Access to substituted cyclobutenes by tandem [3,3]-sigmatropic rearrangement/[2 + 2] cycloaddition of dipropargylphosphonates under Ag/Co relay catalysis

We present herein an unconventional tandem [3,3]-sigmatropic rearrangement/[2 + 2] cycloaddition of simple dipropargylphosphonates to deliver a range of bicyclic polysubstituted cyclobutenes and cyclobutanes under Ag/Co relay catalysis. An interesting switch from allene–allene to allene–alkyne cycloaddition was observed based on the substitution of the substrates, which further diversified the range of compounds accessible from this practical method. Significantly, preliminary biological screening of these new compounds identified promising candidates as suppressors of cellular proliferation.

In situ generation of allenes through [3,3]-sigmatropic rearrangement of propargylphosphonates. Divergent allene–allene or allene–alkyne cycloaddition by Ag/Co relay catalysis. Products as promising suppressors of cellular proliferation.     

Determination of six indolic compounds, including melatonin, in rat pineal using high-performance liquid chromatography with serial fluorimetric-electrochemical detection.

A reversed-phase high-performance liquid chromatographic method has been developed for the simultaneous determination of 5-hydroxytryptophan, 5-hydroxyindoleacetic acid, N-acetylserotonin, tryptophan, 5-hydroxytryptamine (serotonin) and melatonin in rat pineal using a buffered aqueous eluent containing acetonitrile and methanol as organic modifiers and an ion-pairing agent to assist in controlling the retention of compounds containing an amine group. Serial fluorimetric-electrochemical detection provided additional assurance of compound identity. Analyte preparation simply involved the sonication of pineals in dilute perchloric acid containing an antioxidant and a chelating agent, followed by centrifugation to clarify. The method simplifies the determination of this range of indolic compounds, which normally would require at least two separate runs with different eluents. Detection limits for melatonin were 60 and 135 pg for fluorimetric and electrochemical detection, respectively. (This represented the "worst case" considering the levels and detection limits of all compounds present.) Using flow programming and a flow-rate varying between 1 and 1.5 ml/min, the analysis time was 27.5 min, which made the determination of ten samples in a working day possible.     

Synthesis of 1-(o-substituted-phenyl)-3,4-dimethylenepyrrolidines by the thermal elimination of sulfur dioxide

Precursors of 1-(o-substituted-phenyl)-3,4-dimethylenepyrrolidines, 5-(o-substituted-phenyl)-1,3,4,6-tetra-hydrothieno[3,4-c]pyrrole 2,2- dioxides 2 , were synthesized by reacting o-substituted anilines with 3,4-bis(bromomethyl)-2,5-dihydrothiophene 1,1-dioxide. A disubstitution product along with the desired 2 was obtained when excess amine was used to neutralize the amine salts that were formed from nucleophilic substitution. A 1,4-HBr elimination product was obtained in three out of four cases when sodium carbonate was used to neutralize the amine salts. The 1,4-HBr elimination product resulted from a competing base attack on the acidic sulfolene protons. The 3,4-dimethylenepyrrolidines were obtained by thermal elimination of sulfur dioxide from 2 .     

Oxime esters of anthraquinone as photo-induced DNA-cleaving agents for single- and double-strand scissions

Anthraquinone-O-9-(4-cyanobenzoyl)oxime (13) with binding constant of 4.49×10⁴ M⁻¹ exhibited single-strand scission of DNA at the concentration of 10 μM and double-strand scission at 50 μM upon UV irradiation.     

Metallocene and Organo-main Group Trifluoromethanesulfonates

The substituted metallocene compounds Cp₂M(OSO₂CF₃)₂ (Cp=η⁵-C₅H₅; M = Ti, Zr, Hf, Nb, Mo), CpTi(OSO₂CF₃)₃ · 0.75(1,2-dimethoxyethane), and the organo-main group compounds (C₆H₅)₃M′(OSO₂CF₃) (M′=Si, Ge), (C₆H₅)₂Sn(OSO₂CF₃)₂ and (C₆H₅)₃Sb(OSO₂CF₃)₂, were synthesized from the corresponding chloride or bromide compounds and silver trifluoromethanesulfonate (triflate) and characterized spectroscopically, including a detailed analysis of their IR spectra. Triflate coordination is typically monodentate, but CpTi(OSO₂CF₃)₃ · 0.75(1,2-dimethoxyethane) and the organo-germanium triflate show evidence of bidentate CF₃SO ₃⁻ ligands and are likely to have polymeric structures. Conductance measurements in nitromethane, acetone and acetonitrile have demonstrated the ease of triflate substitution, with a limited kinetic study of acetone solvation of the Ti and Hf compounds supporting an associative pathway. Three new catalysts for the polymerization of tetrahydrofuran, Cp₂HfCl₂/Ag(OSO₂CF₃), CpTiCl₃/Ag(OSO₂CF₃) and (C₆H₅)₂SiCl₂/Ag(OSO₂CF₃), are also reported.     

