Fracture resistance of endodontically treated teeth restored with different intraradicular posts with different lengths

Aim: This study compared the resistance to fracture of endodontically treated teeth restored with different intraradicular posts with different lengths and full coverage metallic crowns. Methods: Sixty extracted human canine teeth were randomly divided into 6 groups. Groups CP5, CP75 and CP10 were restored using custom cast post and core (CP) and groups PF5, PF75 and PF10 were restored with provisional pre-fabricated tin post (PF) and composite resin core at 5 mm, 7.5 mm and 10 mm of intraradicular length, respectively. The specimens were submitted to dynamic cyclic loading and those that resisted to this load were submitted to load compression using a universal testing machine. Compressive load was applied at a 45-degree angle to the long axis of the tooth until failure. Results: Kruskal-Wallis one-way analysis of variance by ranks showed statistically significant differences among the groups (p<0.0001). However, when the means were compared using the Tukey’s test, significant differences were noted between groups CP5 and CP10 and between groups CP10 and PF5. All groups presented root fractures and post displacements during mechanical cycling. All teeth in groups CP5 and PF5 failed the dynamic cycling test. Conclusions: This study showed that increasing intraradicular post length also increases resistance to fracture of endodontically treated teeth. On the other hand, most endodontically treated teeth restored with pre-fabricated tin posts (provisional posts) failed in the dynamic cycling test

Thermo and mechanical cycling and veneering method do not influence Y-TZP core/veneer interface bond strength

Objectives: The purpose of this study was to evaluate the influence of thermal and mechanical cycling and veneering technique on the shear bond strength of Y-TZP (yttrium oxide partially stabilized tetragonal zirconia polycrystal) core–veneer interfaces. Materials and methods: Cylindrical Y-TZP specimens were veneered either by layering (n = 20) or by pressing technique (n = 20). A metal ceramic group (CoCr) was used as control (n = 20). Ten specimens for each group were thermal and mechanical cycled and then all samples were subjected to shear bond strength in a universal testing machine with a 0.5 mm/min crosshead speed. Mean shear bond strength (MPa) was analysed with a 2-way analysis of variance and Tukey’s test ( p < 0.05). Failure mode was determined using stereomicroscopy and scanning electron microscopy (SEM). Results: Thermal and mechanical cycling had no influence on the shear bond strength for all groups. The CoCr group presented the highest bond strength value ( p < 0.05) (34.72 7.05 MPa). There was no significant difference between Y-TZP veneered by layering (22.46 2.08 MPa) or pressing (23.58 2.1 MPa) technique. Failure modes were predominantly adhesive for CoCr group, and cohesive within veneer for Y-TZP groups. Conclusions: Thermal and mechanical cycling, as well as the veneering technique does not affect Y-TZP core–veneer bond strength. Clinical significance: Different methods of veneering Y-TZP restorations would not influence the clinical performance of the core/veneer interfaces.

Effect of 2% chlorhexidine digluconate on bond strength of a glass-fibre post to root dentine

Aim: To assess the immediate influence of dentine bonding systems (DBS) associated with 2% chlorhexidine digluconate (CHX) on glass-fibre post-bond strength to root dentine, in terms of coronal, middle and apical thirds. Methodology: Sixty bovine roots were root filled and randomly assigned to 1 of 6 groups (n = 10): SBMP (3-step etch-and-rinse system, Scotchbond Multi-Purpose), SB (2-step etch-and-rinse system, Single Bond 2), SE (2-step self-etching system, Clearfil SE Bond) and SBMP-CHX, SB-CHX and SE-CHX, respectively, associated with CHX. For all groups, a glassfibre post was luted with a dual-cure resin cement, RelyX ARC. After 7-day storage, specimens were subjected to the push-out test. Failure modes were analysed under optical microscopy (40x). Bond strength values were statistically analysed by two-way ANOVA and Bonferroni tests (P < 0.05). Results: The effect of DBS was significant (P < 0.05), and SE reached higher bond strength in comparison with the other DBS tested. CHX association did not show improvement with any DBS (P > 0.05); rather, it negatively affected SE, which was detected for all thirds. There was no difference between thirds (P > 0.05), except for the SE-CHX, which presented lower values for the apical third (P < 0.05). Adhesive cement/dentine adhesive failure was predominant for all groups. CHX did not influence the failure mode for any DBS (P > 0.05). Conclusions: The performance of the dentine bonding systems was material dependent. CHX did not improve immediate bond strength; however, CHX negatively affected the bond strength of the self-etching system, especially in the third apical

Chlorhexidine does not increase immediate bond strength of etch-and-rinse adhesive to caries-affected dentin of primary and permanent teeth

