Quadracyclic Adenine: A Non‐Perturbing Fluorescent Adenine Analogue

Fluorescent‐base analogues (FBAs) comprise a group of increasingly important molecules for the investigation of nucleic acid structure and dynamics as well as of interactions between nucleic acids and other molecules. Here, we report on the synthesis, detailed spectroscopic characterisation and base‐pairing properties of a new environment‐sensitive fluorescent adenine analogue, quadracyclic adenine (qA). After developing an efficient route of synthesis for the phosphoramidite of qA it was incorporated into DNA in high yield by using standard solid‐phase synthesis procedures. In DNA qA serves as an adenine analogue that preserves the B‐form and, in contrast to most currently available FBAs, maintains or even increases the stability of the duplex. We demonstrate that, unlike fluorescent adenine analogues, such as the most commonly used one, 2‐aminopurine, and the recently developed triazole adenine, qA shows highly specific base‐pairing with thymine. Moreover, qA has an absorption band outside the absorption of the natural nucleobases (>300 nm) and can thus be selectively excited. Upon excitation the qA monomer displays a fluorescence quantum yield of 6.8 % with an emission maximum at 456 nm. More importantly, upon incorporation into DNA the fluorescence of qA is significantly less quenched than most FBAs. This results in quantum yields that in some sequences reach values that are up to fourfold higher than maximum values reported for 2‐aminopurine. To facilitate future utilisation of qA in biochemical and biophysical studies we investigated its fluorescence properties in greater detail and resolved its absorption band outside the DNA absorption region into distinct transition dipole moments. In conclusion, the unique combination of properties of qA make it a promising alternative to current fluorescent adenine analogues for future detailed studies of nucleic acid‐containing systems.     

Coherent phonon dynamics in short-period InAs/GaSb superlattices

We have performed ultrafast pump-probe spectroscopy studies on a series of InAs/GaSb-based short-period superlattice (SL) samples with periods ranging from 46 Å to 71 Å. We observe two types of oscillations in the differential reflectivity with fast (∼$\sim$1–2 ps) and slow (∼$\sim$24 ps) periods. The period of the fast oscillations changes with the SL period and can be explained as coherent acoustic phonons generated from carriers photoexcited within the SL. This mode provides an alternative method for determining the SL period. The period of the slow mode depends on the wavelength of the probe pulse and can be understood as a propagating coherent phonon wavepacket modulating the reflectivity of the probe pulse as it travels from the surface into the sample.     

Cysteamine-based functionalization of InAs surfaces: revealing the critical role of oxide interactions in biasing attachment

Attaching functional molecules such as thiols and proteins to semiconductor surfaces is increasingly exploited in functional devices such as sensors. Despite extensive research to understand this interface and demonstrate a robust protocol for attachment, the bonding chemistry of thiolates to III-V surfaces has been under great debate in the literature. This study provides a comprehensive chemical model for the attachment of thiols to InAs, an increasingly device-relevant III-V semiconductor, using cysteamine as a model molecule. We examine the attachment of cysteamine to InAs via the thiol group using X-ray photoelectron spectroscopy and spectroscopic ellipsometry and confirm that thiolate bonding to the substrate occurs preferentially to As sites over In sites as a limit. These experiments explore the interplay of the native oxide chemical properties, the cysteamine concentration, and the evolving InAs surface chemistry with functionalization. The thiol-InAs interaction can be framed as a general acid-base reaction, where the nucleophilic and/or electrophilic attack of the surface (i.e., binding to In sites and/or As sites) depends on the acidity of the thiol. The roles of the initial oxide composition, the solvent of the functionalizing solution, and the cysteamine as a limiting reagent in fully displacing the oxide and creating In-S and As-S bonds are highlighted.     

Progress in adsorption-based CO2 capture by metal-organic frameworks

Metal-organic frameworks (MOFs) have recently attracted intense research interest because of their permanent porous structures, large surface areas, and potential applications as novel adsorbents. The recent progress in adsorption-based CO(2) capture by MOFs is reviewed and summarized in this critical review. CO(2) adsorption in MOFs has been divided into two sections, adsorption at high pressures and selective adsorption at approximate atmospheric pressures. Keys to CO(2) adsorption in MOFs at high pressures and low pressures are summarized to be pore volumes of MOFs, and heats of adsorption, respectively. Many MOFs have high CO(2) selectivities over N(2) and CH(4). Water effects on CO(2) adsorption in MOFs are presented and compared with benchmark zeolites. In addition, strategies appeared in the literature to enhance CO(2) adsorption capacities and/or selectivities in MOFs have been summarized into three main categories, catenation and interpenetration, chemical bonding enhancement, and electrostatic force involvement. Besides the advantages, two main challenges of using MOFs in CO(2) capture, the cost of synthesis and the stability toward water vapor, have been analyzed and possible solutions and path forward have been proposed to address the two challenges as well (150 references).     

