Supermolecular-Chromophore-Sensitized Near-Infrared-to-Visible Photon Upconversion

Selective near-IR (NIR) excitation (780 nm) of the conjugated supermolecule ruthenium(II) [15-(4?-ethynyl-(2,2?;6?,2??-terpyridinyl))-bis[(5,5?,-10,20-di(2?,6?-bis(3,3-dimethylbutoxy)phenyl)porphinato)zinc(II)]ethyne][4?-pyrrolidin-1-yl-2,2?;6?,2??-terpyridine] bis(hexafluorophosphate) (Pyr1RuPZn2) in solutions containing N,N-bis(ethylpropyl)perylene-3,4,9,10-tetracarboxylicdiimide (PDI) or tetracene gives rise to a substantial anti-Stokes energy gain (PDI, 0.70 eV; tetracene, 0.86 eV). Experimental data clearly demonstrate that this upconverted fluorescence signal is produced via Pyr1RuPZn2-sensitized triplet?triplet annihilation (TTA) photochemistry. The TTA process was confirmed by the quadratic dependence of the integrated 1PDI* emission centered at 541 nm derived from 780 nm laser excitation. The T1?Tn excited state absorption decay of Pyr1RuPZn2, monitored at 900 nm as a function of PDI concentration, revealed Stern?Volmer and bimolecular quenching constants of 10?048 M?1 and 5.9 ? 108 M?1 s?1, respectively, for the PDI triplet sensitization process. The T1?Tn PDI extinction coefficient at 560 nm (εT = 6.6 ? 104 M?1 cm?1) was determined through the triplet energy transfer method utilizing anthracene as the donor chromophore. 3PDI* transient triplet absorption dynamics observed as a function of 485 nm incident nanosecond pump laser fluence demonstrate a bimolecular 3PDI*?3PDI* TTA rate constant (kTT = 1.0 ± 0.2 ? 109 M?1 s?1). The maximum quantum yield of the supermolecule-sensitized PDI upconverted emission (ΦUC = 0.0075 ± 0.0002) was determined relative to [Os(phen)3][PF6]2 at an incident laser power of 22 mW at 780 nm. This study successfully demonstrates NIR-to-visible photon upconversion and achieves a new record anti-Stokes shift of 0.86 eV for sensitized TTA, using the supermolecular Pyr1RuPZn2sensitizer. The stability of the Pyr1RuPZn2/PDI chromophore combination is readily apparent as continuous irradiation at 780 nm produces 541 nm centered fluorescence with no significant decrease in intensity measured over time domains exceeding several hours. The molecular components of these NIR-to-vis upconverting compositions illustrate that substantial anti-Stokes energy gains via a TTA process can be effortlessly realized

Rates and controls of nitrification in a large oligotrophic lake

Recent discoveries have altered prevailing paradigms concerning the conditions under which nitrification takes place and the organisms responsible for nitrification in aquatic ecosystems. In Lake Superior, nitrate (NO-3) concentrations have increased fivefold in the past century. Although previous evidence indicated that most NO-3 is generated by nitrification within the lake, important questions remain concerning the magnitude and controls of nitrification, and which microbial groups are primarily responsible for this process. We measured water-column nitrification rates in the western basin of Lake Superior during five research cruises from November 2009 to March 2011. Using in situ bottle incubations at 10 depths, we quantified nitrification rates using both the oxidation of 15N-labeled ammonium (NH+4) and the uptake of 14C associated with nitrification. Average rates of NH+4 oxidation ranged from 18-34 nmol N L-1 d-1 across the five cruises, similar to values reported for the coastal ocean, and two orders of magnitude lower than values reported from other lakes. Low nitrification rates observed in the epilimnion corresponded to the absence of ammonium-oxidizing archaea and nitrite-oxidizing bacteria. The measured rates of nitrification are \u3e 50-fold greater than the long-term NO-3 rise in the lake, indicating that N is actively cycling and that long-term change in this ecosystem is mediated by internal dynamics. © 2013, by the Association for the Sciences of Limnology and Oceanography, Inc

Calculating the carbon footprint:implications for governing emissions and gender relations

