Alkene selenenylation: A comprehensive analysis of relative reactivities, stereochemistry and asymmetric induction, and their comparisons with sulfenylation

A broad perspective of various factors influencing alkene selenenylation has been developed by concurrent detailed analysis of key experimental and theoretical data, such as asymmetric induction, stereochemistry, relative reactivities, and comparison with that of alkene sulfenylation. Alkyl group branching a to the double bond was shown to have the greatest effect on alkene reactivity and the stereochemical outcome of corresponding addition reactions. This is in sharp contrast with other additions to alkenes, which depend more on the degree of substitution on C=C or upon substituent electronic effects. Electronic and steric effects influencing asymmetric induction, stereochemistry, regiochemistry, and relative reactivities in the addition of PhSeOTf to alkenes are compared and contrasted with those of PhSCl.

Addition of diazomethane to armchair single-walled carbon nanotubes and their reaction sequences : A computational study

The sidewall additions of diazomethane to (n, n), n = 3–10 armchair single-walled carbon nanotubes (SWCNTs) on two different orientations of C–C bonds have been studied using the ONIOM(B3LYP/6-31G(d):PM3) approach. The binding energies of SWCNTs complexes with CH2N2, CH2 and their transition-state structures were computed at the B3LYP/6-31G(d) level. The effects of diameters of armchair SWCNTs on their binding energies were studied. Relative reactivities of all the SWCNTs and their complexes based on their frontier orbital energies gaps are reported.

Direct detection of chlorosilylene and time resolved study of some of its reactions in the gas-phase using a new photochemical precursor

Chlorosilylene, ClSiH, was prepared by 193 nm laser flash photolysis of 1-chloro-1-silacyclopent-3-ene in the gas phase. ClSiH was monitored in real time at 457.9 nm using a CW argon ion laser. The kinetics of reactions of ClSiH with C2H4, CH2 = CHCMe3, C2H2, Me2O, SO2, HCl, MeSiH3, Me2SiH2, Me3SiH, MeGeH3, MeGeH3 and precursor have been studied at ambient temperatures for the first time. Addition reactions of ClSiH and reactions with lone pair donors are faster than insertion reactions. Surprisingly ClSiH inserts faster into Si-H than Ge-H bonds. ClSiH is intermediate in reactivity between SiH2 and SiCI2. Relative reactivities of CISiH and SiH2 vary considerably. (c) 2005 Elsevier B.V. All rights reserved.

Structure property relationships in electrically conducting copolymers formed from pyrrole and N-methyl pyrrole

A series of copolymers containing differing proportions of pyrrole and N-methyl pyrrole were prepared electrochemically at various temperatures using acetonitrile as the solvent. The resultant electrical conductivity decreases universally with increasing fraction of N-methyl pyrrole. Films prepared with p-toluene sulfonate as the dopant show a marked variation in structural anisotropy as revealed by X-ray scattering with apparent copolymer content. There is a clear trend between the variation in electrical conductivity and this structural anisotropy. Different patterns of behaviour are observed for films prepared using perchlorate as the dopant and this is attributed to the role of the dopant and final structure in determining the relative reactivities of the pyrrole and N-methyl pyrrole monomers. These observations support the concept that the introduction of methyl substituents into a polypyrrole chain results in a twisted chain conformation. The structure and properties of the resultant copolymer films are particularly sensitive to the preparation conditions.

Relative entropy rate based multiple hidden Markov Model Approximation

This paper proposes a novel relative entropy rate (RER) based approach for multiple HMM (MHMM) approximation of a class of discrete-time uncertain processes. Under different uncertainty assumptions, the model design problem is posed either as a min-max optimisation problem or stochastic minimisation problem on the RER between joint laws describing the state and output processes (rather than the more usual RER between output processes). A suitable filter is proposed for which performance results are established which bound conditional mean estimation performance and show that estimation performance improves as the RER is reduced. These filter consistency and convergence bounds are the first results characterising multiple HMM approximation performance and suggest that joint RER concepts provide a useful model selection criteria. The proposed model design process and MHMM filter are demonstrated on an important image processing dim-target detection problem.

Illegal pedestrian crossing at signalised intersections : Incidence and relative risk

Illegal pedestrian behaviour is common and is reported as a factor in many pedestrian crashes. Since walking is being promoted for its health and environmental benefits, minimisation of its associated risks is of interest. The risk associated with illegal road crossing is unclear, and better information would assist in setting a rationale for enforcement and priorities for public education. An observation survey of pedestrian behaviour was conducted at signalised intersections in the Brisbane CBD (Queensland, Australia) on typical workdays, using behavioural categories that were identifiable in police crash reports. The survey confirmed high levels of crossing against the lights, or close enough to the lights that they should legally have been used. Measures of exposure for crossing legally, against the lights, and close to the lights were generated by weighting the observation data. Relative risk ratios were calculated for these categories using crash data from the observation sites and adjacent midblocks. Crossing against the lights and crossing close to the lights both exhibited a crash risk per crossing event approximately eight times that of legal crossing at signalised intersections. The implications of these results for enforcement and education are discussed, along with the limitations of the study.

The relative age effect in Australian Football League players

Youth sports teams are usually grouped into yearly age groups based on fixed cut-off date (September 1st in the UK and January 1st in Australia). Children born just after this cut-off will be the oldest and most mature in their age group. This gives them an advantage in competitive sport, an advantage which has persisted into adulthood as shown by seasonal patterns in the dates of birth of professional ice hockey, football and basketball players. We were interested in whether a similar seasonal pattern exists in professional Australian Football League (AFL) players. We examined all AFL players in the 2009 season excluding foreign-born players. We compared the observed number of players’ born in each month with the expected number based on national statistics. There was a marked and statistically significant seasonality in players’ dates of birth. There were 33% more players than expected with dates of birth in January, and 25% fewer in December. Players who are relatively older in youth AFL teams have a better chance of turning professional.

Relative income, happiness, and utility : an explanation for the Easterlin paradox and other puzzles

The well-known Easterlin paradox points out that average happiness has remained constant over time despite sharp rises in GNP per head. At the same time, a micro literature has typically found positive correlations between individual income and individual measures of subjective well-being. This paper suggests that these two findings are consistent with the presence of relative income terms in the utility function. Income may be evaluated relative to others (social comparison) or to oneself in the past (habituation). We review the evidence on relative income from the subjective well-being literature. We also discuss the relation (or not) between happiness and utility, and discuss some nonhappiness research (behavioral, experimental, neurological) related to income comparisons. We last consider how relative income in the utility function can affect economic models of behavior in the domains of consumption, investment, economic growth, savings, taxation, labor supply, wages, and migration.