Halothiation as a Method for Oxidation of Primary Halides and Terminal Olefins to Aldehydes

The richly varied reactivity of the aldehyde group frequently imparts pivotal importance to this functionality in organic synthesis. This fact has resulted in the development of several methods for the elaboration of this structural unit from a variety of precursors.² The report delineates the feasibility of two new couplementary approaches which proceed under mild conditions and demonstrate the utility of “halothiation” as applied to the oxidation of primary halides and terminal olefins. We were led to investigate this approach as a direct consequence of our interest in the Ramberg-Bäcklund rearrangement³ where the preliminary step often involves α-chlorination of the sulfide substrate.⁴ Halothiation is defined by us as a three-step transformation involving introduction of an ArS moiety, directed α-chlorination of the resulting sulfide, and hydrolysis. In principle, of course, the ArSCH₂-unit is uniquely an aldehyde synthon and attention is therefore focused specifically on it at this time.     

Synthesis and cation binding properties of fluorescent calix[4]arene derivatives bearing tryptophan units at the lower rim

The fluorescent peptidocalixarenes, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,27-di(O-methyl)-26,28-bis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (2), were prepared by introducing tryptophan subunits at a lower calixarene rim. Coordination abilities of 1 and 2 towards Eu(III) and alkali metal cations were studied by spectrophotometric, spectrofluorimetric, conductometric and potentiometric titrations in acetonitrile at 25°C. Rather strong complexation was observed for smaller alkali metal cations Li⁺ and Na⁺ (log K _Li1 >6, log K _Li2 >6, log K _Na1  = 8.25, log K _Na2  = 6.94), and moderate for K⁺ (log K _K1  = 5.09, log K _K2  = 4.09). Larger Rb⁺ and Cs⁺ cations did not fit in the ion binding site of 1 so no complexation was detected, whereas the more flexible ligand 2 accommodated Rb⁺ cation (log K _Rb2  = 3.44). The fluorescence of 1 (λ_ex = 280 nm, λ_em = 340 nm) was remarkably quenched by Eu(III). Stability constant of 1:1 (Eu³⁺:1) complex determined spectrofluorimetrically amounted to log K _Eu1  = 6.16.     

Biosensors based on gold nanoelectrode ensembles and screen printed electrodes

Gold nanowires were synthesized within polycarbonate membranes according to an electroless deposition method, obtaining nanoelectrode ensembles (NEEs) with special electrochemical features. NEEs were coupled with home-produced carbon graphite screen printed electrodes and the electrochemical properties of the original nanoelectrode ensemble on screen printed substrate (NEE/SPS) assembly has been tested for sensors application. Glucose oxidase has been used as model enzyme in order to verify the feasibility of disposable gold NEE/SPS biosensors. Finally, different immobilisation and electrochemical deposition techniques based on either self assembled monolayers of cysteamine (CYS) or amino-propyl-triethoxysilane (APTES) and conductive polyaniline (PANI) molecular wires were used. Spatial patterning of the enzyme on the polycarbonate surface and of PANI wires on gold nanoelectrodes was obtained. Possible direct electron transfer between the enzyme and the PANI modified gold nanoelectrodes has been evaluated.     

Recoil-proton polarization in high-energy deuteron photodisintegration with circularly polarized photons

We measured the angular dependence of the three recoil-proton polarization components in two-body photodisintegration of the deuteron at a photon energy of 2 GeV. These new data provide a benchmark for calculations based on quantum chromodynamics. Two of the five existing models have made predictions of polarization observables. Both explain the longitudinal polarization transfer satisfactorily. Transverse polarizations are not well described, but suggest isovector dominance.     

High resolution spectroscopy of (lambda)(12)B by electroproduction

An experiment measuring electroproduction of hypernuclei has been performed in hall A at Jefferson Lab on a 12C target. In order to increase counting rates and provide unambiguous kaon identification two superconducting septum magnets and a ring imaging Cherenkov detector were added to the hall A standard equipment. An unprecedented energy resolution of less than 700 keV FWHM has been achieved. Thus, the observed (Lambda)(12)B spectrum shows for the first time identifiable strength in the core-excited region between the ground-state s-wave Lambda peak and the 11 MeV p-wave Lambda peak.