One-step versus stepwise mechanism in protonated amino acid-promoted electron-transfer reduction of a quinone by electron donors and two-electron reduction by a dihydronicotinamide adenine dinucleotide analogue. Interplay between electron transfer and hydrogen bonding

Semiquinone radical anion of 1-(p-tolylsulfinyl)-2,5-benzoquinone (TolSQ(*-)) forms a strong hydrogen bond with protonated histidine (TolSQ(*-)/His x 2 H(+)), which was successfully detected by electron spin resonance. Strong hydrogen bonding between TolSQ(*-) and His x 2 H(+) results in acceleration of electron transfer (ET) from ferrocenes [R2Fc, R = C5H5, C5H4(n-Bu), C5H4Me] to TolSQ, when the one-electron reduction potential of TolSQ is largely shifted to the positive direction in the presence of His x 2 H(+). The rates of His x 2 H(+)-promoted ET from R2Fc to TolSQ exhibit deuterium kinetic isotope effects due to partial dissociation of the N-H bond in His x 2 H(+) at the transition state, when His x 2 H(+) is replaced by the deuterated compound (His x 2 D(+)-d6). The observed deuterium kinetic isotope effect (kH/kD) decreases continuously with increasing the driving force of ET to approach kH/kD = 1.0. On the other hand, His x 2 H(+) also promotes a hydride reduction of TolSQ by an NADH analogue, 9,10-dihydro-10-methylacridine (AcrH2). The hydride reduction proceeds via the one-step hydride-transfer pathway. In such a case, a large deuterium kinetic isotope effect is observed in the rate of the hydride transfer, when AcrH2 is replaced by the dideuterated compound (AcrD2). In sharp contrast to this, no deuterium kinetic isotope effect is observed, when His x 2 H(+) is replaced by His x 2 D(+)-d6. On the other hand, direct protonation of TolSQ and 9,10-phenanthrenequinone (PQ) also results in efficient reductions of TolSQH(+) and PQH(+) by AcrH2, respectively. In this case, however, the hydride-transfer reactions occur via the ET pathway, that is, ET from AcrH2 to TolSQH(+) and PQH(+) occurs in preference to direct hydride transfer from AcrH2 to TolSQH(+) and PQH(+), respectively. The AcrH2(*+) produced by the ET oxidation of AcrH2 by TolSQH(+) and PQH(+) was directly detected by using a stopped-flow technique.     

Neutron Pairing Correlations in an {\alpha}–{n}–{n} Three-Cluster Model of the {^{6}}He Nucleus

An \({\alpha}\)–n–n three-cluster model of the \({^6}\)He nucleus is studied by solving the Faddeev equations, where the cluster potential between \({\alpha}\) and n takes into account the Pauli exclusion correction, using the Fish-Bone Optical Model (Schmid in Z Phys A 297:105, 1980). The resulting binding energy of the ground state (\({0^+}\)) is 0.831 MeV and the resonance energy of the first excited state (\({2^+}\)), 0.60–i0.012 MeV, is extracted from the three-cluster break-up threshold. These theoretical values are in reasonable agreement with the experimental data: 0.973 MeV and 0.824–i0.056 MeV, respectively. In order to investigate the structure of these states, we calculate the angle density matrix for the \({\angle n_1 \alpha n_2}\) angle in the triangle formed by the three clusters. The angle density matrix of the ground state has two peaks and the configuration of \({0^+}\) wave function corresponding to the peaks constitutes a mixture of an acute-angled triangle structure and an obtuse-angled one. This finding is consistent with the former result from a variational approach (Hagino and Sagawa in Phys Rev C 72:044321, 2005). On the other hand, in the case of \({2^+}\) state only a single peak is obtained.     

Unidirectional crystallization of charged colloidal silica due to the diffusion of a base

Dilute aqueous dispersions of charged colloidal silica (particle volume fraction = approximately 0.03-0.04, particle diameter = 110 nm) exhibit unidirectional crystal growth due to the diffusion of a weak base, pyridine (Py). Similar diffusion-crystallization is enabled by a salt of a weak acid and a strong base, sodium hydrogen carbonate (NaHCO3). The resulting crystals consist of columnar (or cubic) crystal grains with a maximum height of a few centimeters and a maximum width of 1 cm. The crystal growth process is attributed to a combination of (i) the diffusion of Py or NaHCO3 accompanied by a charging reaction of the silica particles and (ii) the charge-induced crystallization of the silica colloids. Theoretical growth curves based on the reaction-diffusion model for the case of Py were in good agreement with the observed curves. We also report the immobilization of the resulting large crystals by using a polymer hydrogel matrix.     

