Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior

Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores

In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891)

LensPerfect: Gravitational Lens Massmap Reconstructions Yielding Exact Reproduction of All Multiple Images

We present a new approach to gravitational lens massmap reconstruction. Our massmap solutions perfectly reproduce the positions, fluxes, and shears of all multiple images. And each massmap accurately recovers the underlying mass distribution to a resolution limited by the number of multiple images detected. We demonstrate our technique given a mock galaxy cluster similar to Abell 1689 which gravitationally lenses 19 mock background galaxies to produce 93 multiple images. We also explore cases in which far fewer multiple images are observed, such as four multiple images of a single galaxy. Massmap solutions are never unique, and our method makes it possible to explore an extremely flexible range of physical (and unphysical) solutions, all of which perfectly reproduce the data given. Each reconfiguration of the source galaxies produces a new massmap solution. An optimization routine is provided to find those source positions (and redshifts, within uncertainties) which produce the "most physical" massmap solution, according to a new figure of merit developed here. Our method imposes no assumptions about the slope of the radial profile nor mass following light. But unlike "non-parametric" grid-based methods, the number of free parameters we solve for is only as many as the number of observable constraints (or slightly greater if fluxes are constrained). For each set of source positions and redshifts, massmap solutions are obtained "instantly" via direct matrix inversion by smoothly interpolating the deflection field using a recently developed mathematical technique. Our LensPerfect software is straightforward and easy to use and is made publicly available via our website.Comment: 17 pages, 18 figures, accepted by ApJ. Software and full-color version of paper available at http://www.its.caltech.edu/~coe/LensPerfect

Femininity, Childhood and the Non-Making of a Sporting Celebrity: The Beth Tweddle Case

Gymnastics is regularly classified as a feminine-appropriate sport, embodying grace and elegance and is an Olympic sport which has regularly produced female sporting celebrities. Beth Tweddle is the most successful British gymnast of all time and the first to achieve international success, culminating in a medal at London 2012, yet she has received relatively little media coverage and few corporate endorsements. Employing a 'negative case' methodology, this athlete's relative lack of celebrity is investigated. The article suggests that it can be explained by (a) contradictions underpinning the gender-designation of gymnastics, and (b) the social invisibility of a core audience for the sport: young girls. An implication is that the achievement of celebrity within 'feminine' sport may be increasingly unattainable, especially for female athletes. The article uses mixed methods, including primary analysis of print and social media and secondary analysis of a national survey of young people in the UK

Scalability of Non-intrusive Load Monitoring for Shipboard Applications

The non-intrusive load monitor has been demonstrated as an effective tool for evaluating and monitoring shipboard electro-mechanical systems through analysis of electrical power data. A key advantage of the non-intrusive approach is the ability to reduce sensor count by monitoring collections of loads. This paper reviews trade-offs that affect the likely performance of the NILM in a real world environment.Massachusetts Institute of Technology. Sea Grant College Program; Grainger Foundation; National Science Foundation (U.S.); United States. National Aeronautics and Space Administration; United States. Coast Guard; United States. Office of Naval Research. Electric Ship Research and Development Consortium; NAVSEA; University of North Carolin

Closure between measured and modelled particle hygroscopic growth during TORCH2 implies ammonium nitrate artefact in the HTDMA measurements

International audienceMeasurements of aerosol properties were made in aged polluted and clean background air masses encountered at the North Norfolk (UK) coastline during the second field campaign of the Tropospheric ORganic CHemistry project (TORCH2) in May 2004. Hygroscopic growth factor (GF) measurements were performed at 90% relative humidity (RH) for D0=27?217 nm particles using a Hygroscopicity Tandem Differential Mobility Analyser (HTDMA), while the aerosol composition was simultaneously measured with an Aerodyne aerosol mass spectrometer (Q-AMS). During the clean background events the aerosol was characterised by little size dependence of properties with generally large GFs and inorganic sulphate being the dominant compound. In aged polluted air masses the particles were dominated by inorganic sulphate and nitrate at larger sizes, whereas organics were the largest fraction in smaller particles, thus explaining the trend of smaller GFs at smaller sizes. Organics do contribute to the hygroscopic growth, particularly at small sizes, but generally the dominant contribution to growth at 90% RH comes from inorganic salts. The ZSR mixing rule was used to predict GFs based on the chemical composition, theoretical GFs of pure inorganic salts and a "bulk" GF of ~1.20 for the organics. Good quantitative closure with HTDMA measurements as a function of both particle size and time was achieved in the absence of nitrate. However, GFs were clearly overpredicted at times when a significant fraction of nitrate was present. After careful considerations we attribute the overprediction to substantial evaporation losses of ammonium nitrate in the HTDMA instrument. If true, this implies that the ZSR predictions based on composition might be more representative of the actual "bulk" behaviour of undisturbed ambient particles than the HTDMA measurements. The simplified model approach using the ZSR rule and a constant organic growth factor made high size and time resolution possible, which has proven to be essential for a valid closure study. The ZSR mixing rule appears to be sufficiently accurate, as the GF predictions are more sensitive to the exact GFs of the inorganic compounds than to the growth factor of the moderately hygroscopic organics. Therefore a more detailed analysis and modelling of the organic fraction at the expense of time and size resolution is not worth the effort for an aged aerosol and discrepancies in either direction might even be cancelled out by averaging