Nighttime radical observations and chemistry

The nitrate radical, NO(3), is photochemically unstable but is one of the most chemically important species in the nocturnal atmosphere. It is accompanied by the presence of dinitrogen pentoxide, N(2)O(5), with which it is in rapid thermal equilibrium at lower tropospheric temperatures. These two nitrogen oxides participate in numerous atmospheric chemical systems. NO(3) reactions with VOCs and organic sulphur species are important, or in some cases even dominant, oxidation pathways, impacting the budgets of these species and their degradation products. These oxidative reactions, together with the ozonolysis of alkenes, are also responsible for the nighttime production and cycling of OH and peroxy (HO(2) + RO(2)) radicals. In addition, reactions of NO(3) with biogenic hydrocarbons are particularly efficient and are responsible for the production of organic nitrates and secondary organic aerosol. Heterogeneous chemistry of N(2)O(5) is one of the major processes responsible for the atmospheric removal of nitrogen oxides as well as the cycling of halogen species though the production of nitryl chloride, ClNO(2). The chemistry of NO(3) and N(2)O(5) is also important to the regulation of both tropospheric and stratospheric ozone. Here we review the essential features of this atmospheric chemistry, along with field observations of NO(3), N(2)O(5), nighttime peroxy and OH radicals, and related compounds. This review builds on existing reviews of this chemistry, and encompasses field, laboratory and modelling work spanning more than three decades.     

Direct and β-delayed multi-proton emission from atomic nuclei with a time projection chamber: the cases of 43Cr, 45Fe, and 51Ni

The two-proton radioactivity of ⁴⁵Fe was studied experimentally with a time projection chamber. The aim of the experiment was the reconstruction of the proton tracks in three dimensions. Energy and angular correlations have been determined and the data are compared with theoretical models, in particular with a three-body model. Moreover, the decay of ⁴³Cr was studied and ??-delayed one-, two- and three-proton emission could be established. The correlations observed for ??-delayed two-proton emission favour a sequential emission. Finally, ??-delayed two-proton emission was observed for the first time for ⁵¹Ni.     

Measurements of WW and WZ production in W + jets final states in pp collisions

We study WW and WZ production with ?νqq (?=e,μ) final states using data collected by the D0 detector at the Fermilab Tevatron Collider corresponding to 4.3 fb(-1) of integrated luminosity from pp collisions at sqrt[s]=1.96 TeV. Assuming the ratio between the production cross sections σ(WW) and σ(WZ) as predicted by the standard model, we measure the total WV (V=W,Z) cross section to be σ(WV)=19.6(-3.0)(+3.2) pb and reject the background-only hypothesis at a level of 7.9 standard deviations. We also use b-jet discrimination to separate the WZ component from the dominant WW component. Simultaneously fitting WW and WZ contributions, we measure σ(WW)=15.9(-3.2)(+3.7) pb and σ(WZ)=3.3(-3.3)(+4.1) pb, which is consistent with the standard model predictions.     

Search for universal extra dimensions in pp collisions

We present a search for Kaluza-Klein (KK) particles predicted by models with universal extra dimensions (UED) using a data set corresponding to an integrated luminosity of 7.3 fb(-1), collected by the D0 detector at a pp center-of-mass energy of 1.96 TeV. The decay chain of KK particles can lead to a final state with two muons of the same charge. This signature is used to set a lower limit on the compactification scale of R(-1)>260 GeV in a minimal UED model.     

Measurement of the W boson mass with the D0 detector

We present a measurement of the W boson mass using data corresponding to 4.3 fb(-1) of integrated luminosity collected with the D0 detector during Run II at the Fermilab Tevatron pp collider. With a sample of 1,677,394 W → eν candidate events, we measure M(W) = 80.367 ± 0.026 GeV. This result is combined with an earlier D0 result determined using an independent Run II data sample, corresponding to 1 fb(-1) of integrated luminosity, to yield M(W) = 80.375 ± 0.023 GeV.