The aim of this study was to evaluate the effect of 2% chlorhexidine digluconate (CHX) on immediate bond strength of etch-and-rinse adhesive to sound (SD) and caries-affected (CAD) primary dentin compared with permanent dentin. Flat dentin surfaces from 20 primary molars (Pri) and 20 permanent molars (Perm) were assigned to 8 experimental groups (n=5) according to tooth type (Pri or Perm), dentin condition (SD or CAD - pH-cycling for 14 days) and treatment (control - C or 60 s application of 2% CHX solution after acid etching - CHX). The bonding system (Adper Single Bond 2) was applied according to manufacturer's instructions followed by resin composite application (Filtek Z250). After 24 h water storage, specimens with cross-section area of 0.8 mm² were prepared for being tested under microtensile test (1 mm/min). Data were submitted to ANOVA and Tukey's post hoc test (α=0.05). Failure mode was evaluated using a stereomicroscope at ×400. Treatment with CHX did not result in higher bond strength values than no pre-treatment (C groups), independently of tooth type. Primary teeth and caries-affected dentin showed significantly lower (p<0.05) bond strength means compared with permanent teeth and sound dentin, respectively. Predominance of adhesive/mixed failure was observed for all groups. CHX did not influence the immediate bond strength to sound or caries-affected dentin of primary and permanent teeth.

Influence of alloy microstructure on the microshear bond strength of basic alloys to a resin luting cement

The aim of this study was to evaluate the influence of microstructure and composition of basic alloys on their microshear bond strength (µSBS) to resin luting cement. The alloys used were: Supreme Cast-V (SC), Tilite Star (TS), Wiron 99 (W9), VeraBond II (VBII), VeraBond (VB), Remanium (RM) and IPS d.SIGN 30 (IPS). Five wax patterns (13mm in diameter and 4mm height) were invested, and cast in a centrifugal casting machine for each basic alloy. The specimens were embedded in resin, polished with a SiC paper and sandblasted. After cleaning the metal surfaces, six tygon tubes (0.5 mm height and 0.75 mm in diameter) were placed on each alloy surface, the resin cement (Panavia F) was inserted, and the excess was removed before light-curing. After storage (24 h/37°C), the specimens were subjected to µSBS testing (0.5 mm/min). The data were subjected to a one-way repeated measures analysis of variance and Turkey's test (α=0.05). After polishing, their microstructures were revealed with specific conditioners. The highest µSBS (mean/standard deviation in MPa) were observed in the alloys with dendritic structure, eutectic formation or precipitation: VB (30.6/1.7), TS (29.8/0.9), SC (30.6/1.7), with the exception of IPS (31.1/0.9) which showed high µSBS but no eutectic formation. The W9 (28.1/1.5), VBII (25.9/2.0) and RM (25.9/0.9) showed the lowest µSBS and no eutectic formation. It seems that alloys with eutectic formation provide the highest µSBS values when bonded to a light-cured resin luting cement.

Shear bond strength of nanofilled flowable resins used for indirect bracket bonding

AIM: To evaluate the bond strength of brackets fixed with different materials (two light-cured nanofilled resins - Transbond Supreme LV and Flow Tain LV, a light-cured resin - Transbond XT (control) and two chemically cured resins for indirect bonding - Sondhi Rapid- Set and Custom I.Q.) using the indirect bonding technique after 10 min and 24 h, and evaluate the type of failure. METHODS: One hundred premolars were selected and randomly divided into groups (n=10) according to the material and fixation period. The brackets were bonded through the indirect technique following the manufacturer's instructions and stored in deionized water at 37°C for 10 min or 24 h. After, the specimens were submitted to a shear bond strength (SBS) test (Instron) at 0.5 mm/min and evaluated for adhesive remnant index (ARI). The data were submitted to ANOVA and Tukey's test (p<0.05) and the ARI scores were submitted to the chi-square test. RESULTS: It could be observed a significant difference among the materials (Flow Tain LV = Transbond Supreme LV = Transbond XT> Sondhi Rapid-Set > Custom I.Q.). There was no significant difference in resistance values between 10 min and 24 h, regardless of the materials. Most groups showed adhesive remaining adhered to the enamel (scores 2 and 3) without statistically significant difference (p>0.05). CONCLUSIONS: It was concluded that the light-cured nanofilled materials used in indirect bonding showed greater resistance than the chemically cured materials. The period of fixation had no influence on the resistance for different materials.

