Imposing high-symmetry and tuneable geometry on lanthanide centres with chelating Pt and Pd metalloligands

Exploitation of HSAB preferences allows for high-yield, one-pot syntheses of lanthanide complexes chelated by two Pd or Pt metalloligands, [MII(SAc)4]2− (SAc− = thioacetate, M = Pd, Pt). The resulting complexes with 8 oxygen donors surrounding the lanthanides can be isolated in crystallographically tetragonal environments as either [NEt4]+ (space group: P4/mcc) or [PPh4]+ (space group: P4/n) salts. In the case of M = Pt, the complete series of lanthanide complexes has been structurally characterized as the [NEt4]+ salts (except for Ln = Pm), while the [PPh4]+ salts have been structurally characterized for Ln = Gd–Er, Y. For M = Pd, selected lanthanide complexes have been structurally characterized as both salts. The only significant structural difference between salts of the two counter ions is the resulting twist angle connecting tetragonal prismatic and tetragonal anti-prismatic configurations, with the [PPh4]+ salts approaching ideal D4d symmetry very closely (φ = 44.52–44.61°) while the [NEt4]+ salts exhibit intermediate twist angles in the interval φ = 17.28–27.41°, the twist increasing as the complete 4f series is traversed. Static magnetic properties for the latter half of the lanthanide series are found to agree well in the high temperature limit with the expected Curie behavior. Perpendicular and parallel mode EPR spectroscopy on randomly oriented powder samples and single crystals of the Gd complexes with respectively Pd- and Pt-based metalloligands demonstrate the nature of the platinum metal to strongly affect the spectra. Consistent parametrization of all of the EPR spectra reveals the main difference to stem from a large difference in the magnitude of the leading axial term, B02, this being almost four times larger for the Pt-based complexes as compared to the Pd analogues, indicating a direct Pt(5dz2)–Ln interaction and an arguable coordination number of 10 rather than 8. The parametrization of the EPR spectra also confirms that off-diagonal operators are associated with non-zero parameters for the [NEt4]+ salts, while only contributing minimally for the [PPh4]+ salts in which lanthanide coordination approximates D4d point group symmetry closely.LHD acknowledges support from NSF-CCT EMT 08-517. (08-517 - NSF-CCT EMT

System influences on work disability due to low back pain: an international evidence synthesis

Work disability due to low back pain is a significant global health concern. Current policy and practice aimed at tackling this problem is largely informed by the biopsychosocial model. Resultant interventions have demonstrated some small-scale success, but they have not created a widespread decrease in work disability. This may be explained by the under-representation of the less measurable aspects in the biopsychosocial evidence base; namely the influence of relevant systems. Thus, a ‘best-evidence’ synthesis was conducted to collate the evidence on how compensatory (worker’s compensation and disability benefits), healthcare and family systems (spouse/partner/close others) can act as obstacles to work participation for those with low back pain. Systematic searches of several scientific and grey literature sources were conducted, resulting in 1,762 records. Following a systematic exclusion process, 57 articles were selected and the evidence was assessed using a system adapted from previous large-scale policy reviews conducted in this field. Results indicated how specific features of relevant systems could act as obstacles to individual efforts/interventions aimed at tackling work disability due to LBP. These findings reinforce the need for a ‘whole-systems’ approach, with all key players onside and have implications for the revision of current biopsychosocial-informed policy and practice

PT-symmetry breaking and maximal chirality in a nonuniform PT-symmetric ring

We study the properties of an N-site tight-binding ring with parity and time-reversal (PT) symmetric, Hermitian, site-dependent tunneling and a pair of non-Hermitian, PT-symmetric, loss and gain impurities $\pm i\gamma$. The properties of such lattices with open boundary conditions have been intensely explored over the past two years. We numerically investigate the PT-symmetric phase in a ring with a position-dependent tunneling function $t_\alpha(k)=[k(N-k)]^{\alpha/2}$ that, in an open lattice, leads to a strengthened PT-symmetric phase, and study the evolution of the PT-symmetric phase from the open chain to a ring. We show that, generally, periodic boundary conditions weaken the PT-symmetric phase, although for experimentally relevant lattice sizes $N \sim 50$, it remains easily accessible. We show that the chirality, quantified by the (magnitude of the) average transverse momentum of a wave packet, shows a maximum at the PT-symmetric threshold. Our results show that although the wavepacket intensity increases monotonically across the PT-breaking threshold, the average momentum decays monotonically on both sides of the threshold.Comment: 11 pages, 5 figures, preprin

