Experimental and theoretical investigations of isomerization reactions of ionized acetone and its dimer

Ionization dynamics of acetone and its dimer in supersonic jets is investigated by a combination of experimental and theoretical techniques, both of which have recently been developed. In experiments, the neutral and the cationic structures are explored by infrared predissociation spectroscopy with the vacuum-ultraviolet photoionization detection schemes. Reaction paths following the one-photon ionization of the acetone monomer and its dimer have been studied by the joint use of several theoretical methods including the ab initio molecular dynamics, the global reaction route mapping, the intrinsic reaction coordinate, and the artificial force induced reaction calculations. Upon one-photon ionization, the dimer isomerizes to the H-bonded form, in which the enol cation of acetone is bound to the neutral molecule, while this enolization is energetically forbidden in the acetone monomer. The enolization of the dimer cation occurs through a two-step proton-transfer from the methyl group of the ionized moiety, and is catalyzed by the neutral moiety within the dimer cation.     

Almost Alternating Diagrams and Fibered Links in S3

Let R be a Seifert surface obtained by applying Seifert's algorithmto a connected diagram D for a link L. In this paper, lettingD be almost alternating, we give a practical algorithm to determinewhether L is a fibered link and R is a fiber surface. We furthershow that L is a fibered link and R is a fiber surface for Lif and only if R is a Hopf plumbing, that is, a successive plumbingof a finite number of Hopf bands. It has been known for sometime that this is true if D is alternating, and we show thatit is not always true if D is 2-almost alternating. In the appendix,we partially answer C. Adams's open question concerning almostalternating diagrams. 2000 Mathematical Subject Classification:57M25.     

Asymmetric [2,3]Wittig sigmatropic rearrangement involving a chiral azaenolate as the migrating terminus. A simple synthesis of (+)-verrucarinolactone

The diastereo- and/or enantioselection are described in the title rearrangement of the chiral 2-(2-alkenyloxy)methyl 2-oxazolines which eventually provides optically active -hydroxy, γ,δ- unsaturated esters and (+)-verrucarinolactone.     

Crosscap numbers of 2-bridge knots

We present a practical algorithm to determine the minimal genus of non-orientable spanning surfaces for 2-bridge knots, called the crosscap numbers. We will exhibit a table of crosscap numbers of 2-bridge knots up to 12 crossings (all 362 of them).     

1,3-Bis(pyren-1-yliminomethyl)calix[4]arene as a selective fluorescent turn-on sensor for mercury(II) ion

A novel calixarene-based diimine, 1,3-bis(pyren-1-yliminomethyl)calix[4]arene (5), serves as a turn-on-type fluorescent sensor, which selectively detects Hg²⁺ in THF/H₂O (99:1, v/v) in the presence of various other metal ions. Such selectivity is not seen with half salen 1 derived from salicylaldehyde and 1-aminopyrene. ¹H NMR analysis reveals that it is a chemodosimetric sensor based on its hydrolysis mediated by Hg²⁺ to release 1-aminopyrene molecules as fluorescent chromophores.     

Asymmetric “Acetylenic” [3+2] Cycloaddition of Nitrones Catalyzed by Cationic Chiral PdII Lewis Acid

Highly enantioselective [3+2] cycloaddition of ynones and nitrones has been developed. Very bulky ligand, DTBM‐SEGPHOS, was used for an effective asymmetric induction over distal reaction centers on the linear ynone dipolarophile and for prevention of Pd^II catalyst deactivation by coordination of the nitrones. The reaction has wide scope of substrates in both ynones and nitrones.     

The effect of Ag addition on electrical properties of the thermoelectric compound Ca3Co4O9

Ca₃Co₄O₉/Ag composites incorporating different amounts of Ag were synthesized by solid-state reaction. Scanning electron microscopy revealed Ag particles dispersed among and combined with Ca₃Co₄O₉ grains several times larger in size. The electrical resistivity (ρ) of the composites is favorably lower than that of Ca₃Co₄O₉ alone and decreases with increasing Ag content. It can thus be inferred that the highly conductive Ag particles between the oxide grains contribute to the reduction of ρ. Although minimal in smaller amounts, the addition of Ag also seems to have a negative impact on the Seebeck coefficient (S) of the composites due to its poor S. Since the reduction of ρ is more significant than the degradation of S, the power factor is found to be improved by the addition of 10 wt% Ag.