TiO2 as a gas sensor: The novel carbon structures and noble metals as new elements for enhancing sensitivity – A review

The development of highly selective, stable, and sensitive materials for the various gas emissions is a challenging task concerning the numerous applications: environmental control, security systems, energy, and, more recently, biological monitoring. One of the major challenges to reach this activity's requirements is developing nanostructured functional and smart materials that can selectively detect and monitor the gases at high temperatures. The semiconductor materials based on metallic oxides have gained increasing attention within this scenario, especially titanium dioxide (TiO₂), due to their excellent properties. The literature presents multiple sensors based on TiO₂ nanoparticles to detect various gases: CO, ethanol, benzene, toluene, NO₂, O₂, CO, SO₂, NO_x, NH₃, Cl₂, H₂S, alkanes, among others. This review initially explores some aspects of TiO₂ and its properties regarding the sensor sensitivity's influence. Then, the insertion of noble metals (Ag, Pt, Au, and Ru) and carbon structures (graphene, carbon nanotube, and other carbon forms) was also explored in the search to improve the TiO₂ capacity as a gas sensor. This review focuses on the most significant achievements related to TiO₂ and TiO₂ combined with carbon structures or noble metals for gas sensor applications. Several studies were presented, highlighting the synthesis methods employed, the sensor response/recovery times, and some detection mechanisms after the carbon and noble metal insertion. Finally, the influence of a triple combination between TiO₂-carbon-metal was also explored.     

Western Pine Beetle Populations in Arizona and California Differ in the Composition of Their Aggregation Pheromones

We compared pheromone production and response for populations of western pine beetle, Dendroctonus brevicomis LeConte, from sites in northern Arizona and northern California. Volatiles were collected from individuals of both sexes that had mined as a pair in a Pinus ponderosa log for 1 d, and they were subsequently analyzed by gas chromatography coupled to mass-spectrometry. Principal component analysis of quantities of Dendroctonus pheromone components indicated strong site-associated clustering of blend composition for females but not males. Much of the clustering in females evidently was due to differences in the production of endo- and exo-brevicomin, which occurred in average ratios of 0.1:1 and 19:1 for populations in the California and Arizona sites, respectively. In the California site, exo- was better than endo-brevicomin in enhancing trap catches of both sexes to lures containing the host-tree odor α-pinene and the male-produced aggregation pheromone component frontalin. In an identical test in the Arizona site, endo- was a better adjuvant than exo-brevicomin for male attraction, whereas females did not show a significant preference. At neither location were the isomers antagonistic to one another in activity. Thus, one aggregation pheromone has apparently diverged between these populations, concurrent with published evidence that D. brevicomis on either side of the Great Basin are genetically distinct and are possibly different species. Furthermore, production of and response to the isomers of brevicomin by flying Dendroctonus frontalis Zimmermann in the Arizona site were similar to those of sympatric D. brevicomis. This interspecific signal overlap is likely sustainable since joint species mass-attacks may assist both species in overcoming host defenses, thereby increasing host availability.     

Cold Sintering Process: A Novel Technique for Low‐Temperature Ceramic Processing of Ferroelectrics

Research on sintering of dense ceramic materials has been very active in the past decades and still keeps gaining in popularity. Although a number of new techniques have been developed, the sintering process is still performed at high temperatures. Very recently we established a novel protocol, the “Cold Sintering Process (CSP)”, to achieve dense ceramic solids at extraordinarily low temperatures of <300°C. A wide variety of chemistries and composites were successfully densified using this technique. In this article, a comprehensive CSP tutorial will be delivered by employing three classic ferroelectric materials (KH₂PO₄, NaNO₂, and BaTiO₃) as examples. Together with detailed experimental demonstrations, fundamental mechanisms, as well as the underlying physics from a thermodynamics perspective, are collaboratively outlined. Such an impactful technique opens up a new way for cost‐effective and energy‐saving ceramic processing. We hope that this article will provide a promising route to guide future studies on ultralow temperature ceramic sintering or ceramic materials related integration.     

