A molecular turnstile in para-octanoyl calix[4]arene nanocapsules

The thermal treatment of different inclusion complexes of para-octanoyl calix[4]arene leads to the formation of a guest-free van der Waals nanocapsular structure possessing a remarkable stability caused by the high mobility of alkanoyl arms.     

LC-MS/MS analysis of phosphatidylethanol in dried blood spots versus conventional blood specimens

Phosphatidylethanol (PEth), which is formed extrahepatically by the action of phospholipase D on phosphatidylcholine in the presence of ethanol, has been suggested as a promising marker of alcohol misuse. Analysis of dried blood spots (DBS) is particularly advantageous for the determination of delicate analytes such as PEth. Therefore, measurement of PEth species (18:1/18:1, 16:0/18:1) in DBS versus whole blood was performed to ascertain whether respective results are directly comparable. Samples were obtained from subjects (n = 40) undergoing alcohol detoxification treatment. Analysis involved liquid–liquid extraction from both, DBS and whole blood (100 μL, respectively), with phosphatidylpropanol as the internal standard. Extracts were subjected to LC gradient separation using multiple reaction monitoring of deprotonated molecules. Results from measurements of corresponding DBS and whole blood specimens were compared by estimating the respective mean values and by a Bland and Altman analysis. Concentrations of PEth 18:1/18:1 ranged from 46.1 to 3,360 ng/mL in whole blood (mean, 461.7 ng/mL) and from 35.8 to 3,360 ng/mL in DBS (mean, 457.6 ng/mL); for PEth 16:0/18:1, concentrations were from 900 to 213,000 ng/mL (mean, 23,375 ng/mL) and 922–213,000 ng/mL (mean, 23,470 ng/mL) in blood and DBS, respectively. Estimated mean differences were −4.3 ng/mL for PEth 18:1/18:1 and 95.8 ng/mL for PEth 16:0/18:1. The Bland–Altman plot of both PEth species showed that the variation around the mean difference was similar all through the range of measured values and that all differences except one were within the limits of agreement. It could be shown that the determination of PEth species in DBS is as reliable as in whole blood samples. This assay may facilitate monitoring of alcohol misuse.     

Fourier transform microwave and millimeter wave spectroscopy of quinazoline, quinoxaline, and phthalazine

The pure rotational spectra of the bicyclic aromatic nitrogen heterocycle molecules, quinazoline, quinoxaline, and phthalazine, have been recorded and assigned in the region 13-87 GHz. An analysis, guided by ab initio molecular orbital predictions, of frequency-scanned Stark modulated, jet-cooled millimeter wave absorption spectra (48-87 GHz) yielded a preliminary set of rotational and centrifugal distortion constants. Subsequent spectral analysis at higher resolution was carried out with Fourier transform microwave (FT-MW) spectroscopy (13-18 GHz) of a supersonic rotationally cold molecular beam. The high spectral resolution of the FT-MW instrument provided an improved set of rotational and centrifugal distortion constants together with nitrogen quadrupole coupling constants for all three species. Density functional theory calculations at the B3LYP∕6-311+G?? level of theory closely predict rotational constants and are useful in predicting quadrupole coupling constants and dipole moments for such species.     

Determination of 28 selected elements in textiles by axially viewed inductively coupled plasma optical emission spectrometry

A simple, robust and reliable analytical procedure for the determination of 28 selected elements, namely Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Hg, Mg, Mn, Mo, Na, Ni, Pb, Sc, Si, Se, Sn, Sm, Sr, Tl, V, and Zn in textile materials by inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave digestion of samples was optimized and validated in this work. The total amount of elements present in textile samples was determined after microwave digestion of materials in 7 mol/L nitric acid within the optimal working program: 5 min at 150 °C (power 250 W), 15 min 180 °C (300 W) and 20 min at the maximum temperature of 200 °C (350 W). For the quality control reasons, which were ascertained by analysis of the certified cotton trace elements reference material IAEA-V9, the ICP-OES method was optimized through several parameters: by comparing Meinhard and Gemcone Low Flow nebulizers efficiency, ranging nebulizer gas flows from 0.6 to 1.0 L/min, ranging sample flows from 0.8 to 1.2 mL/min, testing RF power from 1200 to 1400 W, detecting data acquisition time (read time) from 0 to 527 s, ranging washing (delay) time from 0 to 408 s, as well as by checking the occurring interferences for the optimal line selection. Validation included determination of linearity, selectivity, accuracy, reproducibility, precision and limits of detection calculated for all 28 selected elements of interest. The developed analytical procedure was successfully applied on textile fibers (cotton, flax and hemp) as well as on standard knitted textile sample materials (cotton and wool).     

