386 research outputs found
Reduction-induced facile isomerisation of metallacarboranes:synthesis and crystallographic characterisation of 4-Cp-4,1,2-closo-CoC<sub>2</sub>B<sub>9</sub>H<sub>11 </sub>
One-electron reduction of 3-Cp-3,1,2-closo-CoC2B9H11 followed by heating to reflux in DME (b.p. 85 °C) induces isomerisation to 4-Cp-4,1,2-closo-CoC2B9H11.</p
Icosahedral metallacarborane/carborane species derived from 1,1′-bis(o-carborane)
We thank ORSAS (GS) and the EPSRC (DE and DMcK supported by project EP/E02971X/1, WYM supported by project EP/I031545/1) for funding.Examples of singly-metallated derivatives of 1,1[prime or minute]-bis(o-carborane) have been prepared and spectroscopically and structurally characterised. Metallation of [7-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-7,8-nido-C2B9H10]2- with a {Ru(p-cymene)}2+ fragment affords both the unisomerised species [1-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-3-(p-cymene)-3,1,2-closo-RuC2B9H10] (2) and the isomerised [8-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-2-(p-cymene)-2,1,8-closo-RuC2B9H10] (3), and 2 is easily transformed into 3 with mild heating. Metallation with a preformed {CoCp}2+ fragment also affords a 3,1,2-MC2B9-1[prime or minute],2[prime or minute]-C2B10 product [1-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-3-Cp-3,1,2-closo-CoC2B9H10] (4), but if CoCl2/NaCp is used followed by oxidation the result is the 2,1,8-CoC2B9-1[prime or minute],2[prime or minute]-C2B10 species [8-(1[prime or minute]-1[prime or minute],2[prime or minute]-closo-C2B10H11)-2-Cp-2,1,8-closo-CoC2B9H10] (5). Compound 4 does not convert into 5 in refluxing toluene, but does do so if it is reduced and then reoxidised, perhaps highlighting the importance of the basicity of the metal fragment in the isomerisation of metallacarboranes. A computational study of 1,1[prime or minute]-bis(o-carborane) is in excellent agreement with a recently-determined precise crystallographic study and establishes that the {1[prime or minute],2[prime or minute]-closo-C2B10H11} fragment is electron-withdrawing compared to H.Publisher PDFPeer reviewe
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From Transistor to Trapped-ion Computers for Quantum Chemistry
Over the last few decades, quantum chemistry has progressed through the development of computational methods based on modern digital computers. However, these methods can hardly fulfill the exponentially-growing resource requirements when applied to large quantum systems. As pointed out by Feynman, this restriction is intrinsic to all computational models based on classical physics. Recently, the rapid advancement of trapped-ion technologies has opened new possibilities for quantum control and quantum simulations. Here, we present an efficient toolkit that exploits both the internal and motional degrees of freedom of trapped ions for solving problems in quantum chemistry, including molecular electronic structure, molecular dynamics, and vibronic coupling. We focus on applications that go beyond the capacity of classical computers, but may be realizable on state-of-the-art trapped-ion systems. These results allow us to envision a new paradigm of quantum chemistry that shifts from the current transistor to a near-future trapped-ion-based technology.Chemistry and Chemical Biolog
Cavity Design and Optimization for Organic Microcavity OLEDs
We report on detailed simulations of the emission from microcavity OLEDs consisting of widely used organic materials, n,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (NPB) as a hole transport layer and tris (8-hydroxyquinoline) (Alq3) as emitting and electron transporting layer. The thick silver film was considered as a top mirror, while silver or copper films on quartz substrate were considered as bottom mirrors. The electroluminescence emission spectra, electric field distribution inside the device, carrier density and recombination rate were calculated as a function of the position of the emission layer, i.e. interface between NPB and Alq3. In order to achieve optimum emission from a microcavity OLED, it is necessary to align the position of the recombination region with the antinode of the standing wave inside the cavity. Once the optimum structure has been determined, the microcavity OLED devices were fabricated and characterized. The experimental results have been compared to the simulations and the influence of the emission region width and position on the performance of microcavity OLEDs was discussed
Origin and evolution of the octoploid strawberry genome.
