An electrochemical chiral sensor based on electrochemically modified electrode for the enantioselective discrimination of D-/L-tryptophan

Journal of Solid State Electrochemistry - Chirality is a universal characteristic of natural systems and discrimination of enantiomers of a chiral molecule plays a major role particularly in...     

Performance analysis of nitride alternative plasmonic materials for localized surface plasmon applications

We consider methods to define the performance metrics for different plasmonic materials to be used in localized surface plasmon applications. Optical efficiencies are shown to be better indicators of performance as compared to approximations in the quasistatic regime. The near-field intensity efficiency, which is a generalized form of the well-known scattering efficiency, is a more flexible and useful metric for local-field enhancement applications. We also examine the evolution of the field enhancement from a particle surface to the far-field regime for spherical nanoparticles with varying radii. Titanium nitride and zirconium nitride, which were recently suggested as alternative plasmonic materials in the visible and near-infrared ranges, are compared to the performance of gold. In contrast to the results from quasistatic methods, both nitride materials are very good alternatives to the usual plasmonic materials.     

Mechanistic study of stereoselective gas-phase reactions of phosphenium ions with cis- and trans-1,2-diaminocyclohexanes

The 1,3-dioxolane-2-phosphenium ion, 1,3-benzodioxole-2-phosphenium ion, and o-biphenylenephosphenium ion are reported to react in a stereoselective manner with cis- and trans-1,2-diaminocyclohexanes in the gas phase in a Fourier transform ion cyclotron resonance mass spectrometer. Elimination of NH3 from an addition product was observed only for the trans isomer. Several reaction mechanisms were experimentally and computationally examined (B3LYP/6-31G(d)//HF/6-31G(d) + ZPVE level of theory). The most plausible mechanism is initiated by addition of one of the amino groups to the electrophilic phosphorus atom followed by proton transfer between the amino groups. A change to a diaxial conformation for the trans isomer facilitates anchimeric assistance by the now nucleophilic phosphorus atom as the C-N bond breaks to release NH3. Intramolecular proton transfer competes with the conformational change and ultimately leads to ethylene glycol elimination. The transition states for the critical steps of these two reactions are calculated to be nearly equal in magnitude, which rationalizes the observation of both reactions for the trans-diamine. In contrast, the adduct of the cis isomer can eliminate NH3 via a concerted 1,2-hydride shift without a need for a conformational change. However, the barrier associated with this reaction was found to be substantially greater than for proton transfer between the N- and O-atoms. The latter reaction dominates and ultimately leads to ethylene glycol elimination.     

The investigation of complexation properties and synthesis of the (salen and salophen)-bridged Fe/Cr(III) capped complexes of novel Schiff bases

This article describes synthesis of novel Schiff base and its complexation properties with Fe(III) and Cr(III). Firstly 1,3,5-tris (formylphenoxymethyl)benzene (1, TRIPOD) with tris aldehyde groups were synthesized using the 1,3,5-trisbromomethylbenzene and 4-hydroxybezaldehyde. The compound 1 was converted to the Schiff base derivative (2, TCPIM-TRIPOD) with p-aminobenzoic acid. The prepared TCPIM-TRIPOD were reacted with four new trinuclear Fe(III) and Cr(III) complexes involving tetradenta Schiff bases N,N-bis(salicylidene)ethylenediamine-(salenH₂) or bis(salicylidene)-o-phenylenediamine-(salophenH₂) and characterized by means of elemental analysis carrying out infrared spectroscopy (IR), thermogravimetric analysis (TG), nuclear magnetic resonance (¹H-NMR), elemental analysis and magnetic susceptibility measurement. The complexes can also be characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange.     

Reactions of charged phenyl radicals with aliphatic amino acids in the gas phase

Gas-phase reactivity of five differently substituted positively charged phenyl radicals was examined toward six amino acids by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR). The reactivity of the radicals studied was determined by the electrophilicity of the radical, which can be characterized by the radical's electron affinity (EA). The larger the electron affinity of the radical, the higher the overall reaction rate. In addition to the expected H-atom abstraction, several unprecedented reaction pathways were observed, including NH2 abstraction, SH abstraction, and SCH3 abstraction. These reaction pathways dominate for the most electrophilic radicals, and they may not follow radical but rather nucleophilic addition-elimination mechanisms. Hydrogen abstraction from glycine was also investigated theoretically. The results indicate that hydrogen abstraction from alphaC of glycine is both kinetically and thermodynamically favored over the NH2 group. The ordering of transition state energies for hydrogen abstraction from the alphaC and NH2 groups was found to reflect the radicals' EA ordering.     

Measurement of B(0)(d)-B_(0)(d) mixing rate from the time evolution of dilepton events at the upsilon(4S)

We report a determination of the B(0)(d)-&B_(0)(d) mixing parameter Deltam(d) based on the time evolution of dilepton yields in Upsilon(4S) decays. The measurement is based on a 5.9 fb(-1) data sample collected by the Belle detector at KEKB. The proper-time difference distributions for same-sign and opposite-sign dilepton events are simultaneously fitted to an expression containing Deltam(d) as a free parameter. Using both muons and electrons, we obtain Deltam(d) = 0.463+/-0.008 (stat)+/-0.016 (syst) ps(-1). This is the first determination of Deltam(d) from time evolution measurements at the Upsilon(4S). We also place limits on possible CPT violations.     

Quantitative determination of the selectivities of five different phenyl radicals in hydrogen atom abstraction from ethanol

An experimental method is described for obtaining quantitative selectivity information for H-atom abstraction by organic radicals from different sites of a substrate in the gas phase. The method is used to determine the selectivities of five different phenyl radicals toward the three different types of hydrogen atoms in ethanol. This experimental method involves studying the reactivities and selectivities of derivatives of the radicals that contain a chemically inert, charged group (distonic ions), which allows them to be manipulated in a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer.     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

Observation of large CP violation in the neutral B meson system

We present a measurement of the standard model CP violation parameter sin2 phi(1) based on a 29.1 fb(-1) data sample collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. One neutral B meson is fully reconstructed as a J/psi K(S), psi(2S)K(S), chi(c1)K(S), eta(c)K(S), J/psi K(L), or J/psi K(*0) decay and the flavor of the accompanying B meson is identified from its decay products. From the asymmetry in the distribution of the time intervals between the two B meson decay points, we determine sin2 phi(1) = 0.99+/-0.14(stat)+/-0.06(syst). We conclude that we have observed CP violation in the neutral B meson system.