Exploiting cation aggregation in new magnesium amidohaloaluminate electrolytes for magnesium batteries

Mg batteries present an attractive and sustainable alternative to Li-ion batteries, wherein magnesium metal as an anode displays a superior theoretical volumetric energy density of 3833 A h L−1versus 2062 A h L−1 for lithium. An outstanding crucial bottleneck in realising their more widespread uptake is the development of suitable electrolytes, where electrode passivation, a limited electrochemical window, conditioning requirements, low ion mobility and low coulombic efficiencies all contribute to current limitations in Mg batteries. In an area thus far dominated by the thermodynamically stable [Mg2Cl3]+ dinuclear cation, we present here a novel family of magnesium amidohaloaluminate electrolytes [(Dipp)(SiMe3)2NAlCl3]− [MgxCl2x−1]+ where the magnesium chloride cation aggregation has been tailored (x = 1, 2, 3) by substitution of the coordinating ligand to the Mg2+ centre, and show how directly altering this cation affects battery performance (Dipp = 2,6-diisopropylphenyl, Me = methyl). The electrochemical activity of these new electrolytes has been evaluated by cyclic voltammetry, galvanostatic cycling and impedance spectroscopy in Mg–metal symmetrical cells as well as in battery cells with the Mo6S8 Chevrel phase cathode material against magnesium metal. The mononuclear and dinuclear magnesium amidohaloaluminate electrolytes facilitate reversible Mg plating and stripping from the Mg–metal anode with excellent stability, withstanding over 70 hours of continuous cycling. We demonstrate the compatibility of these novel electrolytes with the Mo6S8 Chevrel intercalation cathode material, allowing cycling of a Mg–metal cell up to 100 cycles with coulombic efficiencies above 95%

Structural investigation into the threading intercalation of a chiral dinuclear ruthenium(II) polypyridyl complex through a B-DNA oligonucleotide

Herein we report the separation of the three stereoisomers of the DNA light-switch compound [{Ru(bpy)2}2(tpphz)]4+ (tpphz = tetrapyrido[3,2-a:2',3'-c:3″,2″-h:2‴,3‴-j]phenazine) by column chromatography and the characterization of each stereoisomer by X-ray crystallography. The interaction of these compounds with a DNA octanucleotide d(GCATATCG).d(CGATATGC) has been studied using NMR techniques. Selective deuteration of the bipyridyl rings was needed to provide sufficient spectral resolution to characterize structures. NMR-derived structures for these complexes show a threading intercalation binding mode with slow and chirality-dependent rates. This represents the first solution structure of an intercalated bis-ruthenium ligand. Intriguingly, we find that the binding site selectivity is dependent on the nature of the stereoisomer employed, with Λ RuII centers showing a better intercalation fit

Parity Invariance and Effective Light-Front Hamiltonians

In the light-front form of field theory, boost invariance is a manifest symmetry. On the downside, parity and rotational invariance are not manifest, leaving the possibility that approximations or incorrect renormalization might lead to violations of these symmetries for physical observables. In this paper, it is discussed how one can turn this deficiency into an advantage and utilize parity violations (or the absence thereof) in practice for constraining effective light-front Hamiltonians. More precisely, we will identify observables that are both sensitive to parity violations and easily calculable numerically in a non-perturbative framework and we will use these observables to constrain the finite part of non-covariant counter-terms in effective light-front Hamiltonians.Comment: REVTEX, 9 page

Renormalization of Hamiltonian Field Theory; a non-perturbative and non-unitarity approach

Renormalization of Hamiltonian field theory is usually a rather painful algebraic or numerical exercise. By combining a method based on the coupled cluster method, analysed in detail by Suzuki and Okamoto, with a Wilsonian approach to renormalization, we show that a powerful and elegant method exist to solve such problems. The method is in principle non-perturbative, and is not necessarily unitary.Comment: 16 pages, version shortened and improved, references added. To appear in JHE

