Collisional relaxation of O2(X3Σg(-), υ = 1) and O2(a1Δg, υ = 1) by atmospherically relevant species

Laboratory measurements are reported of the rate coefficient for collisional removal of O(2)(X(3)Σ(g)(-), υ = 1) by O((3)P), and the rate coefficients for removal of O(2)(a(1)Δ(g), υ = 1) by O(2), CO(2), and O((3)P). A two-laser method is employed, in which the pulsed output of the first laser at 285 nm photolyzes ozone to produce oxygen atoms and O(2)(a(1)Δ(g), υ = 1), and the output of the second laser detects O(2)(a(1)Δ(g), υ = 1) via resonance-enhanced multiphoton ionization. The kinetics of O(2)(X(3)Σ(g)(-), υ = 1) + O((3)P) relaxation is inferred from the temporal evolution of O(2)(a(1)Δ(g), υ = 1), an approach enabled by the rapid collision-induced equilibration of the O(2)(X(3)Σ(g)(-), υ = 1) and O(2)(a(1)Δ(g), υ = 1) populations in the system. The measured O(2)(X(3)Σ(g)(-), υ = 1) + O((3)P) rate coefficient is (2.9 ± 0.6) × 10(-12) cm(3) s(-1) at 295 K and (3.4 ± 0.6) × 10(-12) cm(3) s(-1) at 240 K. These values are consistent with the previously reported result of (3.2 ± 1.0) × 10(-12) cm(3) s(-1), which was obtained at 315 K using a different experimental approach [K. S. Kalogerakis, R. A. Copeland, and T. G. Slanger, J. Chem. Phys. 123, 194303 (2005)]. For removal of O(2)(a(1)Δ(g), υ = 1) by O((3)P), the upper limits for the rate coefficient are 4 × 10(-13) cm(3) s(-1) at 295 K and 6 × 10(-13) cm(3) s(-1) at 240 K. The rate coefficient for removal of O(2)(a(1)Δ(g), υ = 1) by O(2) is (5.6 ± 0.6) × 10(-11) cm(3) s(-1) at 295 K and (5.9 ± 0.5) × 10(-11) cm(3) s(-1) at 240 K. The O(2)(a(1)Δ(g), υ = 1) + CO(2) rate coefficient is (1.5 ± 0.2) × 10(-14) cm(3) s(-1) at 295 K and (1.2 ± 0.1) × 10(-14) cm(3) s(-1) at 240 K. The implications of the measured rate coefficients for modeling of atmospheric emissions are discussed.     

Convergence of dip-pen nanolithography and acoustic biosensors towards a rapid-analysis multi-sample microsystem

The present work demonstrates for the first time patterning of a ready-to-use biosensor with several different biomolecules using Dip-Pen Nanolithography (DPN) for the development of a procedure towards more rapid and efficient multi-sample detection. The biosensor platform used is based on a Surface Acoustic Wave (SAW) device integrated with a parallel-channel microfluidic module, termed as "microfluidics-on-SAW" ("μF-on-SAW"), for reproducible multi-sample analysis. Lipids with different functionalized head groups were patterned at distinct, microfluidic-formed rectangular domains with sharp edges all located on the same sensor surface; pattern quality was verified using a fluorescent microscope. The functionality of the head groups, the efficiency of the patterning method, and the suitability of DPN for the surface modification of the acoustic device were subsequently examined through acoustic experiments. The μF-on-SAW configuration was used to detect specific binding between the pre-patterned functionalized lipids with their corresponding biomolecules. The achievement of an improved sensitivity (5-fold compared to previous acoustic configurations) and reduced preparation time by at least 2 h clearly indicates the suitability of DPN as a direct patterning method for ready-to-use acoustic sensor devices like the μF-on-SAW towards integrated, rapid-analysis, multi-sample biosensing microsystem development.     

