Syntheses of Chiral Phosphazenes with Stereogenic Centers: NMR Behavior in the Presence of a Chiral Solvating Agent

The condensation reactions of tetrachloro mono ( 1 and 2 ) and bisferrocenyl spirocyclotriphosphazenes ( 3 – 5 ) with morpholine in tetrahydrofuran gave the partly morpholino‐substituted ferrocenylphosphazenes. When the reactions were carried out with equal amounts of 1 – 5 and morpholine, the mono‐substituted ferrocenylphosphazenes ( 1a, 3a–5a ) formed as the major product. While the reactions were made with 1 equiv of 1–5 and 2 equiv of morpholine, the corresponding geminal–phosphazenes ( 1b–5b ) were isolated. In addition, the condensation reactions of 1 equiv of 1–5 and 3 equiv of morpholine resulted in the formation of di‐( 1b–5b ), tri‐( 2c–5c ), and tetra‐substituted phosphazenes. The tri‐substituted compounds were isolated as major products. Some new phosphazenes have stereogenic P center(s). The stereogenic properties of 1a and 2c were investigated using ³¹P nuclear magnetic resonance (NMR) spectroscopy in the presence of the chiral solvating agent; (S)‐(+)‐2,2,2‐trifluoro‐1‐(9′‐anthryl)ethanol. The structures of all the phosphazenes were characterized by one‐dimensional ¹H, ¹³C, and ³¹P NMR, and two‐dimensional heteronuclear single quantum coherence spectral data. The salient spectral properties of the phosphazenes were presented.     

Modelling length of stay and patient flows: methodological case studies from the UK neonatal care services

The number of babies needing neonatal care is increasing mainly because of technological and therapeutic advances. These advances have implied a decreasing neonatal mortality rate for low birth weight infants and also a falling incidence of preterm stillbirth. Given the structural changes in the National Health Service in England, coupled with recession and capacity constraints, the neonatal system is facing some serious challenges, such as nurse shortages and the lack of cots, which could inevitably impact neonates’ length of stay, and the performance of the system as a whole. These constraints have forced neonatal managers to better understand their organisation and operations in order to optimise their systems. As a result, we have developed three unique methodologies based on length of stay modelling, physical patient pathways, and system dynamics modelling. This paper evaluates these techniques applied to neonatal services in London and showcases their usefulness and implications in practice, particularly focusing on patient flow to determine major drivers of the system, which could reduce inefficiencies, improve patient experience, and reduce cost.     

Phosphorus–nitrogen compounds: Part 19. Syntheses,structural and electrochemical investigations,biological activities,and DNA interactions of new spirocyclic monoferrocenylcyclotriphosphazenes

The reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆, with N-alkyl-N-ferrocenylmethylethylene diamines, FcCH₂NH(CH₂)₂NHR₁ [R₁ = Me (1) and Et (2)], and sodium [3-(N-ferrocenylmethylamino)-1-propanoxide] (3) produce spirocyclic monoferrocenyl tetrachlorophosphazenes (1a–3a). The tetrapyrrolidinophosphazenes (1b–3b) are prepared from the reactions of corresponding phosphazenes (1a–3a) with excess pyrrolidine. The reaction of 1a with excess morpholine affords geminal-morpholino phosphazene (1c), whilst the reactions of 2a and 3a give diethylaminotrimorpholino (2c) and fully substituted morpholino products (3c), respectively. The structural investigations of the compounds are examined by Fourier transform IR, MS, ¹H, ¹³C, ³¹P NMR, DEPT, HETCOR, and HMBC techniques. The crystal structures of 3b and 3c are determined using X-ray crystallography. Cyclic voltammetric and chronoamperometric data show that compounds 1a–3a, 1b–3b, and 1c–3c exhibit electrochemically reversible one-electron oxidation of Fc redox centers which are hardly affected by the substituents on the phosphazene ring. The compounds 1b, 2b, 3b, and 3c are screened for antibacterial activities against Gram-positive and Gram-negative bacteria and for antifungal activities against yeast strains. In addition, the antituberculosis activities (in vitro) of these compounds are evaluated against INH-susceptible reference strain M. tuberculosis H37Rv, and six multi-drug resistant clinical M. tuberculosis isolates. Compound 2b is found to be the most active against the susceptible the reference strain. In addition, 1b, 2b, and 3c are active against all the multidrug-resistant clinical isolates at the highest concentrations. Gel electrophoresis data indicate that the compounds promote the formation of strand breaks in plasmid DNA. Almost all the concentrations lost of supercoiled DNA suggests that the compound 3b is very efficient plasmid-modifier. The compounds inhibit BamHI cleavage of pUC18 DNA while restricting HindIII.     

