Preparation and Structures of Crystalline Aromatic Cation-Radical Salts. Triethyloxonium Hexachloroantimonate as a Novel (One-Electron) Oxidant

Triethyloxonium hexachloroantimonate [Et3O+SbCl6-] is a selective oxidant of aromatic donors (ArH), and it allows the facile preparation and isolation of crystalline paramagnetic salts [ArH+•, SbCl6-] for the X-ray structure determination of various aromatic cation radicals. The mechanistic relationship between the Meerwein salt [Et3O+SbCl6-] and the pure Lewis acid oxidant SbCl5 is based on a prior ethyl transfer from oxygen to chlorine within the ion pair

Novel Synthesis and Structures of Tris-Annelated Benzene Donors for the Electron-Density Elucidation of the Classical Mills−Nixon Effect

A versatile method for the high-yield synthesis of various tris-, bis-, and mono-annelated benzenes (as well as cyclooctatetraene) is based on the Pd-catalyzed coupling of three (or four) ethylenic units comprised of α,β-dibromoalkenes and α‘-alkenyl Grignard reagentsall carried out in a single pot. The particular application to tris(bicyclopentyl)-annelated benzene yields the syn isomer 1s in high purity; X-ray diffraction analysis confirms the aromatic bond alternation relevant to the Mills−Nixon effect. Most importantly, the efficient synthesis of 1s crystals of extraordinary quality allows us (for the first time) to make precise electron-density measurements of the “banana-type” distortion and the ellipticity (π-character) of the various aromatic C−C bondssufficient to identify the electronic origin of the classical Mills−Nixon effect. The unique electron-donor properties of tris-annelated benzenes also relate to their highly reversible one-electron oxidation potentials even in nonpolar solvents

Disproportionation and Structural Changes of Tetraarylethylene Donors upon Successive Oxidation to Cation Radicals and to Dications

The stepwise (one-electron) chemical oxidation of the tetraphenylethylene donor and its substituted analogues (D) can be carried out by electron exchange with aromatic cations or antimony(V) oxidants to selectively afford the cation radical (D+•) initially and then the dication (D2+). The ready interchange of the latter establishes the facile disproportionation (i.e., 2D+• ⇌ D2+ + D) that was originally examined by only transient electrochemical techniques. The successful isolations of the crystalline salts of the tetraanisylethylene cation radical (1+•) as well as the tetraanisylethylene dication (12+) allow X-ray diffraction analysis (for the first time) to quantify the serial changes in the molecular structure upon successive oxidations. Five structural parameters (d, l, θ, φ, and q) are identified as quantitative measures of changes in bond (CαCβ, Cαanisyl) lengths, dihedral (CαCβ)/torsional (anisyl) angles, and quinoidal (anisyl) distortion attendant upon the removal of first one-electron and then another electron from the tetraanisylethylene framework. The linear variation of all five parameters in Chart 3 point to a strongly coupled relaxation of tetraanisylethylene (involving simultaneous changes of d, l, θ, φ, and q) to a severely twisted dication. Most noteworthy is the structure of the cation radical 1+• with d, l, θ, φ, and q values that are exactly one-half those of the dication. The complex molecular changes accompanying the transformation:  D → D+• → D2+ bear directly on the donor properties and the disproportionation processes of various tetraarylethylenes

Technology and Caregiving: Emerging Interventions and Directions for Research.

An array of technology-based interventions has increasingly become available to support family caregivers, primarily focusing on health and well-being, social isolation, financial, and psychological support. More recently the emergence of new technologies such as mobile and cloud, robotics, connected sensors, virtual/augmented/mixed reality, voice, and the evermore ubiquitous tools supported by advanced data analytics, coupled with the integration of multiple technologies through platform solutions, have opened a new era of technology-enabled interventions that can empower and support family caregivers. This paper proposes a conceptual framework for identifying and addressing the challenges that may need to be overcome to effectively apply technology-enabled solutions for family caregivers. The paper identifies a number of challenges that either moderate or mediate the full use of technologies for the benefit of caregivers. The challenges include issues related to equity, inclusion, and access; ethical concerns related to privacy and security; political and regulatory factors affecting interoperability and lack of standards; inclusive/human-centric design and issues; and inherent economic and distribution channel difficulties. The paper concludes with a summary of research questions and issues that form a framework for global research priorities

Spectral Data for Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins

Spectral data created in the course of the research project. Supports specific findings in Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins . A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)3+ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)3. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)3 along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl2, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane

Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins

A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)3+ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)3. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)3 along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl2, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane

Examination Free-Flow Speed Distribution on Two-Lane Rural Roads

[EN] Free-flow speed variation of passenger vehicles along a road segment is one of the most used factors in road safety studies, as a surrogate measure to evaluate road design consistency. Free-flow speed may be measured when a road segment is already built but must be estimated during the design phase. Several studies have been carried out to calibrate models to estimate free-flow speed, with geometric features as explanatory variables. Currently, most free-flow speed models focus only on mean speed or speed in particular percentiles, such as the 85th or 95th. Moreover, most studies have assumed normality in the free-flow speed distribution without checking this hypothesis. The main objective of this study was to analyze the free-flow speed distribution on two-lane rural road curves and tangents. The research focused on two main issues: determining whether speed data were normally distributed at a specific site and analyzing the behavior of the mean and standard deviation of speed on curves and tangents. The study was based on continuous operating speed profiles, which were obtained from a database of more than 16,000 vehicles/km. A total of 63 horizontal curves and 78 tangents were analyzed. According to the results, the normal distribution is not the best distribution in most cases for describing free-flow speeds. In 46 of the curves and 64 of the tangents, free-flow speed cannot be assumed to be normally distributed. Therefore, some other distributions should be tested in further research.The study presented in this paper is part of the research project CASEFU-Estudio experimental de la funcionalidad y seguridad de las carreteras convencionales, subsidized by the Spanish Ministry of Economy and Competitiveness and the European Social Fund. In addition, the authors thank the Center for Studies and Experimentation of Public Works of the Spanish Ministry of Public Works for subsidizing the field data collection, and the Infrastructure and Transportation Department of the General Directorate of Public Works of the Valencian Government, the Valencian Provincial Council, and the Ministry of the Interior, especially the General Directorate of Traffic of Spain, for their cooperation in gathering the field data.García Jiménez, ME.; Pérez Zuriaga, AM.; Llopis-Castelló, D.; Camacho Torregrosa, FJ.; García García, A. (2016). Examination Free-Flow Speed Distribution on Two-Lane Rural Roads. Transportation Research Record Journal of the Transportation Research Board. 2556:86-97. https://doi.org/10.3141/2556-09S8697255

Immersive competence and immersive literacy: Exploring how users learn about immersive experiences

While immersive experiences mediated through near-eye displays are still a relatively immature medium, there are millions of consumer devices in use. The level of awareness of the forms of the interface and media will vary enormously across the potential audience. Users might own personal devices or might encounter immersive systems in various venues. We introduce the term immersive competence to refer to the general practical knowledge and skills that users accumulate about how typical immersive interfaces work—the ways in which buttons are used, main locomotion techniques, etc. We then introduce the term immersive literacy to refer to awareness of how immersive interfaces are unique, when they might be appropriate, typical forms of media, etc. We sketch out how users develop competence and literacy with immersive media, and then highlight various open questions that are raised