In this article, we use fresh empirical evidence, and draw on feminist and critical accounting and organisational theories to contend that carbon calculators can be interpreted as discriminatory control technologies. They do this by providing a new and flexible vocabulary for governing expenses, costs and investments at a distance, avoiding a sense of direct intervention by the government. Thus, given our stance that the carbon calculator cannot be considered a neutral tool, we argue that it has the potential to control personal responsibilities regarding both environmental and family‐based issues

A terminal assessment of stages theory : introducing a dynamic states approach to entrepreneurship

Stages of Growth models were the most frequent theoretical approach to understanding entrepreneurial business growth from 1962 to 2006; they built on the growth imperative and developmental models of that time. An analysis of the universe of such models (N=104) published in the management literature shows no consensus on basic constructs of the approach, nor is there any empirical confirmations of stages theory. However, by changing two propositions of the stages models, a new dynamic states approach is derived. The dynamic states approach has far greater explanatory power than its precursor, and is compatible with leading edge research in entrepreneurship

Measurement of the polarisation of W bosons produced with large transverse momentum in pp collisions at sqrt(s) = 7 TeV with the ATLAS experiment

This paper describes an analysis of the angular distribution of W->enu and W->munu decays, using data from pp collisions at sqrt(s) = 7 TeV recorded with the ATLAS detector at the LHC in 2010, corresponding to an integrated luminosity of about 35 pb^-1. Using the decay lepton transverse momentum and the missing transverse energy, the W decay angular distribution projected onto the transverse plane is obtained and analysed in terms of helicity fractions f0, fL and fR over two ranges of W transverse momentum (ptw): 35 < ptw < 50 GeV and ptw > 50 GeV. Good agreement is found with theoretical predictions. For ptw > 50 GeV, the values of f0 and fL-fR, averaged over charge and lepton flavour, are measured to be : f0 = 0.127 +/- 0.030 +/- 0.108 and fL-fR = 0.252 +/- 0.017 +/- 0.030, where the first uncertainties are statistical, and the second include all systematic effects.Comment: 19 pages plus author list (34 pages total), 9 figures, 11 tables, revised author list, matches European Journal of Physics C versio

Observation of a new chi_b state in radiative transitions to Upsilon(1S) and Upsilon(2S) at ATLAS

The chi_b(nP) quarkonium states are produced in proton-proton collisions at the Large Hadron Collider (LHC) at sqrt(s) = 7 TeV and recorded by the ATLAS detector. Using a data sample corresponding to an integrated luminosity of 4.4 fb^-1, these states are reconstructed through their radiative decays to Upsilon(1S,2S) with Upsilon->mu+mu-. In addition to the mass peaks corresponding to the decay modes chi_b(1P,2P)->Upsilon(1S)gamma, a new structure centered at a mass of 10.530+/-0.005 (stat.)+/-0.009 (syst.) GeV is also observed, in both the Upsilon(1S)gamma and Upsilon(2S)gamma decay modes. This is interpreted as the chi_b(3P) system.Comment: 5 pages plus author list (18 pages total), 2 figures, 1 table, corrected author list, matches final version in Physical Review Letter

Search for displaced vertices arising from decays of new heavy particles in 7 TeV pp collisions at ATLAS

We present the results of a search for new, heavy particles that decay at a significant distance from their production point into a final state containing charged hadrons in association with a high-momentum muon. The search is conducted in a pp-collision data sample with a center-of-mass energy of 7 TeV and an integrated luminosity of 33 pb^-1 collected in 2010 by the ATLAS detector operating at the Large Hadron Collider. Production of such particles is expected in various scenarios of physics beyond the standard model. We observe no signal and place limits on the production cross-section of supersymmetric particles in an R-parity-violating scenario as a function of the neutralino lifetime. Limits are presented for different squark and neutralino masses, enabling extension of the limits to a variety of other models.Comment: 8 pages plus author list (20 pages total), 8 figures, 1 table, final version to appear in Physics Letters

Measurement of the inclusive isolated prompt photon cross-section in pp collisions at sqrt(s)= 7 TeV using 35 pb-1 of ATLAS data

