OBJECTIVES: To evaluate various cements in vitro for adhesion to zirconia, light curing vs. self-curing, the effect of particle abrasion (APA) on the zirconia intaglio for maximizing retention, the effect of thermocycling, and the effect of cement space. METHODS: The tested cements included: Ceramir C&B (Doxa) Panavia F2.0 (Kuraray); Multilink Automix (Ivoclar); Theracem (Bisco); Duolink (Bisco); Bifix (Shofu); CemEZ (Zest Dental). For testing cements retention, custom made zirconia rings 12.5 mm outer diameter, 5.5 mm height and 6.147 mm inner diameter were used to emulate crowns. Round steel rods (McMaster) were manufactured to fit into the zirconia rings allowing a cement space of 50 Microns or 100 Microns. A cementing jig was used to keep the rods at the center of the zirconia rings. Cements were tested using light curing and self-curing (n=10 per each test). Groups of zirconia rings were air braded with 100 Microns aluminum oxide particles for 10 Sec. Half the specimens were stored in water for 24 hours at 37o C in dark environment or thermocycled for 5000 cycles. A ‘push-out’ test using an Instron universal machine at a crosshead speed of 0.5mm/min. Loads to failure were recorded to calculate cements retention. RESULTS: Statistical analysis was performed using JMP Pro 13 software. Data were analyzed using one way ANOVA, multiple t-test, and Tukey-Kramer HSD. For self curing method without APA, retention strength ranking for tested cements were: Ceramir C&B ≥ Theracem > Panavia F2.0 ≥ Duolink ≥ Multilink Automix ≥ Bifix. For light curing method without APA, retention strength ranking for tested cements were: CemEZ ≥ Theracem ≥ Multilink Automix ≥ Duolink ≥ Bifix ≥ Panavia F2.0. There was a significant influence in retention strength for light cured cements compared to self-curing method except for Theracem and Panavia F2.0. For the self-curing method with APA, retention strength ranking for tested cements were: Theracem > Duolink ≥ Panavia F2.0 ≥ Multilink Automix ≥ Bifix > Ceramir C&B. For the light curing method with APA, retention strength ranking for tested cements were: Theracem ≥ Multilink Automix ≥ CemEZ ≥ Duolink ≥ Panavia F.0 ≥ Bifix. A significant increase in retention strength with APA compared to self-curing method with APA. There was no significant effect of thermocycling treatment on retention strength of the cements tested. There was no significant effect of different cement spaces on retention strength except for Ceramir C&B without APA and Multilink Automix with and without APA (P < 0.0001). CONCLUSIONS: 1- There was a significant difference in retention strength to zirconia among tested cements in self and light curing methods. 2- Light curing resin cements influenced retention strength to zirconia for the tested cements. 3- APA influenced the retention strength to zirconia for tested cements except for Ceramir C&B. 4- Increasing the cement space from 50μm to 100μm had no significant difference in retention strength to zirconia except for Ceramir C&B without APA and Multilink Automix with and without APA. 5- Thermocycling had no significant effect of on retention strength to zirconia for the tested cements. / 2020-07-30T00:00:00Z

Introduction: An optimal orthodontic bonding system must minimize damage to the enamel during conditioning, have enough bond strength to prevent bracket de-bonding during treatment, and allow bracket removal at treatment completion, such that minimal damage is inflicted to the tooth.1 Pumice followed by acid etching has been the standard for many years; however, Groman Inc. (Margate, FL, USA) has stated that using their air-abrasion product will result in a tripling of bond strength. This method claims a three-fold increase in bond strength compared to traditional acid etching techniques by substituting air-abrasion using the EtchMaster® (Groman Inc., Margate, FL) 50 μm aluminum oxide in place of pumice prophy prior to acid etching. The purpose of this study is to see if this combination does in fact triple shear bond strength, and if so, what impact it has on the residual enamel surface after bracket removal, or de-bonding. Methods: Ninety recently extracted bovine incisors were randomly divided into three groups. Each of the three groups underwent different conditioning methods prior to bracket bonding. Group A: pumice + acid etch (N=30), Group B: air-abrasion + acid etch (N=30), and Group C: air-abrasion only (N=30). Enamel surface conditions were characterized using a Quanta 200 Scanning Electron Microscope (SEM) (FEI, Hillsboro, OR) and a SZX7 Stereomicroscope System (Olympus, Center Valley, PA). American Orthodontics Master