Nonperturbative Renormalization and the QCD Vacuum

We present a self consistent approach to Coulomb gauge Hamiltonian QCD which allows one to relate single gluon spectral properties to the long range behavior of the confining interaction. Nonperturbative renormalization is discussed. The numerical results are in good agreement with phenomenological and lattice forms of the static potential.Comment: 23 pages in RevTex, 4 postscript figure

Reinforcement determines the timing dependence of corticostriatal synaptic plasticity in vivo

Plasticity at synapses between the cortex and striatum is considered critical for learning novel actions. However, investigations of spike-timing-dependent plasticity (STDP) at these synapses have been performed largely in brain slice preparations, without consideration of physiological reinforcement signals. This has led to conflicting findings, and hampered the ability to relate neural plasticity to behavior. Using intracellular striatal recordings in intact rats, we show here that pairing presynaptic and postsynaptic activity induces robust Hebbian bidirectional plasticity, dependent on dopamine and adenosine signaling. Such plasticity, however, requires the arrival of a reward-conditioned sensory reinforcement signal within 2 s of the STDP pairing, thus revealing a timing-dependent eligibility trace on which reinforcement operates. These observations are validated with both computational modeling and behavioral testing. Our results indicate that Hebbian corticostriatal plasticity can be induced by classical reinforcement learning mechanisms, and might be central to the acquisition of novel actions

Poincare Invariant Algebra From Instant to Light-Front Quantization

We present the Poincare algebra interpolating between instant and light-front time quantizations. The angular momentum operators satisfying SU(2) algebra are constructed in an arbitrary interpolation angle and shown to be identical to the ordinary angular momentum and Leutwyler-Stern angular momentum in the instant and light-front quantization limits, respectively. The exchange of the dynamical role between the transverse angular mometum and the boost operators is manifest in our newly constructed algebra.Comment: 21 pages, 3 figures, 1 tabl

The calibration of the Sudbury Neutrino Observatory using uniformly distributed radioactive sources

The production and analysis of distributed sources of 24Na and 222Rn in the Sudbury Neutrino Observatory (SNO) are described. These unique sources provided accurate calibrations of the response to neutrons, produced through photodisintegration of the deuterons in the heavy water target, and to low energy betas and gammas. The application of these sources in determining the neutron detection efficiency and response of the 3He proportional counter array, and the characteristics of background Cherenkov light from trace amounts of natural radioactivity is described.Comment: 24 pages, 13 figure

Advancement in the pressureless sintering of CP titanium using high-frequency induction heating

High-frequency induction heating is applied as an alternative heating source for pressureless sintering of commercially pure Ti powders, aiming to intensify the sintering process. The effects of the process parameters on the properties of the sintered material are systematically studied. The initial powder compact density is the most influential parameter permitting sintered structures with highly porous to almost fully dense appearance. Short heating time combined with sintering to temperatures just above the β-transus resulted in a strong diffusion bonding between the Ti powder particles, and grain growth is observed at the former boundaries of the neighboring powder particles. The dimpled appearance of the fracture surface at those regions confirmed the strong metallic interparticle bonding. Tensile properties comparable to those of Ti-Grade 3 and Ti-Grade 4 are achieved, which also demonstrates the efficiency of the induction sintering process. A mechanism explaining the fast and efficient sintering is proposed. The process has the added advantage of minimizing the oxygen pickup

Atom-efficient synthesis of a benchmark electrolyte for magnesium battery applications

The benchmark magnesium electrolyte, [Mg2Cl3]+ [AlPh4]−, can be prepared in a 100% atom-economic fashion by a ligand exchange reaction between AlCl3 and two molar equivalents of MgPh2. NMR and vibrational spectroscopy indicate that the reported approach results in a simpler ionic composition than the more widely adopted synthesis route of combining PhMgCl with AlCl3. Electrochemical performance has been validated by polarisation tests and cyclic voltammetry, which demonstrate excellent stability of electrolytes produced via this atom-efficient approach