Luminescence spectroscopy of matrix-isolated z 6P state atomic manganese

The relaxation of electronically excited atomic manganese isolated in solid rare gas matrices is observed from recorded emission spectra, to be strongly site specific. z 6P state excitation of Mn atoms isolated in the red absorption site in Ar and Kr produces narrow a 4D and a 6D state emissions while blue-site excitation produces z 6P state fluorescence and broadened a 4D and a 6D emissions. Mn/Xe exhibits only a single thermally stable site whose emission at 620 nm is similar to the broad a 6D bands produced with blue-site excitation in Ar and Kr. Thus in ArsKrd, excitation of the red site at 393 s400d nm produces narrow line emissions at 427.5 s427.8d and 590 s585.7d nm. From their spectral positions, linewidths, and long decay times, these emission bands are assigned to the a 4D7/2 and a 6D9/2 states, respectively. Excitation of the blue site at 380 s385.5d nm produces broad emission at 413 s416d nm which, because of its nanosecond radiative lifetime, is assigned to resonance z 6P!a 6S fluorescence. Emission bands at 438 s440d and 625 s626.8d nm, also produced with blue-site excitation, are broader than their red-site equivalents at 427.5 and 590 nm s427.8 and 585.7 nm in Krd but from their millisecond and microsecond decay times are assigned to the a 4D and a 6D states. The line features observed in high resolution scans of the red-site emission at 427.5 and 427.8 nm in Mn/Ar and Mn/ Kr, respectively, have been analyzed with the Wp optical line shape function and identified as resolved phonon structure originating from very weak sS=0.4d electron-phonon coupling. The presence of considerable hot-phonon emission seven in 12 K spectrad and the existence of crystal field splittings of 35 and 45 cmâ1 on the excited a 4D7/2 level in Ar and Kr matrices have been identified in Wp line shape fits. The measured matrix lifetimes for the narrow red-site a 6D state emissions s0.29 and 0.65 msd in Ar and Kr are much shorter than the calculated s3 sd gas phase value. With the lifetime of the metastable a 6D9/2 state shortened by four orders of magnitude in the solid rare gases, it is clear that the probability of the âforbiddenâ a 6D!a 6S atomic transition is greatly enhanced in the solid state. A novel feature identified in the present work is the large width and shifted 4D and 6D emissions produced for Mn atoms isolated in the blue sites of Ar and Kr. In contrast, these states produce narrow, unshifted sgas-phase-liked 4D and 6D state emissions from the red site

Laser excitation spectroscopy of the A and B states of jet-cooled copper dimer: evidence for large electronic isotope shifts

Journal ArticleFluorescence excitation spectra recorded for the A-X system of jet-cooled Cu2 show conclusive evidence of a ?? = 0 transition, and the A state is thereby definitively assigned as ??u+. A previous assignment of the B state as ??u+ is confirmed, but the vibrational levels of this state are complicated by the presence of a perturbation at v' = 0. The perturbing state does not, however, appear to be either of the two optically accessible electronic states in this spectral region. Anomalously large electronic isotope shifts are observed for the A and B states, and this behavior is discussed in terms of the correspondingly large "specific mass shifts" observed in the optical spectra of atomic copper for transitions that couple states differing in the number of d electrons. Due to the large spin-orbit coupling constants in the "cMiole" configurations, it is proposed that the low-energy-excited molecular states of Cu2 derived from these configurations should be described by Hund's case (c) coupling. Dynamical effects observed in the gas phase and in solid matrices are briefly discussed in terms of this bonding scheme

Spectroscopic characterization of the Zn(4s(2))center dot Ne[(1)Sigma(+)] and Zn(4s4p pi)center dot Ne[(1)Pi(1)] van der Waals states

The Zn(4s2)·Ne[1Σ+] and the Zn(4s4pπ)·Ne[1Π1] states have been characterized by laser-induced fluorescence spectroscopy. Bond lengths were determined from simulations of the partially-resolved rotational structure of the 1Π ← 1Σ+ transitions, while bond strengths were estimated from a Birge–Sponer extrapolation with allowance for consistent errors resulting from similar procedures in the analogous Cd·Ne and Hg·Ne transitions. The van der Waals bonding in these states is discussed briefly and compared to that in the analogous M·RG states, where M=Mg, Zn, Cd, Hg and RG=Ne, Ar, Kr, Xe

Spectroscopic characterization of the Zn(4s(2))center dot Ne[(1)Sigma(+)] and Zn(4s4p pi)center dot Ne[(1)Pi(1)] van der Waals states

The Zn(4s2)·Ne[1Σ+] and the Zn(4s4pπ)·Ne[1Π1] states have been characterized by laser-induced fluorescence spectroscopy. Bond lengths were determined from simulations of the partially-resolved rotational structure of the 1Π ← 1Σ+ transitions, while bond strengths were estimated from a Birge–Sponer extrapolation with allowance for consistent errors resulting from similar procedures in the analogous Cd·Ne and Hg·Ne transitions. The van der Waals bonding in these states is discussed briefly and compared to that in the analogous M·RG states, where M=Mg, Zn, Cd, Hg and RG=Ne, Ar, Kr, Xe

The role of spin-orbit coupling in the optical spectroscopy of atomic sodium isolated in solid xenon