A novel fused-silica capillary dropping mercury electrode with long drop-time and its application on determination of critical micelle concentration

A novel long drop time mercury electrode has been constructed from common fused-silica capillary (50 μm I.D., 360 μm E.D.). Proposed device provides reproducible mercury drops with typical lifetime 40-120 s. The electrode was used for a set of electrocapillary measurements aimed at determination of critical micelle concentration of anionic surfactants by a convection controlled drop-time technique. A critical micelle concentration of sodium dodecyl sulfate 5.6 ± 0.4 mmol L⁻¹ and 4.3 ± 0.4 mmol L⁻¹ were obtained in 1 mmol L⁻¹ and 5 mmol L⁻¹ phosphate buffer (pH 7.0), respectively. The values were comparable to those obtained from conductometric measurements under the same conditions (7.0 ± 0.1 mmol L⁻¹ and 5.2 ± 0.1 mmol L⁻¹, respectively) and the difference was explained in accordance with theory of hemi-micelle formation.     

N-Methyl inversion and structure of six-membered heterocyclic rings: rotational spectrum of 1-methyl-4-piperidone

The conformational and structural properties of the six-membered heterocyclic ring of 1-methyl-4-piperidone have been observed in a jet-cooled supersonic expansion using Fourier transform microwave spectroscopy (FT-MW). The rotational spectrum evidenced two different conformations originated by nitrogen inversion, with the N-methyl group in either equatorial (most stable) or axial position. Additional observation of the rotational spectra for all possible carbon, nitrogen, and oxygen monosubstituted species (4 × (13)C, (15)N, (18)O) in natural abundance allowed us to determine substitution (r(s)) and effective structures (r(0)) for the equatorial conformer. Additional ab initio and DFT calculations provided comparative rotational parameters, structural data, conformational energies, and the axial-equatorial interconversion barrier. The structural data were compared with the related azabicycle of tropinone, revealing the molecular changes and structural relaxation associated with the presence of the two-carbon bridge in the latter molecule.     

Influenza neuraminidase: a druggable target for natural products

The imminent threat of influenza pandemics and repeatedly reported emergence of new drug-resistant influenza virus strains demonstrate the urgent need for developing innovative and effective antiviral agents for prevention and treatment. At present, influenza neuraminidase (NA), a key enzyme in viral replication, spread, and pathogenesis, is considered to be one of the most promising targets for combating influenza. Despite the substantial medical potential of NA inhibitors (NAIs), only three of these drugs are currently on the market (zanamivir, oseltamivir, and peramivir). Moreover, sudden changes in NAI susceptibility revealed the urgent need in the discovery/identification of novel inhibitors. Nature offers an abundance of biosynthesized compounds comprising chemical scaffolds of high diversity, which present an infinite pool of chemical entities for target-oriented drug discovery in the battle against this highly contagious pathogen. This review illuminates the increasing research efforts of the past decade (2000-2011), focusing on the structure, function and druggability of influenza NA, as well as its inhibition by natural products. Following a critical discussion of publications describing some 150 secondary plant metabolites tested for their inhibitory potential against influenza NA, the impact of three different strategies to identify and develop novel NAIs is presented: (i) bioactivity screening of herbal extracts, (ii) exploitation of empirical knowledge, and (iii) computational approaches. This work addresses the latest developments in theoretical and experimental research on properties of NA that are and will be driving anti-influenza drug development now and in the near future.     

Uncoupling evolutionary groundwater‐surface water flows using the Crank–Nicolson Leapfrog method

Consider an incompressible fluid in a region Ω_f flowing both ways across an interface into a porous media domain Ω_p saturated with the same fluid. The physical processes in each domain have been well studied and are described by the Stokes equations in the fluid region and the Darcy equations in the porous media region. Taking the interfacial conditions into account produces a system with an exactly skew symmetric coupling. Spatial discretization by finite element method and time discretization by Crank–Nicolson LeapFrog give a second‐order partitioned method requiring only one Stokes and one Darcy subphysics and subdomain solver per time step for the fully evolutionary Stokes‐Darcy problem. Analysis of this method leads to a time step condition sufficient for stability and convergence. Numerical tests verify predicted rates of convergence; however, stability tests reveal the problem of growth of numerical noise in unstable modes in some cases. In such instances, the addition of time filters adds stability. © 2012 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2013     

Four dimensional regular algebras with point scheme,anonsingular quadric in P3

In [22], a class of four-dimensional, quadratic, Artin-Schelter regular algebras was introduced, whose point scheme is the graph of an automorphism of a nonsingular quadric in P³. These algebras are the first examples of quadratic Artin-Schelter regular algebras whose defining relations are not determined by the point scheme and, hence, not determined by the algebraic data obtained from the point modules. In this paper, we study these algebras via their line modules. In particular, the set of lines in P³ that correspond to left line modules is not the set of lines in P³ that correspond to right line modules. Our analysis focuses on a distinguished member R _λ of this class of algebras, where R _λ is a twist by a twisting system of the other algebras. We prove that R _λ is a finite module over its center and that its central Proj is a smooth quadric inP⁴.