A simple,rapid and sensitive liquid chromatography–tandem mass spectrometry method for the determination of dienogest in human plasma and its pharmacokinetic applications under fasting

A simple, rapid and sensitive analytical method using liquid chromatography coupled to tandem mass spectrometry (LC‐MS/MS) detection with positive ion electrospray ionization was developed for the determination of dienogest in human K₂EDTA plasma using levonorgestrel d₆ as an internal standard (IS). Dienogest and IS were extracted from human plasma using simple liquid–liquid extraction. Chromatographic separation was achieved on a Zorbax XDB‐Phenyl column (4.6 × 75 mm, 3.5 µm) under isocratic conditions using acetonitrile–5 mm ammonium acetate (70:30, v/v) at a flow rate of 0.60 mL/min. The protonated precursor to product ion transitions monitored for dienogest and IS were at m/z 312.30 → 135.30 and 319.00 → 251.30, respectively. The method was validated with a linearity range of 1.003–200.896 ng/mL having a total analysis time for each chromatograph of 3.0 min. The method has shown tremendous reproducibility with intra‐ and inter‐day precision (coefficient of variation) <3.97 and 6.10%, respectively, and accuracy within ±4.0% of nominal values. The validated method was applied to a pharmacokinetic study in human plasma samples generated after administration of a single oral dose of 2.0 mg dienogest tablets to healthy female volunteers and was proved to be highly reliable for the analysis of clinical samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Message transfer in a communication network

We study message transfer in a 2-d communication network of regular nodes and randomly distributed hubs. We study both single message transfer and multiple message transfer on the lattice. The average travel time for single messages travelling between source and target pairs of fixed separations shows q-exponential behaviour as a function of hub density with a characteristic power-law tail, indicating a rapid drop in the average travel time as a function of hub density. This power-law tail arises as a consequence of the log-normal distribution of travel times seen at high hub densities. When many messages travel on the lattice, a congestion-decongestion transition can be seen. The waiting times of messages in the congested phase show a Gaussian distribution, whereas the decongested phase shows a log-normal distribution. Thus the waiting time distributions carry the signature of congested or decongested behaviour.      

Nanowires and nanorings at the atomic level

The step-flow growth mode is used to fabricate Si and Ge nanowires with a width of 3.5 nm and a thickness of one atomic layer (0.3 nm) by self-assembly. Alternating deposition of Ge and Si results in the formation of a nanowire superlattice covering the whole surface. One atomic layer of Bi terminating the surface is used to distinguish between the elements Si and Ge. A difference in apparent height is measured in scanning tunneling microscopy images for Si and Ge. Also, different kinds of two-dimensional Si/Ge nanostructures like alternating Si and Ge nanorings having a width of 5-10 nm were grown.     

Pyridinium dichlorophosphinomethylides

Seven new pyridinium dichlorophosphinomethylides 2 have been obtained from dichlorophosphinylation of the pyridinium methylides generated in situ. 2 give 1,3‐bis(alkoxycarbonyl)‐2‐phosphaindolizines 4 through 1,5‐electrocyclization of the intermediate, bis(pyridinium ylidyl)phosphenium chloride 3 which is generated either from disproportionation of 2 or from the reaction of 2 with pyridinium methylide. Formation of 3 has been confirmed by carrying out a crossed reaction. 3‐Substituted 2 forms 4 regiospecifically. Intramolecular 1,5‐cyclocondensation of 2‐methylpyridinium dichlorophosphinomethylide is preferred over its disproportionation. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:602–609, 2001     

Computer simulation of third‐order nonlinear singular problems arising in draining and coating flows

In this paper, the nonlinear third‐order singular ordinary differential equations that arise in draining and coating flows are studied and computationally solved by employing the modified Adomian decomposition method, and the series solutions of the governing nonlinear problems are developed. Because of singularity, it is not possible to move a contact line over a no‐slip surface, so we cannot find the solution of such problems. To overcome this difficulty, we modify boundary condition to apply the modified Adomian decomposition method with Padé approximants. Copyright © 2011 John Wiley & Sons, Ltd.     

Substituent-dependent anomeric effects as a source of conformational preference in pyridinium methylides

A systematic density functional theory level investigation of differently substituted pyridinium methylides was carried out to determine the role of C(ylidic) lone-pair-associated hyperconjugative and negative hyperconjugative interactions in deciding conformational preferences. Deviation from the coplanar orientation of the carbanionic center with the pyridine ring and its substituent dependence has been found to correlate well with the relative opportunities for conjugative and negative hyperconjugative interactions of a ylidic moiety with different substituent groups present at the ylidic carbon. The contribution of individual n-->pi* conjugative, n-->sigma* negative hyperconjugative, and sigma-->pi* hyperconjugative interactions in a particular conformation of pyridinium dichlorophosphinomethylides was assessed from donor-acceptor stabilization energies, as obtained from natural bond orbital (NBO) analysis. The relative extent of conjugative and negative hyperconjugative interactions with the substituents present at the ylidic carbon plays an important role in permitting the delocalization of ylidic charge into the pyridine ring, thereby controlling the relative orientation of the latter with the carbanionic plane.     

Study of densities,viscosities, and speeds of sound of binary liquid mixtures of butan-1-ol with n-alkanes (C6, C8, and C10) at T = (298.15, 303.15, and 308.15) K

The densities (ρ) and speeds of sound (u) have been measured over the whole composition range for (butan-1-ol with hexane, or octane, or decane) at T = (298.15, 303.15, and 308.15) K and atmospheric pressure along with the properties of the pure components. Viscosities (η) of these binary mixtures have also been measured over the entire composition range at T = 298.15 K. Experimental values of density, viscosity and speed of sound have been used to evaluate excess properties viz. excess molar volumes (V^E), deviation in viscosity (Δη), deviation in speeds of sound (Δu), deviation in isentropic compressibility (Δκ_s) and excess Gibbs free energy of activation of viscous flow (ΔG^1E). The excess properties have been correlated using the Redlich–Kister polynomial equation. The sign and magnitude of these excess properties have been used to interpret the results in terms of intermolecular interactions and structural effects. The viscosity data have also been correlated by Grunberg and Nissan, Tamura–Kurata, and Hind correlation equations.     

Synthesis and Antioxidant Properties of Novel 1,3,2-Oxazaphospholanes Incorporating 1,2-Dihydropyridines

Novel chiral 1,3,2-oxazaphospholane-2-sulfides incorporating a dihydropyridine ring have been synthesized via phosphorylation of 2-aminopyridinium salts, followed by in situ oxidation and cyclocondensation with 2-(alkylamino)ethanol. Cyclic organothiophosphates thus obtained have been screened for their antioxidant properties.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Detection of the power spectrum of cosmic microwave background lensing by the Atacama Cosmology Telescope

We report the first detection of the gravitational lensing of the cosmic microwave background through a measurement of the four-point correlation function in the temperature maps made by the Atacama Cosmology Telescope. We verify our detection by calculating the levels of potential contaminants and performing a number of null tests. The resulting convergence power spectrum at 2° angular scales measures the amplitude of matter density fluctuations on comoving length scales of around 100 Mpc at redshifts around 0.5 to 3. The measured amplitude of the signal agrees with Lambda cold dark matter cosmology predictions. Since the amplitude of the convergence power spectrum scales as the square of the amplitude of the density fluctuations, the 4σ detection of the lensing signal measures the amplitude of density fluctuations to 12%.