Further studies on the application of vinylogous amides and β-halovinylaldehydes to the regiospecific synthesis of unsymmetrical,polyfunctionalized 2,3,4- and 1,2,3,4- substituted pyrroles

Highly functionalized pyrroles with appropriate regiochemical functionality represent an important class of marine natural products and potential drug candidates. We describe herein a detailed study of the reaction of α-aminoacid esters with vinylogous amides and also β-halovinylaldehydes for the regiospecific synthesis of 2,3,4-trisubstituted and 1,2,3,4-tetrasubstituted pyrroles. Since the vinylogous amides and β-halovinylaldehydes are readily available precursors, rapid access to a wide variety of unsymmetrically substituted pyrroles is accomplished via this methodology.     

Transport properties of copper-doped carbon aerogels

The magnetic susceptibility, conductivity, magnetoresistance (MR) and Hall effect of copper-doped carbon aerogels are measured and compared with corresponding results from the original carbon aerogels. The experimental results indicate that the temperature-dependent magnetic susceptibility of the copper-doped and of the original carbon aerogels is well fit by a Curie function at low temperatures. The copper-doped carbon aerogels show a higher susceptibility and spin concentration than the original carbon aerogel. After doping by copper, the materials exhibit a more linear current-voltage curve than the original carbon aerogel under the same measurement conditions. The electrical resistance of the copper-doped carbon aerogels is strikingly lower than that of the original carbon aerogels, and decreases with increasing copper content in the samples. The temperature-dependent resistivity ρ(T) of all of the copper-doped and original carbon aerogels can be fitted by an exp(T^−1/2) dependence for T<100 K. The copper-doped and pristine carbon aerogels follow a quadratic MR behavior Δρ/ρ=AB² in the magnetic field range B investigated (up to 5 T), except at very low temperatures (T<4 K).     

Quantum chemical computations and Fourier transform infrared spectral studies of a nonlinear food dye E110

Fourier transform infrared (FTIR) spectrum of a well-known food dye sunset yellow FCF (E110) has been recorded and analysed. Assignments of the vibrational spectrum has been facilitated by density functional theory (DFT) calculations. The results of the optimized molecular structure obtained on the basis of B3LYP with 6-31G(d) along with the 'LANL2DZ' basis sets give clear evidence for the intramolecular charge transfer (ICT) and strong hydrogen bonding enhancing the optical nonlinearity of the molecule. The first hyperpolarizability of the acidic monoazo dye 'E110' is computed. Azo stretching frequencies have been lowered due to conjugation and pi-electron delocalization. Hydroxyl vibrations with intramolecular H-bonding are analyzed, supported by the computed results. The natural bond orbitals (NBO) analysis confirms this strong hydrogen bond between the hydrogen of the hydroxyl group and nitrogen of the azo group of the molecule. Assignments of benzene and naphthalene ring vibrations are found to agree well with the theoretical wave numbers.     

Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of p-amino acetanilide

The infrared absorption, Raman spectra and SERS spectra of p-amino acetanilide have been analyzed with the aid of density functional theory calculations at B3LYP/6-311G(d,p) level. The electric dipole moment (mu) and the first hyperpolarizability (beta) values of the investigated molecule have been computed using ab initio quantum mechanical calculations. The calculation results also show that the synthesized molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. Computed geometries reveal that the PAA molecule is planar, while secondary amide group is twisted with respect to the phenyl ring is found, upon hydrogen bonding. The hyperconjugation of the C=O group with adjacent C-C bond and donor-acceptor interaction associated with the secondary amide have been investigated using computed geometry. The carbonyl stretching band position is found to be influenced by the tendency of phenyl ring to withdraw nitrogen lone pair, intermolecular hydrogen bonding, conjugation and hyperconjugation. The existence of intramolecular C=O...H hydrogen bonded have been investigated by means of the natural bonding orbital (NBO) analysis. The influence of the decrease of N-H and C=O bond orders and increase of C-N bond orders due to donor-acceptor interaction has been identified in the vibrational spectra. The SERS spectral analysis reveals that the large enhancement of in-plane bending, out of plane bending and ring breathing modes in the surface-enhanced Raman scattering spectrum indicates that the molecule is adsorbed on the silver surface in a 'atleast vertical' configuration, with the ring perpendicular to the silver surface.     

