Spirocyclic systems derived from pyroglutamic acid.

The synthesis and likely conformational structure of rigid spirocyclic bislactams and lactam-lactones derived from pyroglutamic acid, and their suitability as lead structures for applications in drug development programmes using cheminformatic analysis, has been investgated.

Microstructural evolution and physical behavior of a lithium disilicate glass-ceramic.

BACKGROUND: Elucidating the microstructural responses of the lithium disilicate system like the popular IPS e.max® CAD (LS2), made specifically for computer-aided design and computer-aided manufacturing (CAD-CAM), as a temperature-dependent system unravels new ways to enhance material properties and performance. OBJECTIVE: To study the effect of various thermal processing on the crystallization kinetics, crystallite microstructure, and strength of LS2. METHODS: The control group of the LS2 samples was heated using the standard manufacturer heating-schedule. Two experimental groups were tested: (1) an extended temperature range (750-840°C vs. 820-840°C) at the segment of 30°C/min heating rate, and (2) a protracted holding time (14min vs. 7min) at the isothermal temperature of 840°C. Five other groups of different heating schedules with lower-targeted temperatures were evaluated to investigate the microstructural changes. For each group, the crystalline phases and morphologies were measured by X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. Differential scanning calorimeter (DSC) was used to determine the activation energy of LS2 under non-isothermal conditions. A universal testing machine was used to measure 3-point flexural strength and fracture toughness, and elastic modulus and hardness were measured by a nanoindenter. A one-way ANOVA/Tukey was performed per property (alpha=0.05). RESULTS: DSC, XRD, and SEM revealed three distinct microstructures during LS2 crystallization. Significant differences were found between the control group, the two aforementioned experimental groups, and the five lower-targeted-temperature groups per property (p<0.05). The activation energy for lithium disilicate growth was 667 (±29.0)kJ/mol. CONCLUSIONS: Groups with the extended temperature range (750-840°C) and protracted holding time (820-840°C H14) produced significantly higher elastic-modulus and hardness properties than the control group but showed similar flexural-strength and fracture-toughness properties with the control group. In general, rapid growth of lithium disilicates occurred only when maximum formation of lithium metasilicates had ended.

Contributions of stress corrosion and cyclic fatigue to subcritical crack growth in a dental glass-ceramic.

OBJECTIVE: The objective of this study was to test the following hypotheses: (1) both cyclic degradation and stress-corrosion mechanisms result in subcritical crack growth (SCG) in a fluorapatite glass-ceramic (IPS e.max ZirPress, Ivoclar-Vivadent) and (2) there is an interactive effect of stress corrosion and cyclic fatigue to accelerate subcritical crack growth. METHODS: Rectangular beam specimens were fabricated using the lost-wax process. Two groups of specimens (N=30/group) with polished (15µm) or air-abraded surface were tested under rapid monotonic loading. Additional polished specimens were subjected to cyclic loading at two frequencies, 2Hz (N=44) and 10Hz (N=36), and at various stress amplitudes. All tests were performed using a fully articulated four-point flexure fixture in deionized water at 37°C. The SCG parameters were determined using the ratio of inert strength Weibull modulus to lifetime Weibull modulus. A general log-linear model was fit to the fatigue lifetime data including time to failure, frequency, peak stress, and the product of frequency and logarithm of stress in ALTA PRO software. RESULTS: SCG parameters determined were n=21.7 and A=4.99×10(-5) for 2Hz, and n=19.1 and A=7.39×10(-6) for 10Hz. After fitting the general log-linear model to cyclic fatigue data, the coefficients of the frequency term (α1), the stress term (α2), and the interaction term (α3) had estimates and 95% confidence intervals of α1=-3.16 (-15.1, 6.30), α2=-21.2 (-34.9, -9.73), and α3=0.820 (-1.59, 4.02). Only α2 was significantly different from zero. SIGNIFICANCE: (1) Cyclic fatigue does not have a significant effect on SCG in the fluorapatite glass-ceramic evaluated and (2) there was no interactive effect between cyclic degradation and stress corrosion for this material.

Fatigue loading and R-curve behavior of a dental glass-ceramic with multiple flaw distributions.

OBJECTIVES: To determine the effects of surface finish and mechanical loading on the rising toughness curve (R-curve) behavior of a fluorapatite glass-ceramic (IPS e.max ZirPress) and to determine a statistical model for fitting fatigue lifetime data with multiple flaw distributions. MATERIALS AND METHODS: Rectangular beam specimens were fabricated by pressing. Two groups of specimens (n=30) with polished (15 µm) or air abraded surface were tested under rapid monotonic loading in oil. Additional polished specimens were subjected to cyclic loading at 2 Hz (n=44) and 10 Hz (n=36). All fatigue tests were performed using a fully articulated four-point flexure fixture in 37°C water. Fractography was used to determine the critical flaw size and estimate fracture toughness. To prove the presence of R-curve behavior, non-linear regression was used. Forward stepwise regression was performed to determine the effects on fracture toughness of different variables, such as initial flaw type, critical flaw size, critical flaw eccentricity, cycling frequency, peak load, and number of cycles. Fatigue lifetime data were fit to an exclusive flaw model. RESULTS: There was an increase in fracture toughness values with increasing critical flaw size for both loading methods (rapid monotonic loading and fatigue). The values for the fracture toughness ranged from 0.75 to 1.1 MPam(1/2) reaching a plateau at different critical flaw sizes based on loading method. SIGNIFICANCE: Cyclic loading had a significant effect on the R-curve behavior. The fatigue lifetime distribution was dependent on the flaw distribution, and it fit well to an exclusive flaw model.

Bridged triarylamines: a new class of heterohelicenes.

A series of bridged triarylamines, which constitute a new class of heterohelicenes, have been synthesized using a simple three-step procedure. These compounds are shown to be highly luminescent chromophores and are capable of being oxidized. The solid-state structures of these helicenes show a tendency for pi-stacking interactions into an overall zigzag motif.