Gansu Studio: 'Plug-in' school unit for rural China

Gansú ‘Plug-in’ Studio was a community outreach project based in China developed over a course of 2 years (2014-2016). It proposed a complementary approach of education to improve quality of learning in primary schools in rural areas. The premise for the work was to engage higher education institutions such as UNNC and primary education institutions, such as HEPAN, by exchange of resources, (e.g. physical or human - staff and students as well as contexts as real opportunities for learning). It worked using design as a tool for development and environmental awareness. It worked in partnership with industry and government institutions and it involved over 120 students and 15 staff from 5 different areas (Architecture, Product Design, Environmental Engineering, Film Studies and English/Education). Through interactive workshops with academics and industry practitioners, UNNC students were guided to realise their ideas through innovative design and sustainable engineering solutions, also developed their communication and team working skills for real to help rural education and community development. Meanwhile, pupils and teachers in rural areas could develop sufficiently as their urban counterparts through this connected learning hub. The purpose of this paper is to discuss the processes and outcomes of Gansu Studio. The Plug-in Gansu Unit was designed to be the first net positive energy rural school building in China producing an estimated 18304 kWh/year of renewable energy to the school and reverting back to the county grid an annual extra clean energy 2304kWh/annum upon completion. An estimated 22 tons of water per year would be also saved

Europa: Prospects for an ocean and exobiological implications

As far as we know, Earth is the only planet in our solar system that supports life. It is natural, therefore, that our understanding of life as a planetary phenomenon is based upon Earth-like planets. There are environments in the solar system where liquid water, commonly believed to be a prerequisite for biological activity, may exist in a distinctly non-Earth-like environment. One such location is Europa, one of the Galilean satellites of Jupiter. The possibility that liquid water exists on Europa presents us with some interesting exobiological implications concerning the potential of the satellite to support life. Topics include the following: an ocean on Europa; thermal evolution of Europa; Europa's three models; exobiological implications; early conditions of Europa; low-temperature abiotic chemistry; possibility of the emergence of life on Europa; prerequisites for the habitability of Europa; energy sources for biosynthesis and metabolic activity; habitability of Europa by anaerobic life; and habitability by aerobic life

c-FOS drives reversible basal to squamous cell carcinoma transition.

While squamous transdifferentiation within subpopulations of adenocarcinomas represents an important drug resistance problem, its underlying mechanism remains poorly understood. Here, using surface markers of resistant basal cell carcinomas (BCCs) and patient single-cell and bulk transcriptomic data, we uncover the dynamic roadmap of basal to squamous cell carcinoma transition (BST). Experimentally induced BST identifies activator protein 1 (AP-1) family members in regulating tumor plasticity, and we show that c-FOS plays a central role in BST by regulating the accessibility of distinct AP-1 regulatory elements. Remarkably, despite prominent changes in cell morphology and BST marker expression, we show using inducible model systems that c-FOS-mediated BST demonstrates reversibility. Blocking EGFR pathway activation after c-FOS induction partially reverts BST in vitro and prevents BST features in both mouse models and human tumors. Thus, by identifying the molecular basis of BST, our work reveals a therapeutic opportunity targeting plasticity as a mechanism of tumor resistance

The anions [Cptt2Zr(μ-S)2M(CO)2]- (M = Rh, Ir) as versatile precursors for the synthesis of sulfido-bridged early−late heterotrimetallic (ELHT) compounds

The reaction of [Cp2 ttZr(μ3-S) 2{Ir(CO)2}2] (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with dppe (1,2-bis-(diphenylphosphino)ethane) affords the ion-pair compound [Ir(CO)(dPPe)2][Cp2 ttZr(μ-S) 2Ir(CO)2] (2). The related compound [Rh(dPPe) 2][Cp2 ttZr(μ-S)2Rh(CO) 2] (5) has been obtained in solution under a carbon monoxide atmosphere by reaction of [Cp2 ttZr(μ3-S) 2{Rh(CO)2}2] with dppe through the intermediate heterotrinuclear compound [Cp2 ttZr(μ3-S) 2{Rh(dppe)}{Rh(CO)2}] (4). Reaction of the heterodinuclear anion [Cp2 ttZr(μ-S)2Ir(CO) 2]-, generated in situ, with [Rh(μ-Cl)(cod)] 2, [RhCl2(CO)2]- and [Pd(μ-Cl)-(η3-C3H5)]2 affords the d0-d8-d8 early-late compounds [Cp 2 ttZr(μ3-S)2{Ir(CO) 2}{Rh(cod)}] (6), [Cp2 tt-Zr(μ3-S) 2{Ir(CO)2}{Rh(CO)2}] (7), and [Cp 2 ttZr(μ3-S)2{Ir(CO) 2}{Pd(η3-C3H5)}] (8) each with a symmetrical trigonal-bipyramidal M3(μ3-S)2 heterotrimetallic metal-sulfur core. In the same way, the reaction of [Cp 2 ttZr(μ-S)2M(CO)2]- (M = Rh, Ir) with [AuCl(PPh3)] leads to the preparation of the d 0-d8-d10 early-late compounds [Cp 2 ttZr(μ-S)2(Ir(CO)2}{Au(PPh 3)}] (9) and [Cp2 ttZr(μ-S) 2{Rh(CO)2}{Au(PPh3)}] (10) with an open M 3(μ3-S)(μ2-S) heterotrimetallic metal-sulfur framework. On the other hand, treatment of the bis(hydrosulfido) zirconium compound [Cp2 ttZr(SH)2] with triethylamine followed by addition of [Pd(μ-Cl)(η3-C 3H5)]2 or [AuCl(PPh3)] affords the sulfido-bridged early-late heterobimetallic compounds [Cp2 ttZr(μ3-S)2{Pd(η3-C 3H5)}2] (11) and [Cp2 ttZr(μ-S)2(Au(PPh3)}2] (12). The molecular structure of complexes 9 and 12 determined by X-ray diffraction methods are also described.The financial support from Ministerio de Educación y Ciencia (MEC/FEDER) is gratefully acknowledged (Projects CTQ2006-03973/BQU and Factoría de Cristalización, CONSOLIDER INGENIO-2010).Peer Reviewe