The gas-phase dipeptide analogue acetyl-phenylalanyl-amide: a model for the study of side chain/backbone interactions in proteins

The issue of the influence of the side chain/backbone interaction on the local conformational preferences of a phenylalanine residue in a peptide chain is addressed. A synergetic approach is used, which combines gas-phase UV spectroscopy as well as gas-phase IR/UV double-resonance experiments with DFT and post Hartree-Fock calculations. N-Acetyl-Phe-amide was chosen as a model system for which three different conformers were observed. The most stable conformer has been identified as an extended beta(L) conformation of the peptide backbone. It is stabilized by a weak but significant NH-pi interaction bridging the aromatic ring on the residue (i) with the NH group on residue (i+1), with the aromatic side chain being in an anti conformation. This stable conformation corresponds to the common NH(i+1)-aromatic(i) interaction encountered in proteins for the three aromatic residues (phenylalanine, tyrosine, and tryptophan), which illustrates the relevance of gas-phase investigations to structural biology issues. The two other less abundant conformers have been assigned to two gamma-folded backbone conformations that differ by the orientation of the side chain. In all cases, the IR data provided spectroscopic fingerprints of these interactions. Finally, the strong conformational dependence of the fluorescence yield found for N-acetyl-Phe-amide illustrates the role of the environment on the excited-state dynamics of these species, which is often exploited by biochemists to monitor protein structural changes from tryptophan lifetime measurements.     

Synthesis and characteristics of microcapsules containing electrophoretic particle suspensions

A microcapsule containing titanium dioxide (TiO₂) and halocarbon oil was synthesized via an in situ polymerization using urea, melamine, and formaldehyde (UM/F) as a wall material to examine its potential application as a microcapsule-based electronic ink display technique. Poly(sodium styrene sulfonate) was used as an anionic polymeric surfactant to stabilize a droplet of the suspension, and easily combined with the UM/F prepolymer through ionic adsorption. The microcapsules obtained had an average diameter and wall thickness of approximately 50 μm and 500 nm, respectively. The electrophoretic TiO₂ particles in the microcapsules responded to electric fields with a response time of few seconds.     

Moving focus in the propagation of ultrashort laser pulses in air

The long light filaments generated in air by powerful ultrashort laser pulses, previously attributed to self-channeling, were investigated by use of gigawatt pulses from a Ti:sapphire chirped-pulse-amplification laser system. A filament contained only a small fraction of the pulse energy and always ended at the diffraction length of the beam (~100 m), independently of the pulse energy. These features are explained by the moving-focus model, which is presented as an alternative to the self-channeling model. Computer simulations involving ionization of the air also support the moving-focus model.     

Correlation dimension for iterated function systems

The correlation dimension of an attractor is a fundamental dynamical invariant that can be computed from a time series. We show that the correlation dimension of the attractor of a class of iterated function systems in is typically uniquely determined by the contraction rates of the maps which make up the system. When the contraction rates are uniform in each direction, our results imply that for a corresponding class of deterministic systems the information dimension of the attractor is typically equal to its Lyapunov dimension, as conjected by Kaplan and Yorke.

     

Biohydrogen Production from Mushroom Cultivation Waste by Anaerobic Solid‐state Fermentation

Mushroom cultivation waste (MCW) is a polypropylene bag stuffed with wood flour and nutrients for growing mushroom, which is a feasible feedstock for anaerobic biohydrogen production owing to its abundant availability, high organic and nutrient content. This study optimized the seed inoculum from various waste sludges (sewage sludge, cow dung and pig slurry), nutrient addition and operation conditions (moisture content and MCW powder particle size) for maximal biohydrogen production by solid‐state fermentation (SSF). SSF batch test was operated at a MCW 3 g total volatile solid (TVS)/L, temperature 55 °C and rotation speed of 15 rpm with a vertical rotative shaker. The peak hydrogen production performance of hydrogen production rate (HPR) 9.50 mol H₂/kg‐d and hydrogen yield (HY) 0.29 mmol H₂/g TVS) are obtained using sewage sludge 2 seed inoculum, nutrients addition, moisture content 70 % and particle size of 1.190～0.590 mm. The results show that the MCW has the potential for hydrogen production by anaerobic mixed microflora using solid‐state fermentation. The bioenergy of 1842 kWh while using SSF to conver MCW to produce biohydrogen and it could reduce CO₂ emission of 114–178 kg per year comparing using fossil fuel such as coal, fuel oil and natural gas.