g-engineering in hybrid rotaxanes to create AB and AB2 electron spin systems: EPR spectroscopic studies of weak interactions between dissimilar electron spin qubits

Hybrid [2]rotaxanes and pseudorotaxanes are reported where the magnetic interaction between dissimilar spins is controlled to create AB and AB2 electron spin systems,allowing independent control of weakly interacting S =1=2 centers

Resolution of Lithium Deposition versus Intercalation of Graphite Anodes in Lithium Ion Batteries: An In Situ Electron Paramagnetic Resonance Study

From Wiley via Jisc Publications RouterHistory: received 2021-05-07, rev-recd 2021-07-02, pub-electronic 2021-08-13Article version: VoRPublication status: PublishedFunder: Engineering and Physical Sciences Research Council; Id: http://dx.doi.org/10.13039/501100000266; Grant(s): EP/R023034/1, NS/A000055/1, FIRG001 (EP/S003053/1)Abstract: In situ electrochemical electron paramagnetic resonance (EPR) spectroscopy is used to understand the mixed lithiation/deposition behavior on graphite anodes during the charging process. The conductivity, degree of lithiation, and the deposition process of the graphite are reflected by the EPR spectroscopic quality factor, the spin density, and the EPR spectral change, respectively. Classical over‐charging (normally associated with potentials ≤0 V vs. Li+/Li) are not required for Li metal deposition onto the graphite anode: Li deposition initiates at ca. +0.04 V (vs. Li+/Li) when the scan rate is lowered to 0.04 mV s−1. The inhibition of Li deposition by vinylene carbonate (VC) additive is highlighted by the EPR results during cycling, attributed to a more mechanically flexible and polymeric SEI layer with higher ionic conductivity. A safe cut‐off potential limit of +0.05 V for the anode is suggested for high rate cycling, confirmed by the EPR response over prolonged cycling

Natural hazards in Australia : sea level and coastal extremes

The Australian coastal zone encompasses tropical, sub- and extra-tropical climates and accommodates about 80 % of Australia’s population. Sea level extremes and their physical impacts in the coastal zone arise from a complex set of atmospheric, oceanic and terrestrial processes that interact on a range of spatial and temporal scales and will be modified by a changing climate, including sea level rise. This review details significant progress over recent years in understanding the causes of past and projections of future changes in sea level and coastal extremes, yet a number of research questions, knowledge gaps and challenges remain. These include efforts to improve knowledge on past sea level extremes, integrate a wider range of processes in projections of future changes to sea level extremes, and focus efforts on understanding long-term coastline response from the combination of contributing factors

Functionalized Tris(anilido)triazacyclononanes as Hexadentate Ligands for the Encapsulation of U(III), U(IV) and La(III) Cations

From MDPI via Jisc Publications RouterHistory: accepted 2021-11-24, pub-electronic 2021-11-28Publication status: PublishedFunder: Engineering and Physical Sciences Research Council; Grant(s): EP/G037140/1; EP/L014416/1; EP/K039547/1; EP/S033181/1Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we functionalized the previously reported tris-anilide ligand {tacn(SiMe2NPh)3} (tacn = 1,3,7-triazacyclononane) to incorporate substituted aromatic rings, with the aim of modifying f-element complex solubility and ligand steric effects. We report the synthesis of two proligands, {tacn(SiMe2NHAr)3} (Ar = C6H3Me2-3,5 or C6H4Me-4), and their respective group 1 transfer agents—{tacn(SiMe2NKAr)3}, M(III) complexes [M{tacn(SiMe2NAr)3}] for M = La and U, and U(IV) complexes [M{tacn(SiMe2NAr)3}(Cl)]. These compounds were characterized by multinuclear NMR and FTIR spectroscopy and elemental analysis. The paramagnetic uranium complexes were also characterized by solid state magnetic measurements and UV/Vis/NIR spectroscopy. U(III) complexes were additionally studied by EPR spectroscopy. The solid state structures of all f-block complexes were authenticated by single-crystal X-ray diffraction (XRD), together with a minor byproduct [U{tacn(SiMe2NC6H4Me-4)3}(I)]. Comparisons of the characterization data of our f-element complexes with similar literature examples containing the {tacn(SiMe2NPh)3} ligand set showed minor changes in physicochemical properties resulting from the different aromatic ring substitution patterns we investigated

Non-Extremal D-instantons and the AdS/CFT Correspondence

We investigate non-extremal D-instantons in an asymptotically $AdS_5 \times S^5$ background and the role they play in the $AdS_5 / CFT_4$ correspondence. We find that the holographic dual operators of non-extremal D-instanton configurations do not correspond to self-dual Yang-Mills instantons, and we compute explicitly the deviation from self-duality. Furthermore, a class of non-extremal D-instantons yield Euclidean axionic wormhole solutions with two asymptotic boundaries. After Wick rotating, this provides a playground for investigating holography in the presence of cosmological singularities in a closed universe.Comment: 30 pages, 3 figure