A simple and cost effective method for the quantification of 8-hydroxy-2'-deoxyguanosine from urine using liquid chromatography tandem mass spectrometry

A rapid and high-throughput method for the determination of urinary levels of the oxidative stress biomarker, 8-hydroxy-2'-deoxyguanosine (8-OH-dG), has been developed and validated using liquid chromatography combined with electrospray ionization tandem mass spectrometry (LC-MS/MS). The assay features a cheap and readily available non-isotopic internal standard, a single-step filtration sample preparation, and a total analysis time of 6 min including column re-equilibration. The method was validated based on linearity, accuracy (100-106%), precision (CV < 7%), sample preparation stability (< or =5%, 72 h). Intra-laboratory patient ranges were established comparing children and adults (n = 345).     

Improved efficiency in micellar liquid chromatography using triethylamine and 1-butanol as mobile phase additives to reduce surfactant adsorption

The effect of triethylamine as a mobile phase modifier on chromatographic efficiency in micellar liquid chromatography (MLC) is reported for nine different columns with various bonded stationary phases and silica pore sizes, including large-pore short alkyl chain, non-porous, and perfluorinated. Reduced plate height (h) versus reduced velocity (nu) plots were constructed for each column and the A' and C' terms calculated using a simplified Van Deemter equation introduced in our previous work. To further explore the practicality of using triethylamine in the micellar mobile phase, the efficiency of nine polar and non-polar substituted benzenes was studied on seven columns. Surfactant adsorption isotherms were measured for five columns with three micellar mobile phases to understand the relationship between adsorbed surfactant, mobile phase additive, and column efficiency. Clear improvements in efficiency were observed with the addition of 2% (v/v) triethylamine to a 1-butanol modified aqueous micellar mobile phase. This finding is supported by the lower amount of surfactant adsorbed onto the stationary phase when TEA is present in the mobile phase compared to an SDS only or a 1-butanol modified SDS mobile phase.     

A scalable synthesis of an azabicyclooctanyl derivative, a novel DPP-4 inhibitor

A practical synthetic strategy to a chiral azabicycclooctanyl derivative (1), a potent DPP-4 inhibitor, starting from a commercially available nortropine is described. The stereogenic center of 1 was established employing a modified protocol of Ellman's diastereoselective addition of a benzylic nucleophile to tert-butanesulfinimine. Other key steps include Corey-Chaykovsky reaction, Meinwald rearrangement, and CDMT-promoted amide bond formation involving a sterically hindered amine 2.     

Diffusion-influenced reversible geminate ABCD reaction in the presence of an external field

We investigate a diffusion-influenced ground-state reversible geminate ABCD reaction in the presence of a constant external field in one dimension. In the Laplace domain, we first obtain the nonreactive Green function from which the reactive Green function is derived. Analytic asymptotic expressions of the survival probability are obtained in the time domain for both short and long time regions. There exist four regimes for the equilibrium survival probability according to the signs of the field intensities a1 and a2 that reactant and product states feel, respectively. Analysis of the long-time asymptotic behavior of the survival probability shows two regimes depending on the sign of a parameter K( identical with a(2)(2)D(2) -a(2)(1)D(1)), where D(1) and D(2) are the relative diffusion constants of corresponding states, respectively. Combining these two results, we predict a total of eight regimes for the long-time asymptotic behavior of the survival probability. We find that the long-time asymptotic behavior of the deviation of the effective survival probability shows the t(-3/2) power law when m( identical with min {a(2)(1)D(1), a(2)(2)D(2)}) not equal 0, whereas it shows t(-1/2) power law when m = 0. When one of the fields is turned off, the long-time asymptotic behavior of the survival probability shows a kinetic transition as the sign of the remaining field changes.