An Unexpected Dual-Emissive Luminogen: Tunable Aggregation-Induced Emission with Cyan-White-Red Colors, Stable Inherent Chirality, and Enhanced Chiroptical Property

Herein we report a novel chiral bismacrocycle with unexpected dual emission and tunable aggregation-induced emission colors. A facile four-step synthesis strategy is developed to construct this rigid bismacrocycle, (1,4)[8]cycloparaphenylenophane (SCPP[8]), which possesses a 1,2,4,5-tetraphenylbenzene core locked by two intersecting polyphenylene-based macrocycles. The luminescent behavior of SCPP[8] shows the unique characteristics of both aggregation-caused quenching effect and aggrega-tion-induced emission (AIE) effect, inducing remarkable redshift emission including near white-light emission. SCPP[8] is configurationally stable and possesses a novel shape-persistent bismacrocycle scaffold with a high strain energy (up to 127.83 kcal/mol). In addition, SCPP[8] displays enhanced circularly polarized luminescence properties due to AIE effect.

Specialization of tendon mechanical properties results from interfascicular differences

Tendons transfer force from muscle to bone. Specific tendons, including the equine superficial digital flexor tendon (SDFT), also store and return energy. For efficient function, energy-storing tendons need to be more extensible than positional tendons such as the common digital extensor tendon (CDET), and when tested in vitro have a lower modulus and failure stress, but a higher failure strain. It is not known how differences in matrix organization contribute to distinct mechanical properties in functionally different tendons. We investigated the properties of whole tendons, tendon fascicles and the fascicular interface in the high-strain energy-storing SDFT and low-strain positional CDET. Fascicles failed at lower stresses and strains than tendons. The SDFT was more extensible than the CDET, but SDFT fascicles failed at lower strains than CDET fascicles, resulting in large differences between tendon and fascicle failure strain in the SDFT. At physiological loads, the stiffness at the fascicular interface was lower in the SDFT samples, enabling a greater fascicle sliding that could account for differences in tendon and fascicle failure strain. Sliding between fascicles prior to fascicle extension in the SDFT may allow the large extensions required in energy-storing tendons while protecting fascicles from damage.

Design of O-Rings as an Example of Passive Adaptive Structures

The use of material design to overcome time-dependent material deformation resulting in loss of sealing effectiveness of elastomeric seals was considered. O-ring sections with different stress-strain behavior in different regions of the section were studied. Experimentally validated finite element models were used to characterize the strain energy density distribution and seal-housing contact pressure for various section designs. The design rules extracted from experimental and numerical studies indicate that o-ring sections with lower elastic modulus, softening material located at regions of high strain energy will result in slower growth of permanent seal deformation and so improved seal performance over time. O-ring sections based on this material design were evaluated numerically and improved seal life predicted.

Localized Damage in Vertebral Bone Is Most Detrimental in Regions of High Strain Energy Density

It was hypothesized that damage to bone tissue would be most detrimental to the structural integrity of the vertebral body if it occurred in regions with high strain energy density, and not necessarily in regions of high or low trabecular bone apparent density, or in a particular anatomic location. The reduction in stiffness due to localized damage was computed in 16 finite element models of 10-mm-thick human vertebral sections. Statistical analyses were performed to determine which characteristic at the damage location — strain energy density, apparent density, or anatomic location — best predicted the corresponding stiffness reduction. There was a strong positive correlation between regional strain energy density and structural stiffness reduction in all 16 vertebral sections for damage in the trabecular centrum (p < 0.05, r2 = 0.43–0.93). By contrast, regional apparent density showed a significant negative correlation to stiffness reduction in only four of the sixteen bones (p < 0.05, r2 = 0.47 – 0.58). While damage in different anatomic locations did lead to different reductions in stiffness (p < 0.0001, ANOVA), no single location was consistently the most critical location for damage. Thus, knowledge of the characteristics of bone that determine strain energy density distributions can provide an understanding of how damage reduces whole bone mechanical properties. A patient-specific finite element model displaying a map of strain energy density can help optimize surgical planning and reinforcement of bone in individuals with high fracture risk.

Structural Health Monitoring Using Modal Strain Energy

This research combines analytical and experimental modal analysis techniques to verify the structural integrity or monitor the “health” of a dynamic structure. Central to the procedure is the development of a baseline dynamic fingerprint model of the structure. The dynamic fingerprint is verified with experimental modal analysis and correlation. After the structure is placed into service, damage can be determined by comparing the current dynamic response with the baseline dynamic fingerprint response. The unique aspect of this procedure is that the current dynamic response is enforced on the undamaged baseline dynamic fingerprint model. Should damage exist, the structure is forced to deform in an unnatural manner, and high strain energy results. Significant differences in the normalized modal or operating strain energy density identify structural regions where a loss of stiffness, weakening of the structure, and/or damage has occurred. This identification of a potentially “unhealthy” structural region allows a quick visual inspection of the region or further analytical and/or experimental submodelling of the area to precisely identify the damage. The method is ideally suited to CAE application. The method is demonstrated analytically and experimentally for two structures: an eight-bay cantilevered truss structure and a rectangular plate with various boundary conditions.

Spiro fused β-lactam cyclopropenes

Δ3-1,3,4-Oxadiazolines (1) that share their C2 with C4 of a β-lactam ring in a spiro fusion were prepared. The structures were established through single crystal X-ray diffraction of 1a and by infrared, 1H, and 13C nuclear magnetic resonance spectroscopies. Thermolysis of 1 at 100 °C, in benzene containing dimethyl acetylenedicarboxylate, afforded spiro-fused β-lactam cyclopropene 12 in 33% yield. Similar thermolysis of 1b in the presence of ethyl phenylpropiolate gave spiro-fused β-lactam cyclopropene 13 (32%). The molecular structure of 12, determined by single crystal X-ray diffraction, has the two ester carbonyl carbons out of the plane of the cyclopropene ring by about 0.17 Ǻ, indicating substantial nonbonded steric interactions and suggesting unusually high strain energy. At 154.5 °C, 12 underwent isomerization to 19, presumably through a vinyl carbene intermediate.