Expedient one-pot synthesis of N-aryliminoethers via mild electrophilic activation of secondary amides

Abstract  

The direct transformation of various secondary amides into N-aryliminoethers via mild electrophilic activation with trifluoromethanesulfonic anhydride in the presence of 2-chloropyridine is described. Low temperature amide activation followed by warming to 0 °C and subsequent treatment with phenols provides the desired products with short overall reaction times and moderate to high reaction yields.     

A unified theory of contra-(μ,λ)-continuous functions in generalized topological spaces

We introduce a new notion called contra-(μ,λ)-continuous functions as functions on generalized topological spaces?[8]. We obtain some characterizations and several properties of such functions. The functions enable us to formulate a unified theory of several modifications of contra-continuity due to Dontchev?[18].     

Fluorescence Enhancement of Carbendazim Fungicide in Cucurbit[6]uril

The potential increase in fluorescence of a benzimidazole-type fungicide (carbendazim) due to complexation with cucurbit[6]uril is reported. The fluorescence of the probe carbendazim in aqueous Na₂SO₄ solution (pH=7.61) at room temperature is found to increase by a maximum factor of ∼10.0 and blue-shifted up to ∼11±1 nm with the increase in cucurbit[6]uril concentration up to ∼5 mM. This fluorescence enhancement is the result of formation of a 1:1 guest-host inclusion complex, in which the guest carbendazim is incorporated inside the hydrophobic cavity of the host curbit[6]uril through the amido-ester part. Such mode of inclusion is supported by NMR spectral measurements, in which upon encapsulation, the resonance of the methyl-protons of the amido-ester moiety is shifted significantly to upfield in the ¹H NMR spectrum. Also, to assess the formation of inclusion complex, solid samples prepared by co-evaporation have been studied, using differential scanning calorimetry (DSC). Measurement of the enhancement as a function of cucurbit[6]uril concentrations yielded a value of the equilibrium constant (K _a ) of 271±10 M⁻¹ at 25°C. From the temperature dependence of the equilibrium constants, ΔH and ΔS values have been negative in sign, indicating the dipole-dipole interactions and the steric factors associated with the formation of this inclusion complex. It might be proposed that the spectral changes due to the inclusion of carbendazim are the result of decrease in the polarity of the surrounded media rather than the loss of carbendazim rotational mobility.     

Broadband light generation by noncollinear parametric downconversion

Broadband light generation is demonstrated by noncollinear spontaneous parametric downconversion with a cw pump laser. By use of a suitable noncollinear phase-matching geometry and a tightly focused pump beam, downconverted signals that feature a bell-shaped spectral distribution with a bandwidth approaching 200 nm are obtained. As an application of the generated broadband light, submicrometer axial resolution in an optical coherence tomography scheme is demonstrated; a free-space resolution down to 0.8 microm was achieved.     

Protein splicing in cis and in trans

Intein-mediated protein splicing is a self-catalytic process in which the intervening intein sequence is removed from a precursor protein and the flanking extein segments are ligated with a native peptide bond. Splice junction proximal residues and internal residues within the intein direct these reactions. The identity of these residues varies in each intein, as groups of related residues populate conserved motifs. Although the basics of the four-step protein splicing pathway are known, mechanistic details are still unknown. Structural and kinetic analyses are beginning to shed some light. Several structures were reported for precursor proteins with mutations in catalytic residues, which stabilize the precursors for crystallographic study. Progress is being made despite limitations inherent in using mutated precursors. However, no uniform mechanism has emerged. Kinetic parameters were determined using conditional trans-splicing (splicing of split precursor fragments after intein reassembly). Several groups concluded that the rate of the initial acyl rearrangement step is rapid and Asn cyclization (step 3) is slow, suggesting that this latter step is rate limiting. Understanding the protein splicing pathway has allowed scientists to harness inteins for numerous applications.     

Fine structure of 6A1g → 4A1g, 4Eg (4G) absorption band in MnF2

Systematic spectroscopic measurements of the spectral lines in MnF₂ have been carried out in the temperature range 10–300 K. Observations of exciton and exciton–magnon sidebands in the fine structures of the ⁶A_1g → ⁴A_1g, ⁴E_g (⁴G) state of Mn⁺² ions are reported at low temperatures for MnF₂. The fine structure of the C-band is mainly attributed to spin multiplicity in the ordered state. In addition, the pure exciton bands have been identified and the ratios for the separation energies between these lines are fitted with the ratios expected form Lande interval rule.     

Existence results for non-linear singular integral equations with hilbert kernel in banach spaces

A class of non-linear singular integral equations with Hilbert kernel and a related class of quasi-linear singular integro-differential equations are investigated by applying Schauder's fixed point theorem in Banach spaces.      

The hyperfine properties of a hydrogenated Fe/V superlattice

We study the effect of hydrogen on the electronic, magnetic and hyperfine structures of an iron-vanadium superlattice consisting of three Fe monolayers and nine V monolayers. The contact charge density (ρ), the contact hyperfine field (B_hf) and the electronic field gradient (EFG) at the Fe sites for different H locations and H fillings are calculated using the first principle full-potential linear-augmented-plane-wave (FP-LAPW) method. It is found that sizeable changes in the hyperfine properties are obtained only when H is in the interface region.     

Synthesis of new pyrazolo[1,5‐a]pyrimidines and pyrazolo[3,4‐b]pyridines

While 3(5)‐aminopyrazole reacts with enaminonitrile to yield pyrazolo[1,5‐a]pyrimidines, 3‐amino‐5‐pyrazolone reacts with the same reagents to yields pyrazolo[3,4‐b]pyridines.     

Effective Heuristics for the GPS Survey Network of Malta: Simulated Annealing and Tabu Search Techniques

A GPS network can be defined as a set of stations, co-ordinated by a series of sessions formed by placing receivers on the stations. This paper shows how to search for the best order in which to observe these sessions giving the cheapest schedule. The complexity of observing GPS networks increases with their size and become highly difficult to solve effectively. To obtain good methods to solve this problem a new area of research is implemented. This area is based on developed heuristic techniques that provide an optimal or near optimal solution for large networks. Comparing their outcome in terms of solution quality and computational effort proves the performance of the developed techniques.