Carbon nanotubes/alizarin red S–poly(vinylferrocene) modified glassy carbon electrode for selective determination of dopamine in the presence of ascorbic acid

A modified electrode was fabricated by electrochemical formation of poly(vinylferrocene) on the multi-wall carbon nanotube-alizarin red S matrix covered glassy carbon electrode. A higher electrochemical activity was obtained to the electrocatalytic oxidation of dopamine. The electrode surface was characterized electrochemically and spectroscopically. Poly(vinylferrocene) (PVF) in electrode was used as an electron transfer mediator in the electrochemical oxidation of compounds due to its perfect reversible redox properties. Multi-wall carbon nanotubes (MWCNTs) / alizarin red S (ARS)–PVF electrode was used to the determination of dopamine in the presence of ascorbic acid in 0.1 M sulphate buffer solution at pH 7. The performance of the MWCNTs/ARS–PVF electrode was evaluated by DPV and amperometry.     

Structural results on a batch acceptance problem for capacitated queues

The purpose of this paper is to investigate the structural properties of the optimal batch acceptance policy in a Markovian queueing system where different classes of customers arrive in batches and the buffer capacity is finite. We prove that the optimal policy can possess certain monotonicity properties under the assumptions of a single-server and constant batch sizes. Even though our proof cannot be extended to cases where either one of the assumptions is relaxed, we numerically observe that the optimal policy can still possess the same properties when only the single-server assumption is relaxed. Finally, we present counterexamples that show the non-monotone structure of the optimal policy when the batch sizes are not constant.     

Extremely Increasing the Operating Frequency Range of Mode-Locked Hybrid Soliton Pulse Source

Numerical simulations show that proper fundamental mode-locking repetition range of hybrid soliton pulse source where transform-limited pulses are obtained is extremely increased with the use of linearly chirped tanh apodized fibre Bragg grating. Near transform-limited pulses around a system operating frequency of 2.5 GHz. are generated over a frequency range of 1.6 GHz （1.9-3.4 GHz）     

Sulfate decomposition by bacterial leaching

Sulfate disposal is the main problem of many industrial effluents, such as excess sulfuric acid, gypsum, coal desulfurization byproducts, acid-mine waters, and general metallurgical effluents. It has been established that sulfate present in wastes can be converted to elemental sulfur by bacterial mutualism. This study presents the results of an investigation of the industrial feasibility of utilizing a biological system capable of converting hydrous calcium sulfate (gypsum) to elemental sulfur. Gypsum, which was used in this study, is a byproduct of the fertilizer industry. The biological system is referred to as a bacterial mutualism, and involvesDesulfovibrio desulfuricans for sulfate conversion andChlorobium thiosulfatophilum for hydrogen sulfide conversion. Bacterial mutualism and utilization of sulfate were investigated by means of a two-stage anaerobic system. In the first stage, a gas purge system was used for sulfate conversion to sulfide, and it was found that maximum conversion is 34%. In the second stage, a static culture system was used for sulfide conversion to sulfur with a conversion of 92%.     