Cultivated strawberry emerged from the hybridization of two wild octoploid species, both descendants from the merger of four diploid progenitor species into a single nucleus more than 1 million years ago. Here we report a near-complete chromosome-scale assembly for cultivated octoploid strawberry (Fragaria × ananassa) and uncovered the origin and evolutionary processes that shaped this complex allopolyploid. We identified the extant relatives of each diploid progenitor species and provide support for the North American origin of octoploid strawberry. We examined the dynamics among the four subgenomes in octoploid strawberry and uncovered the presence of a single dominant subgenome with significantly greater gene content, gene expression abundance, and biased exchanges between homoeologous chromosomes, as compared with the other subgenomes. Pathway analysis showed that certain metabolomic and disease-resistance traits are largely controlled by the dominant subgenome. These findings and the reference genome should serve as a powerful platform for future evolutionary studies and enable molecular breeding in strawberry
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Small Molecule-Induced Cytosolic Activation of Protein Kinase Akt Rescues Ischemia-Elicited Neuronal Death
Elevating Akt activation is an obvious clinical strategy to prevent progressive neuronal death in neurological diseases. However, this endeavor has been hindered because of the lack of specific Akt activators. Here, from a cell-based high-throughput chemical genetic screening, we identified a small molecule SC79 that inhibits Akt membrane translocation, but paradoxically activates Akt in the cytosol. SC79 specifically binds to the PH domain of Akt. SC79-bound Akt adopts a conformation favorable for phosphorylation by upstream protein kinases. In a hippocampal neuronal culture system and a mouse model for ischemic stroke, the cytosolic activation of Akt by SC79 is sufficient to recapitulate the primary cellular function of Akt signaling, resulting in augmented neuronal survival. Thus, SC79 is a unique specific Akt activator that may be used to enhance Akt activity in various physiological and pathological conditions
The m.13051G>A mitochondrial DNA mutation results in variable neurology and activated mitophagy.
Maternally inherited mitochondrial DNA (mtDNA) mutations cause symptoms of Leber hereditary optic neuropathy (LHON) in -1 in 30,000 individuals. Most of the affected individuals lack respiratory chain defects1 and there is no proven prophylactic treatment
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Spectators’ Negotiations of Risk, Masculinity and Performative Mobilities at the TT Races
This paper explores the particular assemblage of place, event and individual identity performances that occur each year in the Isle of Man in and through the TT (Tourist Trophy) motorcycle races. These road races are associated with a high degree of risk for the racers and the confluence of over 30,000 visitors and 10,000 motorcycles also presents potential risks for spectators and residents alike. Both motorcycling and risk-taking have been associated with particular forms of masculinity, notably hegemonic, working class and youthful masculinities. Using detailed surveys of spectators we argue that the TT races, while undoubtedly
dominated by men and predicated on a cultural privileging of speed and skill, are grounded in varying combinations of determinate and reflexive attitudes to risk, reflecting the performance of a variety of gendered, ‘biker’ and wider identity-based positionalities. Findings also highlight a particular inter-relation of mobilities and place identities at the TT races and bring to light the highly significant and under-researched embodied, performative and emotional mobilities of spectators. The conceptual and methodological importance of (a) situated research of both mobilities and gender in specific place-temporalities and (b) wider surveys of motorcyclists to complement ethnographic studies of small cohorts are also stressed
Machine-learning based patient classification using Hepatitis B virus full-length genome quasispecies from Asian and European cohorts
Chronic infection with Hepatitis B virus (HBV) is a major risk factor for the development of advanced liver disease including fibrosis, cirrhosis, and hepatocellular carcinoma (HCC). The relative contribution of virological factors to disease progression has not been fully defined and tools aiding the deconvolution of complex patient virus profiles is an unmet clinical need. Vari
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