Synthesis and Characterization,Including Cancer Cell Line Inhibition,of Group VA (Group 15)-Containing Polyesters from Reaction with Camphoric Acid

Polyesters were rapidly synthesized employing interfacial polymerization from reaction of the salt of camphoric acid with Group VA (Group 15) triphenylmetallic dihalides. Yields range from 25 to 46 percent with chain lengths about 250. Infrared spectroscopy shows the formation of two new bands one assigned to the symmetrical M–O stretching and the second assigned to the asymmetrical M–O stretching. The bridging structure about the metal atom increases as the metal atom size increases. MALDI MS and proton NMR are consistent with the formation of the polyester structure. Ion fragment clusters to four to six units are identified. The polymers show good inhibition of a group of cancer cell lines including two pancreatic human cancer cell lines. In comparison with other metal/camphoric acid polymers, the metallocene polymers exhibit low EC₅₀ to the nanogram/ml range, and CI₅₀ values greater than one thousand for the hafnocene and zirconocene products. If this trend continues, the emphasis should be on the Group IVB metallocenes with respect to efforts to create anticancer drugs.     

Carnivore Attractant or Plant Elicitor? Multifunctional Roles of Methyl Salicylate Lures in Tomato Defense

Synthetic plant volatile lures attract natural enemies, but may have non-target effects due to the multifunctional nature of volatile signals. For example, methyl salicylate (MeSA) is used to attract predators, yet also serves as a signaling hormone involved in plant pathogen defense. We investigated the consequences of deploying MeSA lures to attract predators for tomato (Solanum lycopersicum) defense against herbivores. To understand the spatial distribution of the lure’s effect, we exposed tomatoes in the field to MeSA along a linear distance gradient and induced defenses by simulating feeding by hornworm caterpillars in a fully crossed factorial design (+/? MeSA, +/? herbivory). Subsequently, we analyzed activity of several defensive proteins (protease inhibitors, polyphenol oxidase, peroxidase), development of hornworm larvae (Manduca sexta), growth of fungal pathogens (Cladosporium and Alternaria), and attractiveness to herbivores and predators. Overall, MeSA-exposed plants were more resistant to both insects and pathogens. Secondary pathogen infection was reduced by 25% in MeSA exposed plants, possibly due to elevated polyphenol oxidase activity. Interestingly, we found that lures affected plant pathogen defenses equivalently across all distances (up to 4 m away) indicating that horizontal diffusion of a synthetic volatile may be greater than previously assumed. While thrips avoided colonizing hornworm– damaged tomato plants, this induced resistance was not observed upon pre-exposure to MeSA, suggesting that MeSA suppresses the repellant effect induced by herbivory. Thus, using MeSA lures in biological control may inadvertently protect crops from pathogens, but has mixed effects on plant resistance to insect herbivores.     

Cold sintering process: A new era for ceramic packaging and microwave device development

Cold sintering process (CSP) is an extremely low‐temperature sintering process (room temperature to ~200°C) that uses aqueous‐based solutions as transient solvents to aid densification by a nonequilibrium dissolution‐precipitation process. In this work, CSP is introduced to fabricate microwave and packaging dielectric substrates, including ceramics (bulk monolithic substrates and multilayers) and ceramic‐polymer composites. Some dielectric materials, namely Li₂MoO₄, Na₂Mo₂O₇, K₂Mo₂O₇, and (LiBi)_0.5MoO₄ ceramics, and also (1?x)Li₂MoO₄?xPTFE and (1?x)(LiBi)_0.5MoO₄?xPTFE composites, are selected to demonstrate the feasibility of CSP in microwave and packaging substrate applications. Selected dielectric ceramics and composites with high densities (88%‐95%) and good microwave dielectric properties (permittivity, 5.6‐37.1; Q × f, 1700‐30 500 GHz) were obtained by CSP at 120°C. CSP can be also used to potentially develop a new co‐fired ceramic technology, namely CSCC. Li₂MoO₄?Ag multilayer co‐fired ceramic structures were successfully fabricated without obvious delamination, warping, or interdiffusion. Numerous materials with different dielectric properties can be densified by CSP, indicating that CSP provides a simple, effective, and energy‐saving strategy for the ceramic packaging and microwave device development.     

Intermediate temperature oxidative strength degradation of a SiC/SiNC composite with a polymer‐derived matrix

The article describes an experimental investigation of oxidative degradation in mechanical performance of a SiC fiber‐reinforced composite with a SiCN matrix produced by polymer infiltration and pyrolysis. Tensile stress rupture and retained strength tests were performed at 800°C in dry air and in water vapor. Fracture surfaces were examined to determine the degree of fiber pull‐out and constituent oxidation and to measure radii of representative fiber fracture mirrors. The results indicate that degradation in tows adjacent to cut surfaces occurs equally rapidly in water vapor with or without application of stress; regions in the composite interior and near as‐processed (uncut) surfaces appear far less affected. Similar effects are evident but less pronounced in dry air. Although oxidation of fiber coatings is observed in some cases, collectively the results suggest that fiber degradation is the main mechanism leading to reduced composite strength.     