Molecular dynamics calculations, based on the diatomics-in-molecules method, have been used to probe the manifestations of spin-orbit (SO) coupling in the experimental absorption bands of atomic sodium isolated in solid xenon. Inclusion of SO coupling of –320 cm−1 in spectral simulations of the 3p 2P 3s 2S transition leads to unequal band spacings which very closely match the asymmetrical bandshape observed for blue single vacancy (SV) site occupancy. This SO value, extracted in a previous MCD study, reveals the dramatic change in the effective SO coupling constant of the Na atom (from the gas phase value of +17 cm−1 ) in solid Xe when it is close to the 12 xenon atoms in the first surrounding sphere. In contrast, the symmetrical three-fold split band of the red tetra vacancy (TV) site in Na/Xe is not affected nearly as much by SO coupling. This reflects a greatly reduced “external heavy atom” effect when the 24 Xe atoms surrounding the Na atom in TV are located at greater distances. The contrasting behavior of sodium in the SV and TV sites suggests a strong dependence of the SO coupling strength on the Na–Xe distance

Effects of trapping site on the spectroscopy of 1P1 excited group 12 metal atoms in rare gas matrices

A molecular dynamics deposition model has been used to simulate the growth of rare gas matrices doped with atoms of the group 12 elements zinc, cadmium and mercury. This study investigates the sites occupied by Zn, Cd and Hg metal atoms when isolated in the solid rare gases. To probe the results, the resonance 1P1 1 S0 transitions of the matrix-isolated metal atoms were calculated and compared with the recorded spectra of the M/RG solids. The theoretical spectroscopy obtained in this work was generated using the molecular dynamics with quantum transitions method. In Ne matrices the metal atoms preferably occupy tetra- and hexa-vacancy sites while in the case of Xe matrices, only the single vacancy site is formed. For Ar and Kr matrices Zn but especially Cd can be trapped in tetra- and hexa-vacancy sites in addition to single-vacancy sites, while Hg atoms show exclusive occupancy in single vacancy sites

Histone Acetylation-Mediated Regulation of the Hippo Pathway

The Hippo pathway is a signaling cascade recently found to play a key role in tumorigenesis therefore understanding the mechanisms that regulate it should open new opportunities for cancer treatment. Available data indicate that this pathway is controlled by signals from cell-cell junctions however the potential role of nuclear regulation has not yet been described. Here we set out to verify this possibility and define putative mechanism(s) by which it might occur. By using a luciferase reporter of the Hippo pathway, we measured the effects of different nuclear targeting drugs and found that chromatin-modifying agents, and to a lesser extent certain DNA damaging drugs, strongly induced activity of the reporter. This effect was not mediated by upstream core components (i.e. Mst, Lats) of the Hippo pathway, but through enhanced levels of the Hippo transducer TAZ. Investigation of the underlying mechanism led to the finding that cancer cell exposure to histone deacetylase inhibitors induced secretion of growth factors and cytokines, which in turn activate Akt and inhibit the GSK3 beta associated protein degradation complex in drug-affected as well as in their neighboring cells. Consequently, expression of EMT genes, cell migration and resistance to therapy were induced. These processes were suppressed by using pyrvinium, a recently described small molecule activator of the GSK 3 beta associated degradation complex. Overall, these findings shed light on a previously unrecognized phenomenon by which certain anti-cancer agents may paradoxically promote tumor progression by facilitating stabilization of the Hippo transducer TAZ and inducing cancer cell migration and resistance to therapy. Pharmacological targeting of the GSK3 beta associated degradation complex may thus represent a unique approach to treat cancer. © 2013 Basu et al

Celtic FC’s 1967 Lisbon Lions:Why the European Cup victory of the first club from Britain was a defining moment for the Irish diaspora in Scotland

In 1967, in Lisbon, Celtic Football Club, won the European Cup becoming the first club outside of Portugal, Spain and Italy to win it. The win was and is totemic for the Irish Catholic immigrant community in Scotland that has historically supported Celtic. We suggest the significance of the win reveals intersections of ethnicity, religion, nationalism, and the politics of ‘sectarianism’ in Scotland. During a period of discriminatory practices and attitudes towards Irish descended Catholics in Scotland, this iconic win for a Scottish based club born of Irish Catholics personified for this diaspora that (on one level) their day had arrived. This article explores the socio-cultural significance and legacy of ‘Lisbon 67ʹ for insider and outsider groups in Scotland. We reveal that soccer remains a central component of group memory connecting the past, present and future. We suggest Celtic’s win offered confidence and hope to a marginalized group within Scotland

Rise and Fall of a Multi-sheet Intrusive Complex, Elba Island, Italy

Elba Island intrusive complex: multisheet laccoliths, sheeted pluton, mafic dyke swarm. Laccolith magma fed from dykes and emplaced in crustal discontinuities (traps). Pluton growth by downward stacking of three magma pulses. Laccoliths and plutons: different outcomes of similar processes in different conditions. Emplacement of excess magma in a short time led to massive gravity slide

Cognitive Performance in Centenarians and the Oldest Old: Norms from the Georgia Centenarian Study

We present normative data from a large population-based sample of centenarians for several brief, global neurocognitive tasks amenable for frail elders. Comparative data from octogenarians are included. A total of 244 centenarians and 80 octogenarians from Phase III of the Georgia Centenarian Study were administered the Mini-Mental Status Examination, Severe Impairment Battery, and Behavioral Dyscontrol Scale. Centenarians (age 98–107) were stratified into three age cohorts (98–99, 100–101, 102–107), octogenarians into two 5- year cohorts (80–84, 85–89). Highly significant differences were observed between groups on all measures, with greater variation and dispersion in performance among centenarians, as well as stronger associations between age and performance. Descriptive statistics and normative ranges (unweighted and population-weighted) are provided by age cohort. Additional statistics are provided by education level. While most previous centenarian studies have used convenience samples, ours is population-based and likely more valid for comparison in applied settings. Results suggest centenarians look different than do even the oldest age range of most normative aging datasets (e.g., 85–90). Results support using global measures of neurocognition to describe cognitive status in the oldest old, and we provide normative comparisons to do so