2ZrO2·Y2O3 Thermal Barrier Coatings Resistant to Degradation by Molten CMAS: Part I,Optical Basicity Considerations and Processing

The higher operating temperatures in gas‐turbine engines enabled by thermal barrier coatings (TBCs) engender new materials issues, viz silicate particles (sand, volcanic ash, fly ash) ingested by the engine melt on the hot TBC surfaces and form calcium–magnesium–alumino–silicate (CMAS) glass deposits. The molten CMAS glass degrades TBCs, leading to their premature failure. In this context, we have used the concept of optical basicity (OB) to provide a quantitative chemical basis for the screening of CMAS‐resistant TBC compositions, which could also be extended to environmental barrier coatings (EBCs). By applying OB difference considerations to various major TBC compositions and two types of important CMASs—desert sand and fly ash—the 2ZrO₂·Y₂O₃ solid solution (ss) TBC composition, with the potential for high CMAS‐resistance, is chosen for this study. Here, we also demonstrate the feasibility of processing of 2ZrO₂·Y₂O₃(ss) air‐plasma sprayed (APS) TBC using commercially developed powders. The resulting TBCs with typical APS microstructures are found to be single‐phase cubic fluorite, having a thermal conductivity <0.9 W·(m·K)^?1 at elevated temperatures. The accompanying Part II paper presents results from experiments and analyses of high‐temperature interactions between 2ZrO₂·Y₂O₃(ss) APS TBC and the two types of CMASs.     

Modulation of Amyloid‐β Aggregation by Histidine‐Coordinating Cobalt(III) Schiff Base Complexes

Oligomers of the Aβ42 peptide are significant neurotoxins linked to Alzheimer's disease (AD). Histidine (His) residues present at the N terminus of Aβ42 are believed to influence toxicity by either serving as metal–ion binding sites (which promote oligomerization and oxidative damage) or facilitating synaptic binding. Transition metal complexes that bind to these residues and modulate Aβ toxicity have emerged as therapeutic candidates. Cobalt(III) Schiff base complexes (Co–sb) were evaluated for their ability to interact with Aβ peptides. HPLC‐MS, NMR, fluorescence, and DFT studies demonstrated that Co–sb complexes could interact with the His residues in a truncated Aβ16 peptide representing the Aβ42 N terminus. Coordination of Co–sb complexes altered the structure of Aβ42 peptides and promoted the formation of large soluble oligomers. Interestingly, this structural perturbation of Aβ correlated to reduced synaptic binding to hippocampal neurons. These results demonstrate the promise of Co–sb complexes in anti‐AD therapeutic approaches.     

Surface,interface and electronic properties of F8:F8BT polymeric thin films used for organic light‐emitting diode applications

Ultrathin polymeric films consisting of poly(9,9‐di‐n‐octylfluorenyl‐2,7‐diyl) (F8) blended with poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) grown onto PEDOT:PSS/ITO/PET were investigated by X‐ray photoelectron spectroscopy (XPS), depth‐profiling XPS, reflection electron energy loss spectroscopy (REELS) and angle‐dependent X‐ray absorption spectroscopy (XAS) to gain information on the films' electronic, order and interface properties. AFM studies provide valuable information on the films' nanotopographical properties and homogeneity. Spectroscopic ellipsometry and photoluminescence spectroscopy were used also to obtain information on the optoelectronic properties. Well‐ordered films were observed from the XAS analysis, measured at the sulfur K absorption edge. XPS measurements demonstrated that the surface composition of the polymer thin films prepared by a spin‐coating wet‐chemical deposition method matches the expected F8:F8BT blend stoichiometry. The interfacial properties were studied through an argon ion sputtering process coupled to the XPS acquisition, showing an enhancement of oxygen components at the interface. The films' inhomogeneity was verified by AFM images and analysis. We obtained a value of 3.1 eV as the electronic bandgap of the F8:F8BT film from REELS data, whereas analysis of the spectroscopic ellipsometry spectra revealed that the optical bandgap of F8:F8BT has a value of 2.4 eV. A strong green emission was obtained for the produced films, which is in agreement with the expected emission due to the 1:19 ratio of the F8 and F8BT blended polymers. © 2018 Society of Chemical Industry     

Prognostic and Predictive Roles of KRAS Mutation in Colorectal Cancer

The RAS gene family is among the most studied and best characterized of the known cancer-related genes. Of the three human ras isoforms, KRAS is the most frequently altered gene, with mutations occurring in 17%–25% of all cancers. In particular, approximately 30%–40% of colon cancers harbor a KRAS mutation. KRAS mutations in colon cancers have been associated with poorer survival and increased tumor aggressiveness. Additionally, KRAS mutations in colorectal cancer lead to resistance to select treatment strategies. In this review we examine the history of KRAS, its prognostic value in patients with colorectal cancer, and evidence supporting its predictive value in determining appropriate therapies for patients with colorectal cancer.