High proton conductivity in cyanide-bridged metal-organic frameworks: understanding the role of water

We investigate and discuss the proton conductivity properties of the cyanide-bridged metal–organic framework (MOF) [Nd(mpca)2Nd(H2O)6Mo(CN)8]·nH2O (where mpca is 5-methyl-2-pyrazinecarboxylate). This MOF is one of an exciting class of cyanide-bridged materials that can combine porosity with magnetism, luminescence, and proton conductivity. Specifically, we show that this material features highly hydrophilic open channels filled with water molecules. They enable a high proton conductivity, as much as 10−3 S cm−1. A rich hydrogen-bonding network, formed by the ligands' carboxylate groups with both coordinated and lattice water molecules, facilitates this high proton conductivity. Combined thermogravimetric studies, FTIR spectroscopy and PXRD analysis show that upon heating at 80 °C, the lattice water molecules are removed without any change in the framework. Further heating at 130 °C results in a partial removal of the coordinated water molecules, while still retaining the original framework. These activated MOFs shows an increasing conductivity from ∼10−9 S cm−1 to ∼10−3 S cm−1 when the relative humidity increases from 0% to 98%. Our studies show that the increase in proton conductivity is correlated with the re-hydration of the framework with lattice water molecules. The Arrhenius activation energy for the proton conductivity process is low (Ea = 37 kJ mol−1), indicating that the protons “hop” through the channels following the Grotthuss mechanism. The fact that this MOF is remarkably stable both under high humidity conditions and at relatively high temperatures (up to 130 °C) makes it a good candidate for real-life applications

Observation of coherent transients in ultrashort chirped excitation of an undamped two-level system

The effects of Coherent excitation of a two level system with a linearly chirped pulse are studied theoretically and experimentally (in Rb (5s - 5p)) in the low field regime. The Coherent Transients are measured directly on the excited state population on an ultrashort time scale. A sharp step corresponds to the passage through resonance. It is followed by oscillations resulting from interferences between off-resonant and resonant contributions. We finally show the equivalence between this experiment and Fresnel diffraction by a sharp edge.Comment: 4 pages, 4 figures, to appear in PR

Hydrocarbon Oxidation with H2O2, Catalyzed by Iron Complexes with a Polydentate Pyridine-Based Ligand

Metals in Catalysis, Biomimetics & Inorganic Material

FGFR2 signaling underlies p63 oncogenic function in squamous cell carcinoma

Oncogenic transcription factors drive many human cancers, yet identifying and therapeutically targeting the resulting deregulated pathways has proven difficult. Squamous cell carcinoma (SCC) is a common and lethal human cancer, and relatively little progress has been made in improving outcomes for SCC due to a poor understanding of its underlying molecular pathogenesis. While SCCs typically lack somatic oncogene-activating mutations, they exhibit frequent overexpression of the p53-related transcription factor p63. We developed an in vivo murine tumor model to investigate the function and key transcriptional programs of p63 in SCC. Here, we show that established SCCs are exquisitely dependent on p63, as acute genetic ablation of p63 in advanced, invasive SCC induced rapid and dramatic apoptosis and tumor regression. In vivo genome-wide gene expression analysis identified a tumor-survival program involving p63-regulated FGFR2 signaling that was activated by ligand emanating from abundant tumor-associated stroma. Correspondingly, we demonstrate the therapeutic efficacy of extinguishing this signaling axis in endogenous SCCs using the clinical FGFR2 inhibitor AZD4547. Collectively, these results reveal an unanticipated role for p63-driven paracrine FGFR2 signaling as an addicting pathway in human cancer and suggest a new approach for the treatment of SCC

Moving from a Product-Based Economy to a Service-Based Economy for a More Sustainable Future

Traditionally, economic growth and prosperity have been linked with the availability, production and distribution of tangible goods as well as the ability of consumers to acquire such goods. Early evidence regarding this connection dates back to Adam Smith's Wealth of Nations (1776), in which any activity not resulting in the production of a tangible good is characterized as unproductive of any value." Since then, this coupling of economic value and material production has been prevalent in both developed and developing economies throughout the world. One unintended consequence of this coupling has been the exponential increase in the amount of solid waste being generated. The reason is that any production and consumption of material goods eventually generates the equivalent amount of (or even more) waste. Exacerbating this problem is the fact that, with today's manufacturing and supply chain management technologies, it has become cheaper to dispose and replace most products rather than to repair and reuse them. This has given rise to what some call a disposable society." To put things in perspective: In 2012 households in the U.K. generated approximately 22 thousand tons of waste, which amounted to 411 kg of waste generated per person (Department for Environment, Food & Rural Affairs, 2015). During the same time period, households in the U.S. generated 251 million tons of waste, which is equivalent to a person generating approximately 2 kg of waste every day (U.S. Environmental Protection Agency, 2012). Out of these 251 million tons of total waste generated, approximately 20% of the discarded items were categorized as durable goods. The disposal of durable goods is particularly worrisome because they are typically produced using material from non- renewable resources such as iron, minerals, and petroleum-based raw materials

Are the dead taking over Facebook? A Big Data approach to the future of death online

We project the future accumulation of profiles belonging to deceased Facebook users. Our analysis suggests that a minimum of 1.4 billion users will pass away before 2100 if Facebook ceases to attract new users as of 2018. If the network continues expanding at current rates, however, this number will exceed 4.9 billion. In both cases, a majority of the profiles will belong to non-Western users. In discussing our findings, we draw on the emerging scholarship on digital preservation and stress the challenges arising from curating the profiles of the deceased. We argue that an exclusively commercial approach to data preservation poses important ethical and political risks that demand urgent consideration. We call for a scalable, sustainable, and dignified curation model that incorporates the interests of multiple stakeholders

A dual process account of creative thinking

This article explicates the potential role played by type 1 thinking (automatic, fast) and type 2 thinking (effortful, logical) in creative thinking. The relevance of Evans's (2007) models of conflict of dual processes in thinking is discussed with regards to creative thinking. The role played by type 1 thinking and type 2 thinking during the different stages of creativity (problem finding and conceptualization, incubation, illumination, verification and dissemination) is discussed. It is proposed that although both types of thinking are active in creativity, the extent to which they are active and the nature of their contribution to creativity will vary between stages of the creative process. Directions for future research to test this proposal are outlined; differing methodologies and the investigation of different stages of creative thinking are discussed. © Taylor & Francis Group, LLC