Synthesis of titanium and zirconium complexes with 2-pyridonate and 2, 6-pyridinedithiolate ligands

Special Issue: Dedicated to Professor F. Ekkehardt Hahn on the Occasion of His 60th Birthday with our most Sincere Congratulations for his Outstanding Contributions to Chemistry and Best Wishes.Treatment of complex [Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex [Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound [Cp2ZrCl2] did not worked. However, the use of the metallocene [Cptt 2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted [Cptt 2ZrMe2] with methanol affording complex [Cptt 2ZrMe(OMe)] (2), which was characterized in situ by NMR techniques. In the same line, the reaction of [Cptt 2ZrMe2] with 2-hydroxypyridine gave complex [Cptt 2Zr(Me)(Opy)] (3); forcing the conditions of this reaction did not lead to the expected complex [Cptt 2Zr(Opy)2], most probably due to the steric hindrance exerted by the bulky cyclopentadienyl ligands. Further reactions of complex 3 with ligands having acidic protons also led to the recovery of the starting complex. However, when shifting to the bifunctional ligand 2, 6-dimercaptopyridine [py(SH)2] a double protonation of the methyl ligands in [Cptt 2ZrMe2] occurred, allowing the isolation of mononuclear complex [Cptt 2Zr(κS,κS,κN-pyS2)] (4), upon evolution of methane. The molecular structure of complex 4 was determined by X-ray methods, showing the zirconium atom in a highly distorted trigonal bipyramidal arrangement; structural parameters indicate a conventional Zr-N bond, but rather weak Zr-S interactions.Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER, Projects CTQ2012-35665 and CTQ2013-42532-P), MICINN (Project Consolider Ingenio 2010, CSD2009-00050) and Diputación General de Aragón (DGA/ FSE-E07 and E70) is gratefully acknowledged.Peer Reviewe

Estimating the cumulative effects of the nature-based tourism in a coastal dolphin population from southern Kenya

Due to the growth of nature-based tourism worldwide, behavioural studies are needed to assess the impact of this industry on wildlife populations and understand their short-term effect. Tourism impact on dolphin populations remain poorly documented in developing countries. This study investigates the effects of nature-based tourism on the behaviour of the Indo-Pacific bottlenose dolphins (Tursiops aduncus) in southern Kenya. We used Markov chain models to estimate transition probabilities between behavioural states in the presence and absence of tourist boats, and assess the overall behavioural budgets. Based on these data and the tourism intensity in the area, we quantified the potential tourist boat disturbance over the period 2006-2013. Our results demonstrated that tourist boat interactions affected dolphins' behavioural budgets, with a significant decrease in the overall amount of time travelling and an increase in diving. The average duration of travelling and resting decreased significantly in the presence of boats. Although the cumulative tourism exposure was not significant for the dolphin population at their current levels, these impacts should be taken into consideration with the potential tourism growth in the area. This is particularly important if tourism reaches periods of high intensity, as we have shown that these periods could have a significant impact for the species, particularly where home-range and core areas are highly overlap by this activity. Understanding the effect of human disturbance variations from previous years may help to predict the consequences on dolphin populations, towards achieving a more ecological and economic sustainability of the activity

Reversible opening of the triangular structure of a sulfido-bridged ZrRh2 early-late heterobimetallic complex induced by Bis-(diphenylphosphino)methane

Reaction of the early - late heterobimetallic complexes [Cp tt 2Zr(μ3-S)2{M(CO)} 2(μ-dppm)] (M = Rh, Ir) with dppm (bis-(diphenylphosphino)methane) yields the compounds [Cptt 2Zr(μ-S)2M(μ- CO)2(μ-dppm)M(η2-dppm)] (M = Rh (3), Ir (4)). The molecular structure of 3 shows a bent trimetallic ZrRhRh chain with tetrahedral, trigonal-bipyramidal, and square-pyramidal geometries, respectively. This trinuclear compound exhibits a mixed-valence Rh(II) - Rh(0) metal - metal bonded unit that results from the unusual chelating coordination of the metalloligand [Cptt 2Zr(S)2]2- and is further stabilized by the presence of two unsymmetrical bridging carbonyl ligands, which interact with the unsaturated Rh(II) metal. The formation of 3 is reversible, and the equilibrium 1 + dppm ⇄ 3 has been observed in solution (K ≈ 16 at 22 °C in C6D6). The opening of the triangular core in the heterotrimetallic compound [Cptt 2Zr(μ 3-S)2-{Rh(CO)}{Ir(CO)}(μ-dppm)] (5) is not selective and gives the compounds [Cptt 2Zr(μ-S) 2Rh(μ-CO)2(μ-dppm)Ir(η2-dppm)] (6) and [Cptt 2Zr(μ-S)2Ir(μ-CO) 2(μ-dppm)Rh(η2-dppm)] (7) in a 3:1 molar ratio.The generous financial support from Dirección General de Enseñanza Superior e Investigación (DGES) (Project BQU2003-05412-C02-01) is gratefully acknowledged.Peer Reviewe