Series System twin MBT mandibular incisor brackets (Sheboygan, WI, USA) were then bonded to each tooth. Following bonding, teeth were stored for twenty-four hours in water at 37°C +/- 2°C. All groups then underwent thermocycling of five hundred cycles in water baths set at five and fifty-five degrees Celsius. Next, the samples were mounted in dental stone and brackets de-bonded using a universal testing machine (Instron, Canton, MA) to obtain shear bond strength (SBS) values. SEM and optical stereomicroscopy were again utilized to evaluate the enamel surface and determine the adhesive remnant index (ARI) was score of each specimen. Results: The mean of Group A (pumice + acid etch) was 21.52 MPa with a standard deviation of 4.97 MPa. The mean of Group B (air-abrasion + acid etch) was 21.83 MPa with a standard deviation of 7.55 Mpa. The mean of Group C (air-abrasion only) was 8.12 MPa with a standard deviation of 3.05 MPa. Analysis of variance showed a main effect of Group on MPa, F(2, 87) = 60.66, p < 0.001, ηp2= 0.58. Post-hoc analyses using Tukey’s HSD indicated that SBS values were higher for teeth in Group A than for those in Group C (p < 0.001), teeth in Group B had higher SBS values than those in Group C (p < 0.001), but no difference was found for SBS between teeth in Group A and Group B (p =0.981). Results from the Fisher’s Exact test, where we controlled the Type I error using a Bonferroni correction, reveals that ARI scores differed by group (p < 0.001). Stereomicroscope images at 38.75x magnification obtained following enamel conditioning show Groups A (P+AE) and B (AA+AE) are almost indistinguishable; however, Group C (AA) has visual differences. Group C had a speckled reflective property that appeared to be residual aluminum oxide particles. Following de-bond, stereomicroscopic and SEM images showed no enamel defects on the tooth. Conclusions: SBS was not significantly different between Group A (pumice + acid etch) and Group B (air-abrasion + acid etch). SBS was significantly different between Groups A and B, and Group C (air-abrasion only). This means there is not a three-fold increase in SBS when using air-abrasion and acid etch, when compared to pumice and acid etch, as claimed by the manufacturer of the air-abrasion unit used in this study. Additionally, the air-abrasion only group displayed a significantly lower SBS than Group A and B. Air-abrasion only is not a suitable enamel preparation method for orthodontic bonding. Images obtained from the stereomicroscope and SEM reveal no observational damage to the enamel surface topography after de-bonding for any group.

Introduction: The stabilization of dentinal collagen fibers against enzymatic degradation by the use of biocompatible cross-linker agents is of clinical importance for effective dentin bonding to surpass the test of time. Objective: The present study aims to evaluate and compare the effect of the application of two versions of a desensitizer solution to sound coronal dentin, on the microtensile bond strength (μTBS) of the resin-sound coronal dentin using 4th and 6th generation dentin bonding systems. Materials and Methods: Extracted human third molars were collected from an unidentified bank of teeth followed by IRB approval. A flat surface of all 12 teeth was prepared utilizing a water-cooled high-speed diamond disc, leaving an entire hard sound dentinal area for testing. Subsequently, according to the assigned group, specimens followed specific manufacturer’s instructions for application of dentin bonding systems: specimens were subdivided into 6 groups (n=20). Group 1 (G1) First positive control group. Specimens received an application of a 4th generation dentin bonding system (DBS). Group 2 (G2) Second positive control group. Specimens received an application of a 6th generation DBS. Group 3 (G3) Specimens were exposed to Gluma Desensitizer agent, blot-dried and followed by application of a 4th generation DBS. Group 4 (G4) Specimens were exposed to Gluma Desensitizer agent, blot-dried and followed by application of a 6th generation DBS. Group 5 (G5) Specimens were exposed to Gluma Desensitizer PowerGel agent, blot-dried and followed by application of a 4th generation DBS. Group 6 (G6) Specimens were be exposed to Gluma Desensitizer PowerGel agent, blot-dried and received an application of a 6th generation DBS. After application of the adhesive systems, all specimens were restored using a microhybrid resin composite. The root portion was sectioned 1mm below the CEJ, and discarded. All specimens were thermocycled at 5-55 Cº for 7000 cycles on distilled water. Then each restored tooth was sectioned