Sub-micro level monitoring of beryllium ions with a novel beryllium sensor based on 2,6-diphenyl-4-benzo-9-crown-3-pyridine

The 2,6-diphenyl-4-benzo-9-crown-3-pyridine (DPCP) was used as an excellent ionophore in construction of a coated graphite poly(vinyl chloride) (PVC)-based membrane sensor. The best performance was obtained with a membrane composition of 30% poly(vinyl chloride), 60% o-nitrophenyloctyl ether (NPOE), 5% 2,6-diphenyl-4-benzo-9-crown-3-pyridine and 5% sodium tetraphenyl borate (TBP). This sensor shows very good selectivity and sensitivity towards beryllium ion over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. The sensor revealed a great enhancement in selectivity coefficients and sensitivity for beryllium, in comparison with the previously reported beryllium electrodes. The electrode exhibits a Nernstian behavior (with slope of 29.6 mV per decade) over a very wide concentration range (1.0×10⁻⁷ to 1.0×10⁻¹) with a detection limit of 4.0×10⁻⁸ M (360 pg ml⁻¹). It shows relatively fast response time, in whole concentration range (<10 s), and can be used for at least 12 weeks in the pH range of 4.5-8.0. The proposed sensor was successfully used to determination of beryllium in mineral ore.     

Electron affinity and redox potential of tetrafluoro-p-benzoquinone: A theoretical study

The electron affinity of tetrafluoro-p-benzoquinone (2.69 eV) and the mono- (2.10 eV), 2,3-di- (2.29 eV), 2,5-di- (2.28 eV), 2,6-di- (2.31 eV) and tri- (2.48 eV) fluoro derivatives of p-benzoquinone have been calculated via standard ab initio molecular orbital theory at the G3(MP2)-RAD level of theory. Comparison of calculated electron affinities with the available experimental values shows excellent agreement between theory and experiment. The reduction potential of tetrafluoro-p-benzoquinone in acetonitrile vs. SCE (−0.03 V) has been calculated at the same level of theory and employing a continuum model of solvation (CPCM), and is also in excellent agreement with the experimental value (−0.04 V vs. SCE).     

F2 dimer: Improved intermolecular potential energy surface using ab initio calculations

A computational study on the intermolecular potential energy of 44 different orientations of F₂ dimers is presented. Basis set superposition error (BSSE) corrected potential energy surface is calculated using the supermolecular approach at CCSD(T) and QCISD(T) levels of theory. The interaction energies obtained using the aug‐cc‐pVDZ and aug‐cc‐pVTZ basis sets are extrapolated to the complete basis set limit using the latest extrapolation scheme. The basis set effect is checked and it is found that the extrapolated intermolecular energies provide the best compromise between the accuracy and computational cost. Among 1320 energy points of F₂–F₂ system covering more relative orientations, the most stable structure of the dimers was obtained with a well depth of ?146.62 cm^?1 that related to cross configuration, and the most unstable structure is related to linear orientation with a well depth of ?52.63 cm^?1. The calculated second virial coefficients are in good agreement with experimental data. The latest extrapolation scheme of the complete basis set limit at the CCSD(T) level of theory is used to determine the intermolecular potential energy surface of the F₂ dimer. Comparing the results obtained by the latest scheme with those by older schemes show that the new approach provides the best compromise between accuracy and computational cost.     

Polycatenar oligophenylene liquid crystals

We report the synthesis of oligophenylene polycatenar liquid crystals incorporating 1,4‐disubstituted phenyl rings joined by a direct carbon carbon bond and some pyrimidine analogues. The nature of the linkages does appear to affect the mesomorphism significantly. The ratio of the aromatic core to the aliphatic chains is varied systematically by changing the number of 1,4‐disubstituted phenyl rings and the length of the aliphatic chains. This strongly influences the transition temperatures of the mesophases. Some of the compounds are columnar over an extended temperature range of more than 200°C with melting points below room temperature. We suggest that a combination of the poor overlap of the conjugated electron system of the molecular cores making up the columnar structure and the high concentration of aliphatic chains leads to a low charge‐carrier mobility.     

Interaction of double-stranded DNA inside single-walled carbon nanotubes

Deoxyribonucleic acid (DNA) is the genetic material for all living organisms, and as a nanostructure offers the means to create novel nanoscale devices. In this paper, we investigate the interaction of deoxyribonucleic acid inside single-walled carbon nanotubes. Using classical applied mathematical modeling, we derive explicit analytical expressions for the encapsulation of DNA inside single-walled carbon nanotubes. We adopt the 6–12 Lennard–Jones potential function together with the continuous approach to determine the preferred minimum energy position of the dsDNA molecule inside a single-walled carbon nanotube, so as to predict its location with reference to the cross-section of the carbon nanotube. An analytical expression is obtained in terms of hypergeometric functions which provides a computationally rapid procedure to determine critical numerical values. We observe that the double-strand DNA can be encapsulated inside a single-walled carbon nanotube with a radius larger than 12.30 ?, and we show that the optimal single-walled carbon nanotube to enclose a double-stranded DNA has radius 12.8 ?.     

