Photo- and solvatochromic properties of nitrobenzospiropyran in ionic liquids containing the [NTf2]- anion

The photo-, thermo- and solvatochromic properties of 2,3-dihydro-10,30,30-trimethyl-6-nitrospiro- [1-benzopyran-2,20-1H-indole] (BSP-NO2) were studied in ILs containing the anion [NTf2]- by UV-Vis absorption spectroscopy, ab initio molecular orbital theory and density functional theory (DFT) calculations. It was found that the kinetics and thermodynamics of the BSP-NO2 MC (merocyanine) equilibrium was sensitive to the nature of the cation. It was also observed that the imidazolium cation can form a through-space orbital interaction with the MC isomer, rather than a simple electrostatic interaction, thus preventing the MC conversion back to the BSP-NO2 isomer. The BSP-NO2 MC equilibrium thus serves as a model system for studying modes of interaction of the cations in ionic liquids

Comorbidity and response to TNF inhibitors in axial spondyloarthritis : longitudinal analysis of the BSRBR-AS

Acknowledgements: Funding: The BSRBR-AS is funded by the British Society for Rheumatology (BSR) who have received funding for this from Pfizer, AbbVie and UCB. These companies receive advance copies of manuscripts for comments. They have no input in determining the topics for analysis or work involved in undertaking it. Disclosures: The authors declare no conflicts of interest. Contribution: SSZ analysed the data and wrote the manuscript, with significant input from all coauthors. GJM and GTJ are Chief Investigator and Deputy Chief Investigator respectively on BSRBR-AS and designed the study and oversaw its conduct. In the current project they discussed results and provided input into drafts of the manuscript. Data availability: Data from the British Society for Rheumatology Biologics Register for Ankylosing Spondylitis are available to external investigators, on reasonable request. For information on how to access data, see: http://www.rheumatology.org.uk. We are grateful to the staff of the BSRBR-AS register and to the recruiting staff at the clinical centres, details of which are available at: www.abdn.ac.uk/bsrbr-asPeer reviewedPublisher PD

Association between comorbidities and disease activity in axial spondyloarthritis : results from the BSRBR-AS

Funding: The BSRBR-AS is funded by the British Society for Rheumatology (BSR) who have received funding for this from Pfizer, AbbVie and UCB. These companies receive advance copies of manuscripts for comments. They have no input in determining the topics for analysis or work involved in undertaking it. We are grateful to the staff of the BSRBR-AS register and to the recruiting staff at the clinical centres, details of which are available at: http://www.abdn.ac.uk/bsrbr-as S.S.Z. analysed the data and wrote the manuscript, with significant input from all co-authors. G.J.M. and G.T.J. are Chief Investigator and Deputy Chief Investigator, respectively, on BSRBR-AS and designed the study and oversaw its conduct. In the current project they discussed results and provided input into drafts of the manuscript. Disclosure statement: The authors have declared no conflicts of interest.Peer reviewedPublisher PD

Vagueness as Indecision

This essay explores the thesis that for vague predicates, uncertainty over whether a borderline instance x of red/large/tall/good is to be understood as practical uncertainty over whether to treat x as red/large/tall/good. Expressivist and quasi-realist treatments of vague predicates due to John MacFarlane and Daniel Elstein provide the stalking-horse. It examines the notion of treating/counting a thing as F, and links a central question about our attitudes to vague predications to normative evaluation of plans to treat a thing as F. The essay examines how the account applies to normatively defective or contested terms. The final section raises a puzzle about the mechanics of MacFarlane’s detailed implementation for the case of gradable adjectives

Ionic and electronic properties of the topological insulator Bi2_2Te2_2Se investigated using β\beta-detected nuclear magnetic relaxation and resonance of 8^8Li

We report measurements on the high temperature ionic and low temperature electronic properties of the 3D topological insulator Bi$_2$Te$_2$Se using ion-implanted $^8$Li $\beta$-detected nuclear magnetic relaxation and resonance. With implantation energies in the range 5-28 keV, the probes penetrate beyond the expected range of the topological surface state, but are still within 250 nm of the surface. At temperatures above ~150 K, spin-lattice relaxation measurements reveal isolated $^8$Li$^{+}$ diffusion with an activation energy $E_{A} = 0.185(8)$ eV and attempt frequency $\tau_{0}^{-1} = 8(3) \times 10^{11}$ s$^{-1}$ for atomic site-to-site hopping. At lower temperature, we find a linear Korringa-like relaxation mechanism with a field dependent slope and intercept, which is accompanied by an anomalous field dependence to the resonance shift. We suggest that these may be related to a strong contribution from orbital currents or the magnetic freezeout of charge carriers in this heavily compensated semiconductor, but that conventional theories are unable to account for the extent of the field dependence. Conventional NMR of the stable host nuclei may help elucidate their origin.Comment: 17 pages, 12 figures, submitted to Phys. Rev.

