Photochemical activation of the carboxyl group via n-acyl-2-thionothiazolidines

Photolysis of N-acyl derivatives of 2-thionothiazolidine in the presence of ethanol affords ethyl esters; a mechanism involving γ-hydrogen abstraction by sulfur is postulated.     

Computer-aided Modelling of Decision-support Systems

Information systems have become increasingly complex over recent years, underscoring the challenge of designing systems which will provide the different functions in an organization with the information necessary for effective decision-making. With rapidly developing computer technology, it is natural that information systems evolve in a manner which is greatly dependent on computing hardware and software. Yet, there has been little development in the techniques of systems analysis and design to handle new and less well-understood functions which are of increasing interest.This paper demonstrates an application of structural modelling concepts to decision-support system synthesis. With the aid of the computer, structural modelling serves as an effective tool for: (1) partitioning a system into a set of subsystems; (2) specifying subsystems sufficiently to permit separate testing before total system tests; (3) eliminating redundant control information flow; and (4) facilitating decision-maker and system-analyst coordination and participation in the design process.     

Argon matrix absorption spectra of ClO, BrO, and IO and emission spectra of IO

Absorption spectra of ClO, BrO, and IO and the emission spectrum of IO have been observed from argon matrix samples prepared by microwave discharging the reagent mixture before condensation. Vibronic progressions were observed for each system. The spectroscopic scopic constants T_e, ω′_e, ω_ex′_e, ω″_e, and ω_ex″_e were evaluated from the absorption and emission data for comparison with gas-phase constants. Very good agreement is found for ClO. The argon matrix observations dictate a revision of the gas-phase vibronic assignments for BrO. The ground-state vibrational fundamental and T_e for argon matrix isolated IO are similar to the gas-phase values, but a lower excited-state spacing is found in the matrix.     

Bonding of multiple noble-gas atoms to CUO in solid neon: CUO(Ng)n (Ng=Ar, Kr, Xe; n=1, 2, 3, 4) complexes and the singlet-triplet crossover point

Laser-ablated U atoms co-deposited with CO in excess neon produce the novel CUO molecule, which forms distinct Ng complexes (Ng=Ar, Kr, Xe) with the heavier noble gases. The CUO(Ng) complexes are identified through CO isotopic and Ng reagent substitution and comparison to results of DFT frequency calculations. The U[bond]C and U[bond]O stretching frequencies of CUO(Ng) complexes are slightly red-shifted from neon matrix (1)Sigma(+) CUO values, which indicates a (1)A' ground state for the CUO(Ng) complexes. The CUO(Ng)(2) complexes in excess neon are likewise singlet molecules. However, the CUO(Ng)(3) and CUO(Ng)(4) complexes exhibit very different stretching frequencies and isotopic behaviors that are similar to those of CUO(Ar)(n) in a pure argon matrix, which has a (3)A" ground state based on DFT vibrational frequency calculations. This work suggests a coordination sphere model in which CUO in solid neon is initially solvated by four or more Ne atoms. Up to four heavier Ng atoms successively displace the Ne atoms leading ultimately to CUO(Ng)(4) complexes. The major changes in the CUO stretching frequencies from CUO(Ng)(2) to CUO(Ng)(3) provides evidence for the crossover from a singlet ground state to a triplet ground state.     

A parallel synthesis demonstration library of tri-substituted indazoles containing new antimutagenic/antioxidant hits related to benzydamine

A solution phase strategy for the multiple parallel synthesis of a demonstration library of indazoles is described by which regio-selectivity problems inherent to previous syntheses of this nucleus are largely overcome. Synthesis of selected components proceeded satisfactorily indicating that a fully realized library of indazole analogs could readily be produced using this methodology. Simple modifications of the basic nucleophilic aromatic substitution route unambiguously produce a range of N-1 substitutions (alkyl, aryl and aralkyl) in 50-75% yields. Next a range of substituents was introduced at the C-3 position in 50-80% yields by O-alkylation. Careful choice of reagents and reaction conditions were required to prevent by-product formation due to competing alkylation at N-2 (trace to 15% yields). When present, these contaminants were readily removed by chromofiltration. A third diversity site was sketched in at C-5 in 75-90% yield by reductive alkylation or acylation. Screening of some of the demonstration library members in vitro revealed highly active antioxidants suggesting that producing a full library would be worthwhile.     

Mid-infrared metamaterial based on perforated SiC membrane: engineering optical response using surface phonon polaritons

We theoretically and experimentally study electromagnetic properties of a novel mid-infrared metamaterial: optically thin silicon carbide (SiC) membrane perforated by an array of sub-wavelength holes. Giant absorption and transmission is found using Fourier transformed infrared (FTIR) microscopy and explained by introducing a frequency-dependent effective permittivity ε_eff(ω) of the perforated film. The value of ε_eff(ω) is determined by the excitation of two distinct types of hole resonances: delocalized slow surface polaritons (SSPs) whose frequencies are largely determined by the array period, and a localized surface polariton (LSP) corresponding to the resonance of an isolated hole. Only SSPs are shown to modify ε_eff(ω) strongly enough to cause giant transmission and absorption. Because of the sub-wavelength period of the hole array, anomalous optical properties can be directly traced to surface polaritons, and their interpretation is not obscured by diffractive effects. Giant absorbance of this metamaterial can be utilized in designing highly efficient thermal radiation sources. PACS 41.20.Cv; 42.70.Qs; 71.45.Gm