Rapid detection of nitroaromatic and nitramine explosives on chromatographic paper and their reflectometric sensing on PVC tablets

Rapid and inexpensive sensing of explosive traces in soil and post-blast debris for environmental and criminological purposes with optical sensors has recently gained importance. The developed sensing method for nitro-aromatic and nitramine-based explosives is based on dropping an acetone solution of the analyte to an adsorbent surface, letting the solvent to dry, spraying an analytical reagent to produce a persistent spot, and indirectly measuring its reflectance by means of a miniature spectrometer. This method proved to be useful for on-site determination of nitro-aromatics (trinitrotoluene (TNT), 2,4,6-trinitrophenylmethylnitramine (tetryl) and dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)) pre-adsorbed on a poly vinyl chloride (PVC) surface, with the use of different spray reagents for each group of explosives producing different colors. The calibration equations of the tested compounds as reflectance vs. concentration showed excellent linearity (correlation coefficient: 0.998-0.999). The linear quantification interval in terms of absolute quantity of analyte was 0.1-0.5 μg. The developed method was successfully tested for the analysis of military explosives Comp B and Octol, and was validated against high performance liquid chromatography (HPLC). The reflectometric sensing method could also be used for qualitative identification of the nitrated explosives on a chromatographic paper. The reagent-impregnated paper could also serve as sensor, enabling semi-quantitative determinations of TNT and tetryl.     

Light-scattering experiments in dye-doped liquid crystals both to determine crystal parameters and to construct consistent neural network empirical physical formulas for scattering amplitudes

The aim of this paper is two-fold. Firstly, static laser light-scattering amplitude measurements in azo-dye doped nematic liquid crystals (NLCs) were made versus scattering angle, temperature and applied bias voltage. Three NLC parameters were determined: the elastic constant ratios K₁₁/K₂₂ by regression, phase transition temperatures, and Freedericksz voltages from the graphs. They were all doping ratio dependent. Secondly, as a novel approach, by a nonlinear universal function approximator layered feedforward neural network (LFNN) we constructed an explicit form of empirical physical formulas (EPFs) for theoretically unknown nonlinear azo-dye doped NLC scattering amplitude functions. Excellent LFNN test set (i.e. yet-to-be measured experimental data) predictions prove that the constructed LFNN-EPPs estimate unknown amplitude functions consistently. The LFFN-EPFs, too, confirmed the doping-ratio dependency. Also, comparing LFNN and regression amplitude fits, the LFNN fits were significantly better. In conclusion, physical laws embedded in the physical data can be consistently extracted by LFNN. One major potential application in the nonlinear optics domain is that these LFNN-EPFs, by differentiation, integration, minimization, etc., can be used to obtain further NLC scattering amplitude related molecular structural physical quantities. This could in turn help us to develop new nonlinear optical materials.     

Influence of molecular weight on the short‐channel effect in polymer‐based field‐effect transistors

In this study, we demonstrate how the intrinsic properties of a polymer can influence the electrical characteristics of organic field‐effect transistors (OFETs). OFETs fabricated with three batches of poly[2‐methoxy,5‐(3′,7′‐dimethyl‐octyloxy)]‐p‐phenylene vinylene (MDMO‐PPV) were investigated. The properties of the polymers were initially investigated using Fourier transform infrared spectroscopy (FTIR), impedance spectroscopy (IS), gel permeation chromotography (GPC), and cyclic voltammetry (CV), respectively. The structure and purity of the polymer batches were found to be very comparable, but the molecular weight (M_n and M_w) and polydispersity (PDI = M_w/M_n), varied between the samples and the HOMO and LUMO levels of the polymers were found to depend on the molecular weight properties. OFETs were then fabricated with the polymers and electrically characterized. It was observed that the channel current and the field‐effect mobility increase with increasing polymer molecular weight. The output characteristics of the transistors, on the other hand, were found to depend on the PDI of the polymer. Saturation of the channel current occurs at higher source–drain voltages and short‐channel behavior was observed to start at longer channel lengths for polymers with a higher PDI. This behavior is observed to be thickness dependent, and the short‐channel behavior was more pronounced for thicker MDMO‐PPV films. These results are explained in terms of influences of chain packing and ordering and high bulk currents on the FET output and transistor parameters. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 117–124, 2012