Epitaxy: Programmable Atom Equivalents

The programmability of DNA makes it an attractive structure-directing ligand for the assembly of nanoparticle (NP) superlattices in a manner that mimics many aspects of atomic crystallization. However, the synthesis of multilayer single crystals of defined size remains a challenge. Though previous studies considered lattice mismatch as the major limiting factor for multilayer assembly, thin film growth depends on many interlinked variables. Here, a more comprehensive approach is taken to study fundamental elements, such as the growth temperature and the thermodynamics of interfacial energetics, to achieve epitaxial growth of NP thin films. Both surface morphology and internal thin film structure are examined to provide an understanding of particle attachment and reorganization during growth. Under equilibrium conditions, single crystalline, multilayer thin films can be synthesized over 500 × 500 μm² areas on lithographically patterned templates, whereas deposition under kinetic conditions leads to the rapid growth of glassy films. Importantly, these superlattices follow the same patterns of crystal growth demonstrated in atomic thin film deposition, allowing these processes to be understood in the context of well-studied atomic epitaxy and enabling a nanoscale model to study fundamental crystallization processes. Through understanding the role of epitaxy as a driving force for NP assembly, we are able to realize 3D architectures of arbitrary domain geometry and size.United States. Air Force Office of Scientific Research (AFOSR FA9550-11-1-0275)United States. Air Force Office of Scientific Research (FA9550-12-1-0280)United States. Department of Defense (N00014-15-1-0043)United States. Department of Energy (Grant DE-SC0000989-0002)National Science Foundation (U.S.) (Award DMR-1121262

Multiple photosynthetic transitions, polyploidy, and lateral gene transfer in the grass subtribe Neurachninae

The Neurachninae is the only grass lineage known to contain C3, C4, and C3–C4 intermediate species, and as such has been suggested as a model system for studies of photosynthetic pathway evolution in the Poaceae; however, a lack of a robust phylogenetic framework has hindered this possibility. In this study, plastid and nuclear markers were used to reconstruct evolutionary relationships among Neurachninae species. In addition, photosynthetic types were determined with carbon isotope ratios, and genome sizes with flow cytometry. A high frequency of autopolyploidy was found in the Neurachninae, including in Neurachne munroi F.Muell. and Paraneurachne muelleri S.T.Blake, which independently evolved C4 photosynthesis. Phylogenetic analyses also showed that following their separate C4 origins, these two taxa exchanged a gene encoding the C4 form of phosphoenolpyruvate carboxylase. The C3–C4 intermediate Neurachne minor S.T.Blake is phylogenetically distinct from the two C4 lineages, indicating that intermediacy in this species evolved separately from transitional stages preceding C4 origins. The Neurachninae shows a substantial capacity to evolve new photosynthetic pathways repeatedly. Enablers of these transitions might include anatomical pre-conditions in the C3 ancestor, and frequent autopolyploidization. Transfer of key C4 genetic elements between independently evolved C4 taxa may have also facilitated a rapid adaptation of photosynthesis in these grasses that had to survive in the harsh climate appearing during the late Pliocene in Australia

AAPT Diagnostic Criteria for Fibromyalgia

Acknowledgements Support was provided by the Analgesic, Anesthetic, and Addictions Clinical Trial Translations, Innovations, Opportunities, and Networks public-private partnership with the US Food and Drug Administration (FDA).Peer reviewedPublisher PD

Kondo screening in d-wave superconductors in a Zeeman field and implications for STM spectra of Zn-doped cuprates

We consider the screening of an impurity moment in a d-wave superconductor under the influence of a Zeeman magnetic field. Using the Numerical Renormalization Group technique, we investigate the resulting pseudogap Kondo problem, in particular the field-induced crossover behavior in the vicinity of the zero-field boundary quantum phase transition. The impurity spectral function and the resulting changes in the local host density of states are calculated, giving specific predictions for high-field STM measurements on impurity-doped cuprates.Comment: 5 pages, 4 figs, (v2) remark on c-axis field added, discussion extended, (v3) final version as publishe