Antideuteron yield at the AGS and coalescence implications

We present Experiment 864's measurement of invariant antideuteron yields in 11.5A GeV/c Au + Pt collisions. The analysis includes 250 million triggers representing 14 billion 10% central interactions sampled for events with high mass candidates. We find (1/2 pi pt) d^(2)N/dydpt = 3.5 +/- 1.5 (stat.) +0.9,-0.5 (sys.) x 10^(-8) GeV^(-2)c^(2) for 1.8=0.35 GeV/c (y(cm)=1.6) and 3.7 +/- 2.7 (stat.) +1.4,-1.5 (sys.) x 10^(-8) GeV^(-2)c^(2) for 1.4=0.26 GeV/c, and a coalescence parameter B2-bar of 4.1 +/- 2.9 (stat.) +2.3,-2.4 (sys.) x 10^(-3) GeV^(2)c^(-3). Implications for the coalescence model and antimatter annihilation are discussed.Comment: 8 pages, 4 figures, Latex, submitted to Phys. Rev. Let

Beyond 'Global Production Networks': Australian Fashion Week's Trans-Sectoral Synergies

When studies of industrial organisation are informed by commodity chain, actor network, or global production network theories and focus on tracing commodity flows, social networks, or a combination of the two, they can easily overlook the less routine trans-sectoral associations that are crucial to the creation and realisation of value. This paper shifts attention to identifying the sites at which diverse specialisations meet to concentrate and amplify mutually reinforcing circuits of value. These valorisation processes are demonstrated in the case of Australian Fashion Week, an event in which multiple interests converge to synchronize different expressions of fashion ideas, actively construct fashion markets and enhance the value of a diverse range of fashionable commodities. Conceptualising these interconnected industries as components of a trans-sectoral fashion complex has implications for understanding regional development, world cities, production location, and the manner in which production systems “touch down” in different places

The Bright End of the z~9 and z~10 UV Luminosity Functions using all five CANDELS Fields

The deep, wide-area (~800-900 arcmin**2) near-infrared/WFC3/IR + Spitzer/IRAC observations over the CANDELS fields have been a remarkable resource for constraining the bright end of high redshift UV luminosity functions (LFs). However, the lack of HST 1.05-micron observations over the CANDELS fields has made it difficult to identify z~9-10 sources robustly, since such data are needed to confirm the presence of an abrupt Lyman break at 1.2 microns. We report here on the successful identification of many such z~9-10 sources from a new HST program (z9-CANDELS) that targets the highest-probability z~9-10 galaxy candidates with observations at 1.05 microns, to search for a robust Lyman-break at 1.2 microns. The potential z~9-10 candidates are preselected from the full HST, Spitzer/IRAC S-CANDELS observations, and the deepest-available ground-based optical+near-infrared observations. We identified 15 credible z~9-10 galaxies over the CANDELS fields. Nine of these galaxies lie at z~9 and 5 are new identifications. Our targeted follow-up strategy has proven to be very efficient in making use of scarce HST time to secure a reliable sample of z~9-10 galaxies. Through extensive simulations, we replicate the selection process for our sample (both the preselection and follow-up) and use it to improve current estimates for the volume density of bright z~9 and z~10 galaxies. The volume densities we find are 5(-2)(+3)x and 8(-3)(+9)x lower, respectively, than found at z~8. When compared with the best-fit evolution (i.e., dlog_{10} rho(UV)/dz=-0.29+/-0.02) in the UV luminosities densities from z~8 to z~4 integrated to 0.3L*(z=3) (-20 mag), these luminosity densities are 2.6(-0.9)(+1.5)x and 2.2(-1.1)(+2.0)x lower, respectively, than the extrapolated trends. Our new results are broadly consistent with the "accelerated evolution" scenario at z>8, as seen in many theoretical models.Comment: 23 pages, 15 figures, 7 tables, updated to match the version in press, including some minor textual corrections identified at the proof stag