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Direct covariance measurement of CO2 gas transfer velocity during the 2008 Southern Ocean Gas Exchange Experiment: Wind speed dependency
Direct measurements of air-sea heat, momentum, and mass (including CO2, DMS, and water vapor) fluxes using the direct covariance method were made over the open ocean from the NOAA R/V Ronald H. Brown during the Southern Ocean Gas Exchange (SO GasEx) program. Observations of fluxes and the physical processes associated with driving air-sea exchange are key components of SO GasEx. This paper focuses on the exchange of CO2 and the wind speed dependency of the transfer velocity, k, used to model the CO2 flux between the atmosphere and ocean. A quadratic dependence of k on wind speed based on dual tracer experiments is most frequently encountered in the literature. However, in recent years, bubble-mediated enhancement of k, which exhibits a cubic relationship with wind speed, has emerged as a key issue for flux parameterization in high-wind regions. Therefore, a major question addressed in SO GasEx is whether the transfer velocities obey a quadratic or cubic relationship with wind speed. After significant correction to the flux estimates (primarily due to moisture contamination), the direct covariance CO2 fluxes confirm a significant enhancement of the transfer velocity at high winds compared with previous quadratic formulations. Regression analysis suggests that a cubic relationship provides a more accurate parameterization over a wind speed range of 0 to 18 m sâ1. The Southern Ocean results are in good agreement with the 1998 GasEx experiment in the North Atlantic and a recent separate field program in the North Sea
Real-time detection of TDP1 activity using a fluorophore-quencher coupled DNA-biosensor
Real-time detection of enzyme activities may present the easiest and most reliable way of obtaining quantitative analyses in biological samples. We present a new DNA-biosensor capable of detecting the activity of the potential anticancer drug target tyrosyl-DNA phosphodiesterase 1 (TDP1) in a very simple, high throughput, and real-time format. The biosensor is specific for Tdp1 even in complex biological samples, such as human cell extracts, and may consequently find future use in fundamental studies as well as a cancer predictive tool allowing fast analyses of diagnostic cell samples such as biopsies. TDP1 removes covalent 3'DNA adducts in DNA single-strand break repair. This enzymatic activity forms the basis of the design of the TDP1-biosensor, which consists of a short hairpin-forming oligonucleotide having a 5'fluorophore and a 3'quencher brought in close proximity by the secondary structure of the biosensor. The specific action of TDP1 removes the quencher, thereby enabling optical detection of the fluorophore. Since the enzymatic action of TDP1 is the only "signal amplification" the increase in fluorescence may easily be followed in real-time and allows quantitative analyses of TDP1 activity in pure enzyme fractions as well as in crude cell extracts. In the present study we demonstrate the specificity of the biosensor, its ability to quantitatively detect up- or down-regulated TDP1 activity, and that it may be used for measuring and for analyzing the mechanism of TDP1 inhibition
Influence of ligand structure and molecular geometry on the properties of d6 polypyridinic transition metal complexes
Different strategies to improve the excited state properties of polypyridinic complexes by varying ligand structure and molecular geometry are described. Bidentate and tetradentate ligands based on fragments as dipyrido[3,2-a:2âČ,3âČ-c]phenazine, dppz, and pyrazino[2,3-f][1,10]-phenanthroline, ppl, have been used. Quinonic residues were fused to these basic units to improve acceptor properties. Photophysical studies were performed in order to test theoretical predictions
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, 4845â4859). They have been isolated as their PF_6â 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 ÎČ 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 â Ï^* metal-to-ligand charge-transfer (MLCT) and Ï â Ï^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant ÎČ_0 responses as high as ca. 600 Ă 10^(â30) esu. These pseudo-C_(2v) chromophores show two substantial components of the ÎČ tensor, ÎČ_(zzz) and ÎČ_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, ÎČ_(zzz) dominates in all cases, whereas the Stark analyses indicate that ÎČ_(zyy) is dominant in the shorter chromophores, but ÎČ_(zzz) and ÎČ_(zyy) are similar for the extended species. In contrast, finite field calculations predict that ÎČ_(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 Ï-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, 3880â3891)
Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability
In this article, we present a detailed study of structureâactivity relationships in diquaternized 2,2âČ-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, Ï-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^â salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense Ï â Ï^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities ÎČ 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 ÎČ_0. The directly and indirectly derived ÎČ values are large and increase with the extent of Ï-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 ÎČ_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 âoff-diagonalâ ÎČ_(zyy) components. The most significant findings of these studies are: (i) ÎČ_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4âČ-(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
