Cross-coupling reactions of gold(I) alkynyl and polyyndiyl complexes

Gold(I) alkynyl complexes are shown to efficiently couple with aryl iodides under mild conditions in the presence of both Pd(II) and Cu(I) co-catalysts. The reaction is not gold catalysed, but rather the Au(I) centre serves to transfer the alkynyl moiety to Cu(I), which then enters the conventional Sonogashira cycles. Using this method, a small range of 1,4-disubstituted diynes, including examples of differentially substituted compounds ArCCCCAr′, have been prepared directly from [(Ph₃P)AuCCCCAu(PPh₃)] and aryl iodides ArI.     

Phonetic variability of stops and flaps in spontaneous and careful speech

Variability is perhaps the most notable characteristic of speech, and it is particularly noticeable in spontaneous conversational speech. The current research examines how speakers realize the American English stops /p, k, b, g/ and flaps (? from /t, d/), in casual conversation and in careful speech. Target consonants appear after stressed syllables (e.g., "lobby") or between unstressed syllables (e.g., "humanity"), in one of six segmental/word-boundary environments. This work documents the degree and types of variability listeners encounter and must parse. Findings show greater reduction in connected and spontaneous speech, greater reduction in high frequency phrases (but not within high frequency words), and greater reduction between unstressed syllables than after a stress. Although highly reduced productions of stops and flaps occur often, with approximant-like tokens even in careful speech, reduction does not lead to a large amount of overlap between phonological categories. Approximant-like realizations of expected stops and flaps in some conditions constitute the majority of tokens. This shows that reduced speech is something that listeners encounter, and must perceive, in a large proportion of the speech they hear.     

Aurones: Small Molecule Visible Range Fluorescent Probes Suitable for Biomacromolecules

Aurones, derivatives of 2-benylidenebenzofuran-3(2H)-one, are natural products that serve as plant pigments. There have been reports that some of these substances fluoresce, but little information about their optical properties is in the literature. In this report, series of aurone derivatives were synthesized as possible fluorescent probes that can be excited by visible light. We found that an amine substituent shifted the lowest energy absorption band from the near-UV to the visible region of the electromagnetic spectrum. Four amine-substituted aurone derivatives were synthesized to explore the effect of this substituent on the absorption and emission properties of the aurone chromophore. The emission maxima and intensities of the molecules are strongly dependent on the nature of the substituent and the solvent polarity. Overall, the emission intensity increases and the maximum wavelength decreases in less polar solvents; thus, the aurones may be useful probes for hydrophobic sites on biological molecules. A limited investigation with model protein, nucleic acid and fixed cells supports this idea. It is known that the sulfur analog of aurone can undergo photo-induced E/Z isomerization. This possibility was investigated for one of the aminoaurones, which was observed to reversible photoisomerize. The two isomers have similar absorption spectra, but the emission properties are distinct. We conclude that appropriately substituted aurones are potentially useful as biological probes and photoswitches.     

The size-Ramsey number of powers of paths

Given graphs and and a positive integer , say that is -Ramsey for , denoted , if every -coloring of the edges of contains a monochromatic copy of . The size-Ramsey number of a graph is defined to be . Answering a question of Conlon, we prove that, for every fixed , we have , where is the th power of the -vertex path (ie, the graph with vertex set and all edges such that the distance between and in is at most ). Our proof is probabilistic, but can also be made constructive.     

On the Role of Interacting Particles and Limited Resources in the Regulation of Lattice Length Dynamics

Journal of Statistical Physics - Motivated by the significant effect of particle–particle interactions on the driven stochastic transport system, we examine how interacting particles control...     

Some new inequalities involving the Hardy operator

In this paper we derive some new inequalities involving the Hardy operator, using some estimates of the Jensen functional, continuous form generalization of the Bellman inequality and a Banach space variant of it. Some results are generalized to the case of Banach lattices on $(0,b],0<b\le \infty$.     

Weighted Hardy and singular operators in Morrey spaces

We study the weighted boundedness of the Cauchy singular integral operator SΓ in Morrey spaces Lp,λ(Γ) on curves satisfying the arc-chord condition, for a class of “radial type” almost monotonic weights. The non-weighted boundedness is shown to hold on an arbitrary Carleson curve. We show that the weighted boundedness is reduced to the boundedness of weighted Hardy operators in Morrey spaces Lp,λ(0,?), ?>0. We find conditions for weighted Hardy operators to be bounded in Morrey spaces. To cover the case of curves we also extend the boundedness of the Hardy-Littlewood maximal operator in Morrey spaces, known in the Euclidean setting, to the case of Carleson curves.     

The robustness in dynamics of out of equilibrium bidirectional transport systems with constrained entrances

Macroscopic and microscopic long-distance bidirectional transfer depends on connections between entrances and exits of various transport mediums. Persuaded by the associations, we introduce a small system module of Totally Asymmetric Simple Exclusion Process including oppositely directed species of particles moving on two parallel channels with constrained entrances. The dynamical rules which characterize the system obey symmetry between the two species and are identical for both the channels. The model displays a rich steady-state behavior, including symmetry breaking phenomenon. The phase diagram is analyzed theoretically within the mean-field approximation and substantiated with Monte Carlo simulations. Relevant mean-field calculations are also presented. We further compared the phase segregation with those observed in previous works, and it is examined that the structure of phase separation in proposed model is distinguished from earlier ones. Interestingly, for phases with broken symmetry, symmetry with respect to channels has been observed as the distinct particles behave differently while the similar type of particles exhibits the same conduct in the system. For symmetric phases, significant properties including currents and densities in the channels are identical for both types of particles. The effect of symmetry breaking occurrence on the Monte Carlo simulation results has also been examined based on particle density histograms. Finally, phase properties of the system having strong size dependency have been explored based on simulations findings.     

Games and general distributive laws in Boolean algebras

The games and are played by two players in -complete and max -complete Boolean algebras, respectively. For cardinals such that or , the -distributive law holds in a Boolean algebra iff Player 1 does not have a winning strategy in . Furthermore, for all cardinals , the -distributive law holds in iff Player 1 does not have a winning strategy in . More generally, for cardinals such that , the -distributive law holds in iff Player 1 does not have a winning strategy in . For regular and , implies the existence of a Suslin algebra in which is undetermined.

     

The hydrogenation of α-methylstyrene by tricarbonyl(cyclopentadienyl)hydride compounds of tungsten and molybdenum; support for a radical mechanism

Rates of reaction of the hydrides of tungsten and molybdenum of the form HM(η5-C₅H₅(CO)₃, with β-methylstyrene have been determined. The rate law is first order in olefin and in hydride. A mechanism involving a rate limiting step of hydrogen atom transfer to the olefin is consistent with the rate law, isotope effect and the absence of CO inhibition. The activation enthalpy for the reactions of HW(η5-C₅H₅)(CO)₃ and HMo(η5-C₅H₅)(CO)₃ are 97.5 ± 4.2 and 89.1 ± 3.3 kJ/mol, respectively. The rate constant for the reaction of styrene and HW(β5-C₅H₅)(CO)₃ is approximately that of β-methylstyrene, while β-methylstyrene was not observed to react under the conditions of the previous determinations. This suggests that attack by the hydride occurs at the β-carbon and this process is inhibited by substituents at that location.