Tuning the effective width of the optical stop band in colloidal photonic crystals

The optical stop band in colloidal crystals is characterized by the central frequency and bandwidth. Although the former is known to be highly tunable by changing the lattice constant, the latter is basically determined by the refractive index contrast between the particles and the background medium that is intrinsic to the materials. In this study, we show that the effective bandwidth in gelled colloidal crystals can also be tuned by controlling the fabrication conditions. Single-domain gelled colloidal crystals were prepared by photopolymerization under various photoirradiation conditions. It was observed that the width of the stop band in the transmission or reflectance spectrum could be expanded by simply adjusting the irradiation time.     

Partial-Wave Decomposition for Meson-Exchange Currents in Few-Nucleon Systems

 We develop an approach for calculating matrix elements of meson-exchange current operators between three-nucleon basis states in -coupling and a three-nucleon bound state. The contributions generated by π- and ρ-exchanges are included into the consideration. The matrix elements are expressed in terms of multiple integrals in momentum space. We apply a technique of partial-wave decompositions and carry out some angular integrations in closed form. Different representations appropriate for numerical calculations are derived for the matrix elements of interest. The momentum dependences of the matrix elements are studied and benchmark results are presented. The approach developed is of interest for investigations of deuteron-proton radiative capture and ³He photo- and electrodisintegration when the interactions in the initial or final states are taken into account by solving the Faddeev equations. Received April 2, 1999; accepted for publication December 30, 1999     

A one-pot procedure for trifluoroacetylation of arylamines using trifluoroacetic acid as a trifluoroacetylating reagent

A convenient procedure for the preparation of aryl trifluoroacetamides from aryl amines is described that employs 2-4 M equiv of trifluoroacetic acid in refluxing xylene as a trifluoroacetylating agent. Addition of an amount of pyridine that is equimolar to the amount of trifluoroacetic acid present in the reaction mixture facilitates the trifluoroacetylation of rather basic arylamines.     

Potential-modulated fluorescence spectroscopy of the membrane potential-sensitive dye di-4-ANEPPS at the 1,2-dichloroethane/water interface

The spectrofluorometric behavior of a membrane potential-sensitive dye, 1-(3-sulfonatopropyl)-4-[β-{2-(di-N-butylamino)-6-naphthyl}vinyl]pyridinium betaine (di-4-ANEPPS), at the polarized 1,2-dichloroethane/water interface was studied by means of potential-modulated fluorescence (PMF) spectroscopy. The results, combined with those from cyclic and alternating current voltammetry, clearly suggested that the dye adsorbed at the interface underwent a reorientation with increasing the interfacial potential, giving a well-developed PMF response as well as a voltammetric response. In addition to the PMF response, another PMF response was observed by addition of dilauroyl phosphatidylcholine (DLPC). This additional response was well explained in terms of a reorientation of di-4-ANEPPS at the interface, which would be induced by the potential-dependent desorption of DLPC from the interface. Thus, the present study supported the reorientation/solvatochromic mechanism for the membrane potential-sensitive dye rather than the electrochromic mechanism.     

An OFF-OFF-ON fluorescence sensor for metal ions in stepwise complex formation of 2,3,5,6-tetrakis(2-pyridyl)pyrazine with metal ions

The fluorescence intensity of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (TPPZ) begins to increase at concentrations of metal ions (Mn+) above the 1:2 ratio of metal ion concentration to the initial concentration of TPPZ ([Mn+]/[TPPZ]0 > 0.5), when a 2:1 complex of TPPZ with Mn+ [(TPPZ)2-Mn+] is converted to a 1:1 complex of TPPZ with Mn+ (TPPZ-Mn+), which exhibits strong fluorescence.     

Low-energy neutron-deuteron reactions with N 3 LO chiral forces

Based on the preformed cluster model (PCM), we have extended our earlier study on cluster decays of heavy parent nuclei to analyze the effects of different nuclear proximity potentials in the ground-state clusterization of superheavy nuclei with Z = 113, 115 and 117. In order to look for the possible role of deformations, calculations are performed for spherical as well as β ₂-deformed choices of fragmentation. The relevance of “hot compact” over “cold elongated” configurations due to orientations is also explored, in addition to the role of Q value and angular momentum ℓ effects. As the PCM is based on collective clusterization picture, the preformation and penetration probabilities get modified considerably, and hence do so the decay constants and half-lives of the clusters, with the use of different nuclear proximity potentials. The comparative importance of nuclear proximity potentials Prox-1977 and Prox-2000 is analyzed and the calculated decay half-lives in the framework of PCM are compared with the recent predictions of the analytical super-asymmetric fission model (ASAFM). The possible role of shell corrections is also investigated for understanding the dynamics of heavy particle radioactivity. Finally, the potential energy surfaces are compared for different proton and neutron magic numbers in superheavy mass region.