James Bond will return: der serielle Charakter der James Bond-Filme

Die James Bond-Filme: seit über 40 Jahren sind sie ein unübersehbarer Bestandteil der Populärkultur. Anfang der 60er Jahre unter völlig anderen historischen, sozialen und nicht zuletzt filmtechnischen Voraussetzungen aus der Taufe gehoben, gelingt es ihnen auch heute noch, ein Massenpublikum für sich zu gewinnen. Inwiefern kann man bei einer so langen Laufzeit überhaupt noch von einer homogenen Serie sprechen? Und was für Gemeinsamkeiten, Unterschiede und auch Weiterentwicklungen von der ursprünglichen Machart sind hier zu beobachten? Dies sind die Grundfragen der vorliegenden Dissertation. Bei der Benennung der seriellen Eigenschaften werden sowohl inhaltliche als auch dramaturgische und filmtechnisch-formale Aspekte betrachtet. Die Figurenkonstellation von Held, Gegenspieler und der weiblichen Hauptfigur, die zwischen den beiden steht und häufig die Seiten wechselt, ist ein Schema das - kaum variiert - schon in den Romanvorlagen Ian Flemings zum Einsatz kam und auch das Rückgrat der Film-Plots bildet. Dennoch ließ dieses Gerüst den mittlerweile fünf verschiedenen Darstellern, die James Bond nacheinander verkörperten, genügend Freiraum für das Ausarbeiten eines eigenen Rollenkonzepts, das auf ihren speziellen Schauspielstil ausgerichtet war. Dadurch erhielt die James Bond-Figur jeweils eine Neuinterpretation, die sich insbesondere in ihrem sozialen Habitus bemerkbar macht, der je nach Darsteller zwischen provokantem Aufsteigertyp und aristokratischem Gentleman changierte. Zum unverwechselbaren Erkennungsmerkmal der Bond-Serie avancierte die so genannte 'gun-barrel'-Sequenz, die in den ersten Sekunden jedes Films abläuft. Auch die sich anschließende Vortitelsequenz, eine auf Spannung oder Action angelegte Szene, die einen Vorgeschmack auf den folgenden Film liefern soll, ist ein Element, das der Machart von Fernsehserien entnommen ist. Neben diesen bewusst eingesetzten Markenzeichen lässt sich auch in der Gestaltungsweise der Filme - in Kameraführung, Schnitt, Musik und Set Design - eine stilistische Kontinuität feststellen, die insbesondere dadurch bedingt ist, dass die Serie seit jeher von den Produzenten ähnlich wie ein Familienunternehmen geführt wurde und - zumindest bis Ende der 80er Jahre - auch die kreativen Köpfe der Filme konsequent im eigenen Team ausgebildet wurden.

New synthetic strategies to tethered bilayer lipid membranes

Tethered bilayer lipid membranes provide an efficient, stable and versatile platform for the investigation of integrated membrane proteins. However, the incorporation of large proteins, as well as of proteins with a large submembrane part is still a very critical issue and therefore, further optimisation of the system is necessary. The central element of a tBLM is a lipid bilayer. Its proximal leaflet is, at least to some extend, covalently attached to a solid support via a spacer group. The anchor lipid consists of three distinct parts, a lipid headgroup, a spacer group and an anchor. All parts together influence the final bilayer properties. In the frame of this work, the synthesis of new thiolipids for tBLMs on gold has been investigated. The aim was to obtain molecules with longer spacers in order to increase the submembrane space. The systems obtained have been characterized using SPR and EIS. The results obtained during this study are multiple. First, the synthesis of a previously synthesized architecture was successfully scaled up in an industrial lab using a new synthetic approach. The synthesis of large amounts is now feasible. Then, the synthesis of the new thiolipids was carried out taking into account the following requirements: the increase of the submembrane space by having longer ethyleneglycol spacers, the attachment of the molecules to a gold substrate via a thiol bond, and the tunability of the lateral mobility by changing the lipid headgroup. Three different synthetic strategies have been investigated. The polymeric approach did not prove to be successful, merely because of the broad molecular weight distribution. The synthesis of heterofunctionally protected oligoethyleneglycols allowed to obtain ethyleneglycol moieties with 6 and 8 units, but the tedious purification steps gave very low yields. Finally, the block by block synthesis using ethyleneglycol precursors proved to be an efficient and fast method to synthesize the target molecules. Indeed, these were obtained with very high yields, and the separation was very efficient. A whole family of new compounds was obtained, having 6, 8 and 14 ethyleneglycol units and with mono- or diphytanyl lipid headgroups. This new pathway is a very promising synthetic strategy that can be used further in the development of new compounds of the tether system. The formation of bilayers was investigated for the different thiolipids mainly by using EIS. The electrical properties of a bilayer define the quality of the membrane and allow the study of the functionality of proteins embedded in such a system. Despite multiple trials to improve the system using self assembly, Langmuir Blodgett transfer, and detergent mixed vesicles, the new polymer thiolipids did not show as high electrical properties as tBLMs reported in the literature. Nevertheless, it was possible to show that a bilayer could be obtained for the different spacer lengths. These bilayers could be formed using self assembly for the first monolayer, and two different methods for bilayer formation, namely vesicle fusion and solvent exchange. We could furthermore show functional incorporation of the ion carrier valinomycin: the selective transport of K+ ions could be demonstrated. For DPHL, it was even possible to show the functional incorporation of the ion channel gramicidin. The influence of the spacer length is translated into an increase of the spacer capacitance, which could correspond to an increase in the capacity of charge accumulation in the submembrane space. The different systems need to be further optimised to improve the electrical properties of the bilayer. Moreover, the incorporation of larger proteins, and proteins bearing submembrane parts needs to be investigated.