A measurement of the differential cross-section for the inclusive production of isolated prompt photons in pp collisions at a center-of-mass energy sqrt(s) = 7 TeV is presented. The measurement covers the pseudorapidity ranges |eta|<1.37 and 1.52<=|eta|<2.37 in the transverse energy range 45<=E_T<400GeV. The results are based on an integrated luminosity of 35 pb-1, collected with the ATLAS detector at the LHC. The yields of the signal photons are measured using a data-driven technique, based on the observed distribution of the hadronic energy in a narrow cone around the photon candidate and the photon selection criteria. The results are compared with next-to-leading order perturbative QCD calculations and found to be in good agreement over four orders of magnitude in cross-section.Comment: 7 pages plus author list (18 pages total), 2 figures, 4 tables, final version published in Physics Letters

T-cell regulation in Erythema Nodosum Leprosum.

Leprosy is a disease caused by Mycobacterium leprae where the clinical spectrum correlates with the patient immune response. Erythema Nodosum Leprosum (ENL) is an immune-mediated inflammatory complication, which causes significant morbidity in affected leprosy patients. The underlying cause of ENL is not conclusively known. However, immune-complexes and cell-mediated immunity have been suggested in the pathogenesis of ENL. The aim of this study was to investigate the regulatory T-cells in patients with ENL. Forty-six untreated patients with ENL and 31 non-reactional lepromatous leprosy (LL) patient controls visiting ALERT Hospital, Ethiopia were enrolled to the study. Blood samples were obtained before, during and after prednisolone treatment of ENL cases. Peripheral blood mononuclear cells (PBMCs) were isolated and used for immunophenotyping of regulatory T-cells by flow cytometry. Five markers: CD3, CD4 or CD8, CD25, CD27 and FoxP3 were used to define CD4+ and CD8+ regulatory T-cells. Clinical and histopathological data were obtained as supplementary information. All patients had been followed for 28 weeks. Patients with ENL reactions had a lower percentage of CD4+ regulatory T-cells (1.7%) than LL patient controls (3.8%) at diagnosis of ENL before treatment. After treatment, the percentage of CD4+regulatory T-cells was not significantly different between the two groups. The percentage of CD8+ regulatory T-cells was not significantly different in ENL and LL controls before and after treatment. Furthermore, patients with ENL had higher percentage of CD4+ T-ells and CD4+/CD8+ T-cells ratio than LL patient controls before treatment. The expression of CD25 on CD4+ and CD8+ T-cells was not significantly different in ENL and LL controls suggesting that CD25 expression is not associated with ENL reactions while FoxP3 expression on CD4+ T-cells was significantly lower in patients with ENL than in LL controls. We also found that prednisolone treatment of patients with ENL reactions suppresses CD4+ T-cell but not CD8+ T-cell frequencies. Hence, ENL is associated with lower levels of T regulatory cells and higher CD4+/CD8+ T-cell ratio. We suggest that this loss of regulation is one of the causes of ENL

Measurement of D*+/- meson production in jets from pp collisions at sqrt(s) = 7 TeV with the ATLAS detector

This paper reports a measurement of D*+/- meson production in jets from proton-proton collisions at a center-of-mass energy of sqrt(s) = 7 TeV at the CERN Large Hadron Collider. The measurement is based on a data sample recorded with the ATLAS detector with an integrated luminosity of 0.30 pb^-1 for jets with transverse momentum between 25 and 70 GeV in the pseudorapidity range |eta| < 2.5. D*+/- mesons found in jets are fully reconstructed in the decay chain: D*+ -> D0pi+, D0 -> K-pi+, and its charge conjugate. The production rate is found to be N(D*+/-)/N(jet) = 0.025 +/- 0.001(stat.) +/- 0.004(syst.) for D*+/- mesons that carry a fraction z of the jet momentum in the range 0.3 < z < 1. Monte Carlo predictions fail to describe the data at small values of z, and this is most marked at low jet transverse momentum.Comment: 10 pages plus author list (22 pages total), 5 figures, 1 table, matches published version in Physical Review