<0.0001). Conclusion: SBS of Lava Ultimate was more affected by six months storage and by the cement used than was VITA ENAMIC.

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

With the purpose of rational design of optical materials, distributed atomic polarizabilities of amino acid molecules and their hydrogen-bonded aggregates are calculated in order to identify the most efficient functional groups, able to buildup larger electric susceptibilities in crystals. Moreover, we carefully analyze how the atomic polarizabilities depend on the one-electron basis set or the many-electron Hamiltonian, including both wave function and density functional theory methods. This is useful for selecting the level of theory that best combines high accuracy and low computational costs, very important in particular when using the cluster method to estimate susceptibilities of molecular-based materials.

Materials properties from electron density distributions: Molecular magnetism and linear optical properties

The general goal of this thesis is correlating observable properties of organic and metal-organic materials with their ground-state electron density distribution. In a long-term view, we expect to develop empirical or semi-empirical approaches to predict materials properties from the electron density of their building blocks, thus allowing to rationally engineering molecular materials from their constituent subunits, such as their functional groups. In particular, we have focused on linear optical properties of naturally occurring amino acids and their organic and metal-organic derivatives, and on magnetic properties of metal-organic frameworks. For analysing the optical properties and the magnetic behaviour of the molecular or sub-molecular building blocks in materials, we mostly used the more traditional QTAIM partitioning scheme of the molecular or crystalline electron densities, however, we have also investigated a new approach, namely, X-ray Constrained Extremely Localized Molecular Orbitals (XC-ELMO), that can be used in future to extracted the electron densities of crystal subunits. With the purpose of rationally engineering linear optical materials, we have calculated atomic and functional group polarizabilities of amino acid molecules, their hydrogen-bonded aggregates and their metal-organic frameworks. This has enabled the identification of the most efficient functional groups, able to build-up larger electric susceptibilities in crystals, as well as the quantification of the role played by intermolecular interactions and coordinative bonds on modifying the polarizability of the isolated building blocks. Furthermore, we analysed the dependence of the polarizabilities on the one-electron basis set and the many-electron Hamiltonian. This is useful for selecting the most efficient level of theory to estimate susceptibilities of molecular-based materials. With the purpose of rationally design molecular magnetic materials, we have investigated the electron density distributions and the magnetism of two copper(II) pyrazine nitrate metal-organic polymers. High-resolution X-ray diffraction and DFT calculations were used to characterize the magnetic exchange pathways and to establish relationships between the electron densities and the exchange-coupling constants. Moreover, molecular orbital and spin-density analyses were employed to understand the role of different magnetic exchange mechanisms in determining the bulk magnetic behaviour of these materials. As anticipated, we have finally investigated a modified version of the X-ray constrained wavefunction technique, XC-ELMOs, that is not only a useful tool for determination and analysis of experimental electron densities, but also enables one to derive transferable molecular orbitals strictly localized on atoms, bonds or functional groups. In future, we expect to use XC-ELMOs to predict materials properties of large systems, currently challenging to calculate from first-principles, such as macromolecules or polymers. Here, we point out advantages, needs and pitfalls of the technique. This work fulfils, at least partially, the prerequisites to understand materials properties of organic and metal-organic materials from the perspective of the electron density distribution of their building blocks. Empirical or semi-empirical evaluation of optical or magnetic properties from a preconceived assembling of building blocks could be extremely important for rationally design new materials, a field where accurate but expensive first-principles calculations are generally not used. This research could impact the community in the fields of crystal engineering, supramolecular chemistry and, of course, electron density analysis.