perpendicular to the bonding interface into 1mm x 1mm x 8mm beams with a slow speed diamond wafering blade under thorough irrigation. Then specimens were subjected to μTBS testing at a crosshead speed of 1mm/min. Subsequently; specimens were subjected to fracture analysis and SEM evaluation of the different failure’s mode of the involved surfaces. Statistical analysis was performed by usingone- way ANOVA, two-way ANOVA and Fisher’s PLSD test (p<0.05). Results: For the first aim of the study and after obtaining the μTBS in MPa: Group G1: 15.50 ± 6.28, Group G2: 13.06 ± 11.53, Group G3: 19.20 ± 9.43, Group G4: 12.76 ± 4.61, Group G5: 14.38 ± 5.95, Group G6: 18.54 ± 9.49. Statistical analysis showed that there is no significant influence of variables on the μTBS (Welch ANOVA [F (5,114) =2.21, p=0.057]). Treatment with Gluma desensitizing agent and Gluma desensitizing PowerGel has no significant influence on the bond strength. For the second aim of the study and to analyze group differences for type of fracture data was first recoded into two groups: (1) Adhesive failure and (2) Cohesive failure. Group differences were analyzed by type of fracture using a Fisher’s exact test. No difference was found between the groups by type offracture (5, N = 120) = 8.62, p = 0.090 Conclusion: Within the limitations of this in vitro study it can be concluded that Gluma desensitizing agent and Gluma desensitizing PowerGel did not significantly affect the μTBS of both 4th and 6th generation bonding system using extracted human teeth.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19300号 / 工博第4097号 / 新制||工||1631(附属図書館) / 32302 / 京都大学大学院工学研究科建築学専攻 / (主査)教授 金子 佳生, 教授 田中 仁史, 教授 竹脇 出 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Background: The impact of climate change on people's health and lives is a growing concern, with viruses, malnutrition, and heat stress potentially causing up to 250,000 deaths per year between 2030-2050. To address this issue, organizations and institutions are taking action to create a more sustainable world. One major step was signing the Paris Agreement in 2015, and financial investors have also taken on greater responsibility for the environmental transition. In response, green bonds have become increasingly popular. The key difference between a green and conventional bond is that the green bond is issued with the specific purpose of financing green projects. However, investors are still unsure about the financial performance of green bonds compared to conventional bonds, as the costs of issuing them may impact profitability and economic benefits. Purpose: This report examines how the premium on green corporate bonds, i.e., greenium, evolves over time. The main objective is to assess the performance of green bonds compared to conventional bonds in terms of yield to maturity and the impact of a bond’s green label. To gain a thorough understanding of the development of greenium over time, it is important to examine the factors that influence the yield differences between green and conventional bonds. This analysis of the existence and evolution of greenium and its driving forces can offer valuable insights to investors interested in sustainable finance and green instruments. Method: This study analyzed 267 green corporate bonds and 3,997 conventional corporate bonds issued globally between 2015-2022. The greenium was calculated by comparing green and conventional bonds' average yield to maturity. Additionally, three OLS regressions were conducted to assess the impact of a bond's green label and factors driving the yield to maturity of both green and conventional bonds, respectively. The regressions included control variables such as green label, issuer rating, time to maturity, seniority, and local currency. Conclusion: After analyzing the results, we found that conventional bonds performed better in yields than green bonds over the entire sample. However, in specific individual years, the green bonds outperformed the conventional bonds, indicating that the greenium is not negative each year separately. Regardless, conventional bonds generate higher yields over the whole sample period, implying that greenium exists. The green label does not significantly influence the variance of bond returns in all time periods, suggesting that investors' preference for environmentally friendly bonds is inconsistent across the entire sample. Additionally, the determining factors for conventional bonds are more predictable than for green bonds, and the future events of green bonds can be challenging to forecast due to the larger variation in the effects on yield to maturity.