Adaptive step-size modified fractional least mean square algorithm for chaotic time series prediction

This paper presents an adaptive step-size modified fractional least mean square （AMFLMS） algorithm to deal with a nonlinear time series prediction. Here we incorporate adaptive gain parameters in the weight adaptation equation of the original MFLMS algorithm and also introduce a mechanism to adjust the order of the fractional derivative adaptively through a gradient-based approach. This approach permits an interesting achievement towards the performance of the filter in terms of handling nonlinear problems and it achieves less computational burden by avoiding the manual selection of adjustable parameters. We call this new algorithm the AMFLMS algorithm. The predictive performance for the nonlinear chaotic Mackey Glass and Lorenz time series was observed and evaluated using the classical LMS, Kernel LMS, MFLMS, and the AMFLMS filters. The simulation results for the Mackey glass time series, both without and with noise, confirm an improvement in terms of mean square error for the proposed algorithm. Its performance is also validated through the prediction of complex Lorenz series.     

Synthesis and characterization of ordered mesoporous carbon as electrocatalyst for simultaneous determination of epinephrine and acetaminophen

In this research, we report an easy method for synthesis of ordered mesoporous carbon (OMC) with hexagonal arrays of tubes (CMK-5). The synthesized OMC was characterized using X-ray diffraction (XRD), scanning electronic microscopy (SEM) and nitrogen sorption isotherms techniques. Due to the large surface area and high conductivity of OMC, OMC-modified glassy carbon (OMCs/GC) electrode was prepared. The unique electrochemical activity of OMCs/GC electrode was illustrated using cyclic voltammetry (CV) and electron impedance spectroscopy (EIS) in which OMC showed a faster electron transfer rate, as compared with glassy carbon electrode. The electrochemical behavior of epinephrine (EN) and acetaminophen (AP) at OMC/GC electrode was also investigated using cyclic voltammetry. The OMC/GC electrode exhibited high electrocatalytic activities toward oxidation of EN and AP and displayed good voltammetric peak separation between them. In differential pulse voltammetry technique, both EN and AP give sensitive oxidation peaks at 120?mV and 320?mV, respectively. Therefore, investigated method was applied for simultaneous determination of EN and AP. AP and EN give linear response over the range of 0.2–15?μM and 4–100?μM, respectively. The lower detection limits were found to be 0.07?μM for AP and 0.94?μM for EN.     

Preparation and characterization of a suite of ephedra-containing standard reference materials

The National Institute of Standards and Technology, the U.S. Food and Drug Administration, Center for Drug Evaluation and Research and Center for Food Safety and Applied Nutrition, and the National Institutes of Health, Office of Dietary Supplements, are collaborating to produce a series of Standard Reference Materials (SRMs) for dietary supplements. A suite of ephedra materials is the first in the series, and this paper describes the acquisition, preparation, and value assignment of these materials: SRMs 3240 Ephedra sinica Stapf Aerial Parts, 3241 E. sinica Stapf Native Extract, 3242 E. sinica Stapf Commercial Extract, 3243 Ephedra-Containing Solid Oral Dosage Form, and 3244 Ephedra-Containing Protein Powder. Values are assigned for ephedrine alkaloids and toxic elements in all 5 materials. Values are assigned for other analytes (e.g., caffeine, nutrient elements, proximates, etc.) in some of the materials, as appropriate. Materials in this suite of SRMs are intended for use as primary control materials when values are assigned to in-house (secondary) control materials and for validation of analytical methods for the measurement of alkaloids, toxic elements, and, in the case of SRM 3244, nutrients in similar materials.     

Time-reversal simulations for detection in randomly layered media

A time-reversal mirror is, roughly speaking, a device which is capable of receiving an acoustic signal in time, keeping it in memory and sending it back into the medium in the reversed direction of time. In this paper, we employ an accurate numerical method for simulating waves propagating in complex one-dimensional media. We use numerical simulations to reproduce the time-reversal self-averaging effect which takes place in randomly layered media. This is done in the regime where the inhomogeneities are smaller than the pulse, which propagates over long distances compared to its width. We show numerical evidence for possible use of an expanding window time-reversal technique for detecting anomalies buried in the medium.