PT-Symmetric Electronics

We show both theoretically and experimentally that a pair of inductively coupled active LRC circuits (dimer), one with amplification and another with an equivalent amount of attenuation, display all the features which characterize a wide class of non-Hermitian systems which commute with the joint parity-time PT operator: typical normal modes, temporal evolution, and scattering processes. Utilizing a Liouvilian formulation, we can define an underlying PT-symmetric Hamiltonian, which provides important insight for understanding the behavior of the system. When the PT-dimer is coupled to transmission lines, the resulting scattering signal reveals novel features which reflect the PT-symmetry of the scattering target. Specifically we show that the device can show two different behaviors simultaneously, an amplifier or an absorber, depending on the direction and phase relation of the interrogating waves. Having an exact theory, and due to its relative experimental simplicity, PT-symmetric electronics offers new insights into the properties of PT-symmetric systems which are at the forefront of the research in mathematical physics and related fields.Comment: 17 pages, 7 figure

Extreme climatic events down-regulate the grassland biomass response to elevated carbon dioxide

Terrestrial ecosystems are considered as carbon sinks that may mitigate the impacts of increased atmospheric CO2 concentration ([CO2]). However, it is not clear what their carbon sink capacity will be under extreme climatic conditions. In this study, we used long-term (1998–2013) data from a C3 grassland Free Air CO2 Enrichment (FACE) experiment in Germany to study the combined effects of elevated [CO2] and extreme climatic events (ECEs) on aboveground biomass production. CO2 fertilization effect (CFE), which represents the promoted plant photosynthesis and water use efficiency under higher [CO2], was quantiffied by calculating the relative differences in biomass between the plots with [CO2] enrichment and the plots with ambient [CO2]. Down-regulated CFEs were found when ECEs occurred during the growing season, and the CFE decreases were statistically significant with p well below 0.05 (t-test). Of all the observed ECEs, the strongest CFE decreases were associated with intensive and prolonged heat waves. These findings suggest that more frequent ECEs in the future are likely to restrict the mitigatory effects of C3 grassland ecosystems, leading to an accelerated warming trend. To reduce the uncertainties of future projections, the atmosphere-vegetation interactions, especially the ECEs effects, are emphasized and need to be better accounted

An exactly solvable quantum-lattice model with a tunable degree of nonlocality

An array of N subsequent Laguerre polynomials is interpreted as an eigenvector of a non-Hermitian tridiagonal Hamiltonian $H$ with real spectrum or, better said, of an exactly solvable N-site-lattice cryptohermitian Hamiltonian whose spectrum is known as equal to the set of zeros of the N-th Laguerre polynomial. The two key problems (viz., the one of the ambiguity and the one of the closed-form construction of all of the eligible inner products which make $H$ Hermitian in the respective {\em ad hoc} Hilbert spaces) are discussed. Then, for illustration, the first four simplest, $k-$parametric definitions of inner products with $k=0,k=1,k=2$ and $k=3$ are explicitly displayed. In mathematical terms these alternative inner products may be perceived as alternative Hermitian conjugations of the initial N-plet of Laguerre polynomials. In physical terms the parameter $k$ may be interpreted as a measure of the "smearing of the lattice coordinates" in the model.Comment: 35 p

Hyperspectral Data Analysis in R: The hsdar Package

Hyperspectral remote sensing is a promising tool for a variety of applications including ecology, geology, analytical chemistry and medical research. This article presents the new hsdar package for R statistical software, which performs a variety of analysis steps taken during a typical hyperspectral remote sensing approach. The package introduces a new class for efficiently storing large hyperspectral data sets such as hyperspectral cubes within R. The package includes several important hyperspectral analysis tools such as continuum removal, normalized ratio indices and integrates two widely used radiation transfer models. In addition, the package provides methods to directly use the functionality of the caret package for machine learning tasks. Two case studies demonstrate the package's range of functionality: First, plant leaf chlorophyll content is estimated and second, cancer in the human larynx is detected from hyperspectral data