The first section of this dissertation (Chapter I-III) describes the development of new methodologies for the rhodium catalyzed C-N bond formation between sp3 hybridized carbon atom of phenyl substituted alpha-lactams and the nitrogen atom of indole derivatives. Phenyl substituted alpha-lactams generated in situ from the corresponding alpha-bromoamides reacted with indoles in the presence of rhodium catalyst to afford the ring opening products of alpha-lactams. The scope of this methodology was extended to various types of indole derivatives including electron donating and withdrawing substituents. Furthermore, a series of functionalized phenyl substituted alpha-lactams generated in situ reacted with indole to assess the viability of this methodology. The developed method provides an atom-economical approach for the formation of substituted alpha-amino amides in good to excellent yields. The main goal of the research described in the second section (Chapter IV-VII) is the synthesis of the corannulene-based molecular receptors with polar tethers and their immobilization on silica gel. First, we have considered a preparation of bis-corannulenoanthracene, formally possessing the pentacene core as a potential precursor for a series of barrelene based bis-corannulene receptors with polar groups. Bis-corannulenoanthracene was synthesized by the double Diels-Alder cycloaddition of isocorannulenofuran with bis-benzyne precursor, followed by deoxygenation of the endoxide adducts. While bis-corannulenoanthracene is stable enough to be isolated and stored, its pentacene core undergoes facile cycloaddition with maleic anhydride to afford bis-corannulene molecular receptor with the barrelene tether adorned with the anhydride moiety. The 1H NMR titration experiments carried out in chlorobenzene-d5 proved the high binding affinity of the receptor toward C60. In addition, the presence of polar anchors on its tether allowed for its deposition on silica gel through the (3-aminopropyl)triethoxysilane linker.

Urea formaldehyde (UF) resins are widely used as adhesives for wood-based composites. These thermosetting polymers have advantages of relative low price, fast curing speed, and relative good bonding performance. However, UF resin bonded composites are designed for interior applications due to its weak water resistance. Moreover, traditional prevalent ways for recycling wood-based composites face problems caused by UF resins. In this project, the reuse of cured UF resins was systematically studied. The verification and characterization of crystalline structures in cured UF resins were conducted. The results showed that the crystalline regions were accounted for nearly 14.48% in a typical 1.2 formaldehyde to urea (F/U) molar ratio UF resin. The details of the resin crystalline regions, such as grain sizes and interplanar spacing (d-spacing), were characterized. The crystalline structures, nevertheless, did not affect the UF resin hydrothermal hydrolysis in this study. The reuse of cured UF resin was started with a hydrothermal hydrolysis. Under 140 °C and 2 h of hydrothermal process, 20 mL of 30 w.t. % formaldehyde water solution was able to depolymerize up to 1.7 g of cured UF resin. The hydrolyzed formaldehyde solutions were directly used as normal formaldehyde solutions for UF resin synthesis. The synthesized resin (named as UUF resin) contained about 6 w.t. % of cured UF resin and presented similar chemical structures and bonding performance as normal UF resins. Hybrid resins made of UUF resin and polymeric 4-4 diphenyl methane diisocyanate (pMDI) were prepared. The pMDI was found evenly dispersed in the hybrid resins by using acetone as its solvent. These hybrid resins resulted in faster curing and stronger bonding performance than pure UUF resins. Furthermore, the hybrid resin was used in a new bonding design, which used southern pine wood radial section features. This design generated finger joint like bonding interfaces by hot pressing two resin coated wood radial sections. The bonding strength and bond line stability were enhanced by this design.

The present thesis comprises synthesis and stoichiometric model reactions of well-defined NHC-stabilized copper(I) complexes (NHC = N-heterocyclic carbene) in order to understand their basic reactivity in borylation and cross-coupling reactions. This also includes the investigations of the reactivity of the ligands used (NHCs and CaaCs = cyclic alkyl(amino)carbenes) with the substrates, i.e. diboron(4) esters and arylboronates, which are addressed in the second part of the thesis. / Die dargelegte Arbeit gliedert sich in zwei Teile. In einem ersten wird die Synthese sowie stöchiometrische Modell-Reaktionen von definierten NHC-stabilisierten Kupfer(I)-Komplexen (NHC = N-heterocyclisches Carben) untersucht, um Einblick in das grundlegende Reaktionsverhalten in Borylierungs- und Kreuzkupplungsreaktionen zu erlangen. Der zweite Teil adressiert die Reaktivität der eingesetzten Liganden (NHCs und CaaCs = cyclische Alkyl Amino Carbene) gegenüber verwendeten sowie möglichen Substraten (Arylboronsäureester und Diboran(4)-Verbindungen).