Design and Fabrication of Bond Wire Micro-Magnetics

This thesis presents a new approach for the design and fabrication of bond wire magnetics for power converter applications by using standard IC gold bonding wires and micro-machined magnetic cores. It shows a systematic design and characterization study for bond wire transformers with toroidal and race-track cores for both PCB and silicon substrates. Measurement results show that the use of ferrite cores increases the secondary self-inductance up to 315 µH with a Q-factor up to 24.5 at 100 kHz. Measurement results on LTCC core report an enhancement of the secondary self-inductance up to 23 µH with a Q-factor up to 10.5 at 1.4 MHz. A resonant DC-DC converter is designed in 0.32 µm BCD6s technology at STMicroelectronics with a depletion nmosfet and a bond wire micro-transformer for EH applications. Measures report that the circuit begins to oscillate from a TEG voltage of 280 mV while starts to convert from an input down to 330 mV to a rectified output of 0.8 V at an input of 400 mV. Bond wire magnetics is a cost-effective approach that enables a flexible design of inductors and transformers with high inductance and high turns ratio. Additionally, it supports the development of magnetics on top of the IC active circuitry for package and wafer level integrations, thus enabling the design of high density power components. This makes possible the evolution of PwrSiP and PwrSoC with reliable highly efficient magnetics.

Tuning of magnetic exchange interactions between organic radicals through bond and space

The dissertation entitled "Tuning of magnetic exchange interactions between organic radicals through bond and space" comprises eight chapters. In the initial part of chapter 1, an overview of organic radicals and their applications were discussed and in the latter part motivation and objective of thesis was described. As the EPR spectroscopy is a necessary tool to study organic radicals, the basic principles of EPR spectroscopy were discussed in chapter 2. rnAntiferromagnetically coupled species can be considered as a source of interacting bosons. Consequently, such biradicals can serve as molecular models of a gas of magnetic excitations which can be used for quantum computing or quantum information processing. Notably, initial small triplet state population in weakly AF coupled biradicals can be switched into larger in the presence of applied magnetic field. Such biradical systems are promising molecular models for studying the phenomena of magnetic field-induced Bose-Einstein condensation in the solid state. To observe such phenomena it is very important to control the intra- as well as inter-molecular magnetic exchange interactions. Chapters 3 to 5 deals with the tuning of intra- and inter-molecular exchange interactions utilizing different approaches. Some of which include changing the length of π-spacer, introduction of functional groups, metal complex formation with diamagnetic metal ion, variation of radical moieties etc. During this study I came across two very interesting molecules 2,7-TMPNO and BPNO, which exist in semi-quinoid form and exhibits characteristic of the biradical and quinoid form simultaneously. The 2,7-TMPNO possesses the singlet-triplet energy gap of ΔEST = –1185 K. So it is nearly unrealistic to observe the magnetic field induced spin switching. So we studied the spin switching of this molecule by photo-excitation which was discussed in chapter 6. The structural similarity of BPNO with Tschitschibabin’s HC allowed us to dig the discrepancies related to ground state of Tschitschibabin’s hydrocarbon(Discussed in chapter 7). Finally, in chapter 8 the synthesis and characterization of a neutral paramagnetic HBC derivative (HBCNO) is discussed. The magneto liquid crystalline properties of HBCNO were studied by DSC and EPR spectroscopy.rn

Synthesis and dynamic study of atropisomeric compounds containing boron-carbon bond

In this thesis we studied the stereodynamic behavior of 1,2-azaborines variously substituted on boron (7a, 7b, 13). Depending on the hindrance of the asymmetric aryl substituent the resulting conformations could be stereolabile or configurationally stable. Through dynamic NMR and lineshape simulation, the energy rotational barriers of the different conformers are obtained. When the barrier is higher than 22-23 kcal/mol stable atropisomers that are fisically separable could be obtained (case of compound 13) and the free activation energy barrier is determinable by kinetic analysis. Absolute configuration of two atropisomers were assigned by comparison between computational calculations and experimental ECD. Isosteric compound 21 is then synthesized in order to compare the rotational barrier around B-Caryl with the one around Cnaphth-Caryl bond.