Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 2. Preparation,dissociations, and energetics of 3-hydroxyoxolan-3-yl radical and cation

The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C(2)H(3)O and C(2)H(4)O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3(+)) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at approximately 590 and approximately 400 nm.     

Vinyl acetate formation by the reaction of ethylene with acetate species on oxygen-covered Pd(111)

The reaction pathway of vinyl acetate synthesis is scrutinized by reacting gas-phase ethylene (at an effective pressure of 1 x 10-4 Torr) with eta2-acetate species (with a coverage of 0.31 +/- 0.02 monolayer) on a Pd(111)-O(2x2) model catalyst surface in ultrahigh vacuum. It is found that the 1414 cm-1 infrared feature due to the symmetric OCO stretching mode of the acetate species decreases in intensity due to reaction with gas-phase ethylene, while temperature-programmed desorption experiments demonstrate that vinyl acetate is formed. The formation of ethylidyne species is detected when almost all of the acetate species have been removed. The experimental removal kinetics are reproduced by a model in which adsorbed acetates react with an ethylene-derived (possibly ethylene or vinyl) species, where ethylene adsorption is blocked by the acetate present on the surface.     

Pressure induced self-oxidation of Fe(OH)2

M?ssbauer spectroscopy, x-ray diffraction, and electrical resistance [R(P,T)] studies in Fe(OH)(2) to 40 GPa revealed an unforeseen process by which a gradual Fe2+ oxidation takes place, starting at approximately 8 GPa reaching 70% Fe3+ abundance at 40 GPa. The nonreversible process Fe2+-->Fe3++e(-) occurs with no structural transition. The "ejected" electrons form a deep band within the high-pressure electronic manifold becoming weakly localized at P>50 GPa. This process is attributed to an effective ionization potential created by the pressure induced orientationally deformed (OH) dipoles and the unusual small binding energy of the valence electron in Fe2+(OH)(2).     

Solvent-mediated self-association of a Horning-crown macrocycle

A member of a new class of novel macrocycles possessing both polyether and phenolic functionalities, forms dimers in both the solid-state and in solution when exposed to chloroform, dichloromethane or toluene, but does not self-associate in the presence of dimethyl sulfoxide.     

On approximation of affine Baire-one functions

It is known (G. Choquet, G. Mokobodzki) that a Baire-one affine function on a compact convex set satisfies the barycentric formula and can be expressed as a pointwise limit of a sequence of continuous affine functions. Moreover, the space of Baire-one affine functions is uniformly closed. The aim of this paper is to discuss to what extent analogous properties are true in the context of general function spaces. In particular, we investigate the function spaceH(U), consisting of the functions continuous on the closure of a bounded open setU⊂ℝ ^m and harmonic onU, which has been extensively studied in potential theory. We demonstrate that the barycentric formula does not hold for the spaceB ₁ ^b (H(U)) of bounded functions which are pointwise limits of functions from the spaceH(U) and thatB ₁ ^b (H(U)) is not uniformly closed. On the other hand, every Baire-oneH(U)-affine function (in particular a solution of the generalized Dirichlet problem for continuous boundary data) is a pointwise limit of a bounded sequence of functions belonging toH(U). It turns out that such a situation always occurs for simplicial spaces whereas it is not the case for general function spaces. The paper provides several characterizations of those Baire-one functions which can be approximated pointwise by bounded sequences of elements of a given function space. Research supported in part by grants GA ČR No. 201/00/0767 from the Grant Agency of the Czech Republic, GA UK 165/99 from the Grant Agency of Charles University, and in part by grant number MSM 113200007 from the Czech Ministry of Education.     

N-Sequence RSNS Ambiguity Analysis

The robust symmetrical number system (RSNS) is a modular system formed using Nges2 integer sequences and ensures that two successive RSNS vectors (paired terms from all N sequences) differ by only one integer. This integer Gray-code property reduces the possibility of encoding errors and makes the RSNS useful in applications such as folding analog-to-digital converters (ADCs), direction finding antenna architectures, and photonic processors. This paper determines the length of combined sequences that contain no vector ambiguities. This length or longest run of distinct vectors we call the RSNS dynamic range (Mcirc). The position of Mcirc which is the starting point in the sequence is also derived. Computing Mcirc and the position of Mcirc allows the integer Gray-code properties of the RSNS to be used in practical applications. We first extend our two-sequence results to develop a closed-form expression for Mcirc for a three-sequence RSNS with moduli of the form 2^r-1,2^r,2^r+1. We then extend the results to solving the N-sequence RSNS ambiguity locations in general     

A novel three-dimensional system to study interactions between endothelial cells and neural cells of the developing central nervous system

Background  

During angiogenesis in the developing central nervous system (CNS), endothelial cells (EC) detach from blood vessels growing on the brain surface, and migrate into the expanding brain parenchyma. Brain angiogenesis is regulated by growth factors and extracellular matrix (ECM) proteins secreted by cells of the developing CNS. In addition, recent evidence suggests that EC play an important role in establishing the neural stem cell (NSC) niche. Therefore, two-way communication between EC and neural cells is of fundamental importance in the developing CNS. To study the interactions between brain EC and neural cells of the developing CNS, a novel three-dimensional (3-D) murine co-culture system was developed. Fluorescent-labelled brain EC were seeded onto neurospheres; floating cellular aggregates that contain NSC/neural precursor cells (NPC) and smaller numbers of differentiated cells. Using this system, brain EC attachment, survival and migration into neurospheres was evaluated and the role of integrins in mediating the early adhesive events addressed.     

Alternative charge stabilisation and a changing reactivity of 1,3,5-triazine based starburst compounds as studied by in situ ESR/UV–vis–NIR spectroelectrochemistry

The role of the chemical structure in an alternative charge stabilisation and a changing reactivity of star-shaped compounds with a central triazine ring linked to aryl groups like thiophene, furan or ethylenedioxythiophene synthesized by a Stille cross-coupling procedure, is followed by spectroelectrochemical measurements. While cathodic reduction leads to stable anion radicals with a delocalised spin on the central triazine moiety, dimerisation and oligomerisation occurs upon anodic oxidation. The stability of the charged states in the polymer film increased substantially using an EDOT (3,4-ethylenedioxythiophene) side group. The location of the charged states on the molecules has been proved by computations. These star-shaped molecules are excellent model structures for studies of the competition of dimerisation and oligomerisation processes based on the variation of the electron and spin distribution in the molecules.     

The origins of the sampling theorem

The publications of Claude E. Shannon brought the sampling theorem to the broad attention of communication engineers. This article demonstrates how practicians, theoreticians, and mathematicians discovered the implications of the sampling theorem almost independent of one another