Cytomolecular identification of individual wheat-wheat chromosome arm associations in wheat-rye hybrids
Chromosome pairing in the meiotic metaphase I of wheatrye
hybrids has been characterized by sequential genomic
and fluorescent in situ hybridization allowing not only the
discrimination of wheat and rye chromosomes, but also the
identification of the individual wheat and rye chromosome
arms involved in the chromosome associations. The majority
of associations (93.8%) were observed between the wheat
chromosomes. The largest number of wheat-wheat chromosome
associations (53%) was detected between the A and D
genomes, while the frequency of B-D and A-B associations
was significantly lower (32 and 8%, respectively). Among the
A-D chromosome associations, pairing between the 3AL and
3DL arms was observed with the highest frequency, while
the most frequent of all the chromosome associations (0.113/
cell) was found to be the 3DS-3BS. Differences in the pairing
frequency of the individual chromosome arms of wheat-rye
hybrids have been discussed in relation to the homoeologous
relationships between the constituent genomes of
hexaploid wheat
Search for the standard model Higgs boson in the H to ZZ to 2l 2nu channel in pp collisions at sqrt(s) = 7 TeV
A search for the standard model Higgs boson in the H to ZZ to 2l 2nu decay
channel, where l = e or mu, in pp collisions at a center-of-mass energy of 7
TeV is presented. The data were collected at the LHC, with the CMS detector,
and correspond to an integrated luminosity of 4.6 inverse femtobarns. No
significant excess is observed above the background expectation, and upper
limits are set on the Higgs boson production cross section. The presence of the
standard model Higgs boson with a mass in the 270-440 GeV range is excluded at
95% confidence level.Comment: Submitted to JHE
Search for anomalous t t-bar production in the highly-boosted all-hadronic final state
A search is presented for a massive particle, generically referred to as a
Z', decaying into a t t-bar pair. The search focuses on Z' resonances that are
sufficiently massive to produce highly Lorentz-boosted top quarks, which yield
collimated decay products that are partially or fully merged into single jets.
The analysis uses new methods to analyze jet substructure, providing
suppression of the non-top multijet backgrounds. The analysis is based on a
data sample of proton-proton collisions at a center-of-mass energy of 7 TeV,
corresponding to an integrated luminosity of 5 inverse femtobarns. Upper limits
in the range of 1 pb are set on the product of the production cross section and
branching fraction for a topcolor Z' modeled for several widths, as well as for
a Randall--Sundrum Kaluza--Klein gluon. In addition, the results constrain any
enhancement in t t-bar production beyond expectations of the standard model for
t t-bar invariant masses larger than 1 TeV.Comment: Submitted to the Journal of High Energy Physics; this version
includes a minor typo correction that will be submitted as an erratu
Combined search for the quarks of a sequential fourth generation
Results are presented from a search for a fourth generation of quarks
produced singly or in pairs in a data set corresponding to an integrated
luminosity of 5 inverse femtobarns recorded by the CMS experiment at the LHC in
2011. A novel strategy has been developed for a combined search for quarks of
the up and down type in decay channels with at least one isolated muon or
electron. Limits on the mass of the fourth-generation quarks and the relevant
Cabibbo-Kobayashi-Maskawa matrix elements are derived in the context of a
simple extension of the standard model with a sequential fourth generation of
fermions. The existence of mass-degenerate fourth-generation quarks with masses
below 685 GeV is excluded at 95% confidence level for minimal off-diagonal
mixing between the third- and the fourth-generation quarks. With a mass
difference of 25 GeV between the quark masses, the obtained limit on the masses
of the fourth-generation quarks shifts by about +/- 20 GeV. These results
significantly reduce the allowed parameter space for a fourth generation of
fermions.Comment: Replaced with published version. Added journal reference and DO
Measurement of the t t-bar production cross section in the dilepton channel in pp collisions at sqrt(s) = 7 TeV
The t t-bar production cross section (sigma[t t-bar]) is measured in
proton-proton collisions at sqrt(s) = 7 TeV in data collected by the CMS
experiment, corresponding to an integrated luminosity of 2.3 inverse
femtobarns. The measurement is performed in events with two leptons (electrons
or muons) in the final state, at least two jets identified as jets originating
from b quarks, and the presence of an imbalance in transverse momentum. The
measured value of sigma[t t-bar] for a top-quark mass of 172.5 GeV is 161.9 +/-
2.5 (stat.) +5.1/-5.0 (syst.) +/- 3.6(lumi.) pb, consistent with the prediction
of the standard model.Comment: Replaced with published version. Included journal reference and DO
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