Marilines A-C: novel phthalimidines from the sponge-derived fungus Stachylidium sp

A marine-derived fungus of the genus Stachylidium was isolated from the sponge Callyspongia cf. C. flammea. Chemical investigation of the bioactive fungal extract led to the isolation of the novel phthalimidine derivatives marilines A(1) (1a), A(2) (1b), B (2), and C (3). The absolute configurations of the enantiomeric compounds 1a and 1b were assigned by a combination of experimental circular dichroism (CD) investigations and quantum chemical CD calculations. The skeleton of marilines is most unusual, and its biosynthesis is suggested to require uncommon biochemical reactions in fungal secondary metabolism. Both enantiomers, marilines A(1) (1a) and A(2) (1b), inhibited human leukocyte elastase (HLE) with an IC(50) value of 0.86 μM.     

Statistical anisotropy from vector curvaton in D-brane inflation

We investigate the possibility of embedding the vector curvaton paradigm in D-brane models of inflation in type IIB string theory in a simple toy model. The vector curvaton is identified with the U(1)$U(1)$ gauge field that lives on the world volume of a D3-brane, which may be stationary or undergoing general motion in the internal space. The dilaton is considered as a spectator field which modulates the evolution of the vector field. In this set-up, the vector curvaton is able to generate measurable statistical anisotropy in the spectrum and bispectrum of the curvature perturbation assuming that the dilaton evolves as e^−?∝a²$e^{-?}\propto a^2$ where a(t)$a(t)$ is the scale factor. Our work constitutes a first step towards exploring how such distinctive features may arise from the presence of several light fields that naturally appear in string theory models of cosmology.     

Large deviations for multiscale diffusion via weak convergence methods

We study the large deviations principle for locally periodic SDEs with small noise and fast oscillating coefficients. There are three regimes depending on how fast the intensity of the noise goes to zero relative to homogenization parameter. We use weak convergence methods which provide convenient representations for the action functional for all regimes. Along the way, we study weak limits of controlled SDEs with fast oscillating coefficients. We derive, in some cases, a control that nearly achieves the large deviations lower bound at prelimit level. This control is useful for designing efficient importance sampling schemes for multiscale small noise diffusion.     

Extremal subgraphs of random graphs

We prove that there is a constant c > 0, such that whenever p ≥ n^‐c, with probability tending to 1 when n goes to infinity, every maximum triangle‐free subgraph of the random graph G_n,p is bipartite. This answers a question of Babai, Simonovits and Spencer (Babai et al., J Graph Theory 14 (1990) 599–622). The proof is based on a tool of independent interest: we show, for instance, that the maximum cut of almost all graphs with M edges, where M ? n and M ≤ /2, is “nearly unique”. More precisely, given a maximum cut C of G_n,M, we can obtain all maximum cuts by moving at most \begin{align*}\mathcal{O}(\sqrt{n^3/M})\end{align*} vertices between the parts of C. © 2012 Wiley Periodicals, Inc. Random Struct. Alg., 2012     

Sharp load thresholds for cuckoo hashing

The paradigm of many choices has influenced significantly the design of efficient data structures and, most notably, hash tables. Cuckoo hashing is a technique that extends this concept. There, we are given a table with n locations, and we assume that each location can hold one item. Each item to be inserted chooses randomly k ≥ 2 locations and has to be placed in any one of them. How much load can cuckoo hashing handle before collisions prevent the successful assignment of the available items to the chosen locations? Practical evaluations and theoretical analysis of this method have shown that one can allocate a number of elements that is a large proportion of the size of the table, being very close to 1 even for small values of k such as 4 or 5. In this paper we show that there is a critical value for this proportion: with high probability, when the amount of available items is below this value, then these can be allocated successfully, but when it exceeds this value, the allocation becomes impossible. We give explicitly for each k ≥ 3 this critical value. This answers an open question posed by Mitzenmacher (ESA '09) and underpins theoretically the experimental results. Our proofs are based on the translation of the question into a hypergraph setting, and the study of the related typical properties of random k ‐uniform hypergraphs.© 2012 Wiley Periodicals, Inc. Random Struct., 2012