Thermal annealing effects on the energy storage properties of BST ceramics

Thermal annealing treatments with different atmospheres (air, oxygen, and reducing atmospheres, respectively) were employed for the conventionally sintered (Ba_0.4Sr_0.6)TiO₃ (BST) ceramics. The effect of thermal annealing on the energy storage properties of BST ceramics was investigated, where oxygen vacancies played an important role. The dielectric loss, bulk resistivity and dielectric breakdown strength (BDS) were found to be sensitive to the annealing process, leading to the different energy densities in the range of 0.30‐0.80 J/cm³. Temperature‐dependent dielectric measurement and thermally stimulated depolarization current analysis were conducted to understand the impacts of oxygen vacancies on the macroscopic properties, which were found to be closely associated with the annealing conditions.     

Gold nanoparticle colorants as traditional ceramic glaze alternatives

Historically, Roman stained glass has been a standard for high‐temperature color stability since biblical times but was not properly characterized as emission from nanoparticle plasmon resonance until the 1990s. The methods under which it was created have been lost, but some efforts have recently been made to recreate these properties using gold nanoparticle inks on glassy surfaces. This body of work employs gold nanoparticle systems ranging from 0.015% to 0.100% (wt/wt), suspended in a clear glaze body. The glazes are fired with traditional ceramic methods—in both gas reduction and electric oxidation kilns—in which nanoparticles are retained and can be imaged via TEM. Various colors intensities are reported in addition to changes in nanoparticle size after application and firing. The nanoparticle glazes are compared to traditional red glazes, highlighting the significantly lower metal loading required (5%‐10% for traditional glazes vs 0.100% for gold (wt/wt)), therein. Finally, proof of concept is provided with a functional gold nanoparticle mug, fired in reduction, that costs roughly 0.98$ USD in gold used.     

Thermal behavior of mullite between 4 K and 1320 K

The evolution of metric parameters of 2:1 and 3:2 mullites have been measured between 4 K and 1320 K using neutron and X‐ray powder diffraction. Negative thermal expansion was observed at low temperature for the a‐cell parameter and consequently for the cell‐volume, which is more pronounced for 2:1 mullite than those for 3:2 mullite. Each parameter is simulated using Grüneisen first‐order approximation for the zero pressure equation of state at 0 K, where the vibrational energy was calculated using microscopic approach. While the b‐ and c‐cell parameters require only one Debye term, a second Debye spectrum with negative Grüneisen parameter was required to fit the a‐cell parameter as well as the cell volume. At 4 K, 300 K and 1320 K the model, respectively, calculates the volume thermal expansion coefficients of 0.09x10^?6 K^?1, 9x10^?6 K^?1, and 17.3x10^?6 K^?1 for 2:1 mullite, and 0.09x10^?6 K^?1, 8.7x10^?6 K^?1, and 17.3x10^?6 K^?1 for 3:2 mullite. Temperature‐dependent Raman spectra and phonon density of states hint for the possible microscopic sources of the cell contraction at low temperature. A simple polynomial approach is presented to calculate the elastic stiffness coefficients of the 3:2 mullite, which are not available from experiments.     

The {110} reflection in X‐ray diffraction of MXene films: Misinterpretation and measurement via non‐standard orientation

It has been claimed that disappearance of the {110} reflection in powder X‐ray diffraction of MXene films and powders is indicative of shearing or general disorder of restacking of the flakes. Here we show this to be incorrect and provide experimental justification. The disappearance of this peak arises from a combination of sample texture and orientation. Furthermore, our methods provide a simple way to estimate a unit cell parameters when the relevant reflections are not present in most reports of MXene films.     

Laser shock processing of polycrystalline alumina ceramics

Laser shock processing (LSP) has been applied to polycrystalline α‐Al₂O₃ ceramics. X‐ray characterizations have revealed that LSP results in significant compressive residual stresses which can extend to a depth of more than 1.2 mm from the surface. The presence of compressive residual stresses improves the resistance of α‐Al₂O₃ ceramics to indentation cracking. Microstructural characterization suggests that the majority of α‐Al₂O₃ grains on the surface remains intact after LSP. However, damaged regions are occasionally present, which shows intergranular fractures and a limited plastic deformation in the vicinity of grain boundaries.     

Characterization of C–S–H and C–A–S–H phases by electron microscopy imaging,diffraction, and energy dispersive X‐ray spectroscopy

Improving concrete sustainability by increasing durability requires a detailed knowledge about microstructural properties. Due to the nanoscale nature of hydrate phases that determine concrete properties, microstructural characterization remains a challenge. Analytical electron microscopy offers promising techniques to characterize cement hydrates. In this study, electron microscopy imaging, diffraction, and energy dispersive X‐ray spectroscopic information are combined in order to compare the structural properties of calcium silicate hydrate (C–S–H) and calcium aluminum silicate hydrate (C–A–S–H) phases. Results are shown for 28 days hydrated C–(A)–S–H of portland cement and cement containing ground granulated blast‐furnace slag (GGFBS). Electron diffraction patterns of single fibrous C–S–H and foil‐like C–A–S–H phases reveal a nanocrystalline structure. Also, it is shown by electron diffraction pattern that the crystal structures of C–S–H and C–A–S–H phases are similar. It is confirmed that the crystal structure of 14 Å tobermorite serves as good base for the structure of C–S–H. The electron diffraction patterns of fibrous C–S–H show streaks which indicate stacking faults, proofing that polymerization of silicate chains in C–S–H is limited. Here, we demonstrate for the first time that the dreierketten silicate chains contained in the C–S–H structure are oriented in parallel to the long axis of C–S–H fibers. This finding should be implemented in modeling of crystal growth of C–S–H.