Phosphorus-Nitrogen Compounds: Part 25. Syntheses,Spectroscopic, Structural and Electrochemical Investigations,Antimicrobial Activities,and DNA Interactions of Ferrocenyldiaminocyclotriphosphazenes

Abstract

The condensation reactions of hexachlorocyclotriphosphazene (N₃P₃Cl₆) with mono (1 and 2) and bisferrocenyldiamines (3–5 and 7) resulted in the formation of tetrachloro mono- (8 and 9) and bisferrocenylspirocyclotriphosphazenes (10–13). In addition the tetramorpholino mono- (8a and 9a) and bisferrocenylphosphazenes (10a–12a) were obtained from the reactions of the corresponding tetrachlorophosphazenes (8–12) with excess morpholine. The structures of all the phosphazenes were determined using FTIR, MS, ¹H, ¹³C, and ³¹P NMR and 2-dimensional NMR techniques. The structures of 9a and 13 were determined by single crystal X-ray diffraction techniques. Cyclic voltammetric investigations of compounds 8a, 9a, and 11a revealed that ferrocene redox centers undergo reversible oxidation. These ferrocenylphosphazenes appear to be quite robust electrochemically. Interactions between the compounds 8a, 9a, 11a, and 12a and pBR322 plasmid DNA were investigated by agarose gel electrophoresis.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.]     

Applied electric field effect on light-scattering birefringence of dye-doped liquid crystal molecule and consistent neural network empirical physical formula construction for scattering intensities

In this paper, we realized two objectives. Firstly, birefringence of azo and anthraquinone dye-doped nematic liquid crystal (NLC) molecules was investigated by applied electric field dependent laser scattering intensities. The birefringence was essentially calculated from ordinary and extraordinary ray phase difference, which is determined from the measured intensities corresponding to parallel and perpendicular orientations of analyzer to polarizer. The birefringence was found to be dependent on both applied voltage and the kind of the doping dye. As the second objective, by nonlinear universal function approximator layered feedforward neural network (LFNN), we constructed explicit form of empirical physical formulas (EPFs) for experimentally measured dye-doped NLC nonlinear scattering intensities. Excellent LFNN test set predictions over yet-to-be measured experimental data proved that the constructed LFNN-EPFs estimated the measured intensities consistently. The correlation coefficients assessing the goodness of predictions were about r = 0.998for all cases. The LFNN-EPFs also extracted the intensity dependency on the kind of dye used. When theoretical and LFNN-EPFs intensities are compared, we conclude that given certain experimental conditions, theoretical and LFNN-EPFs predictions are in excellent agreement. In this sense, we can say that the physical laws embedded in the birefringence scattering data can be consistently extracted by LFNN. Therefore, judging from the consistent extraction of the molecular dependencies of pure and doped NLC intensities, we predict that the LFNN-EPFs can help to identify unknown molecular structural parameters in liquid crystal extracts. More concretely, by suitable mathematical operations such as differentiation, integration, minimization on these intensity LFNN-EPFs, some useful information into the charge distributions of the LC molecules can be gained.     

Ultrasound assisted biobleaching of cotton

In this study, the effect of ultrasound on the activity of the glucose oxidase (GOx) enzyme for bleaching of the cotton fabrics was investigated. Hydrogen peroxide generation with the GOx enzyme from glucose was carried out under ultrasonic homogenizer (UH) and ultrasonic bath support. The aim of using ultrasonic support was to increase the yield of the enzyme reactions. The enzymatically generated hydrogen peroxide was used for bleaching of cotton fabrics. The bleaching process was performed at 90 °C and pH 11 (with NaOH) for 60 min, followed by rinsing at 70 and 50 °C then cold washing. The whiteness degrees of the cotton samples that were bleached by the generated peroxide were compared to the whiteness degrees of the conventionally bleached cotton fabrics. Sufficient whiteness degrees in cotton fabrics could be obtained by enzymatically generated hydrogen peroxide by UH support. The initial whiteness degree of the cotton fabric was 59.9 Stensby degrees; the whiteness was increased to 75.6 Stensby degrees by the GOx enzyme under UH support where the conventional bleaching process yielded a whiteness value of 76.7 Stensby degrees. For efficient cotton bleaching by the GOx enzyme, UH support contributed to the concentration of enzymatically generated hydrogen peroxide by the GOx enzyme. Bleaching of cotton by the GOx enzyme was approved as a more environmentally friendly process compared to the conventional bleaching method in respect of the results of chemical oxygen demand tests.     

Phosphorus–nitrogen compounds Part 55. Syntheses of 4-methoxybenzylspiro(N/N)cyclotriphosphazenes: chemical,structural and biological properties

Research on Chemical Intermediates - The N3P3 ring of hexachlorocyclotriphosphazene, N3P3Cl6 (1) (HCCP; trimer), was used significantly as a scaffold for the syntheses of...     

Enabling better management of patients: discrete event simulation combined with the STAR approach

Squeezed budgets and funding cuts are expected to become a feature of the healthcare landscape in the future, forcing decision makers such as service managers, clinicians and commissioners to find effective ways of allocating scarce resources. This paper discusses the development of a decision support toolkit (DST) that facilitates the improvement of services by identifying cost savings and efficiencies within the pathway of care. With the help of National Health Service and commercial experts, we developed a discrete event simulation model for deep vein thrombosis (DVT) patients and adapted the socio-technical allocation of resources (STAR) approach to answer crucial questions like what sort of interventions should we spend our money on? Where will we get the most value for our investment? How will we explain the choices we have made? The DST enables users to model their own services by working with the DST interface allowing users to specify local DVT services. They can input local estimates, or data of service demands and capacities, thus creating a baseline discrete event simulation model. The user can then compare the baseline with potential changes in the patient pathway in the safety of a virtual environment. By making such changes key decision makers can easily understand the impact on activity, cost, staffing levels, skill-mix, utilisation of resources and, more importantly, it allows them to find the interventions that have the highest benefit to patients and provide best value for money.     

Quantum‐chemical,IR, NMR,and X‐ray diffraction studies on 2‐(4‐chlorophenyl)‐1‐methyl‐ 1H‐benzo[d]imidazole

The title molecule, 2‐(4‐chlorophenyl)‐1‐methyl‐1H‐benzo[d]imidazole (C₁₄H₁₁ClN₂), was prepared and characterized by ¹H NMR, ¹³C NMR, IR, and single‐crystal X‐ray diffraction. The molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) ¹H and ¹³C NMR chemical shift values of the title compound in the ground state have been calculated by using the Hartree‐Fock (HF) and density functional theory (DFT/B3LYP) method with 6‐31G(d) basis sets, and compared with the experimental data. The calculated results show that the optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies and GIAO ¹H and ¹³C NMR chemical shifts show good agreement with experimental values. The energetic behavior of the title compound in solvent media has been examined using B3LYP method with the 6‐31G(d) basis set by applying the Onsager and the polarizable continuum model (PCM). Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis, and nonlinear optical (NLO) properties of the title compound were investigated by theoretical calculations. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Temperature activated ionic conductivity in gallium and indium phthalocyanines

The effects of introducing gallium and indium metals into phthalocyanine molecules were investigated via temperature and frequency dependent dielectric spectroscopy. The dielectric properties of Ga(III) and In(III) phthalocyanine pellets were measured at frequencies from 1 kHz to 1 MHz in the temperature range 300-530 K. The temperature dependence of the real part of the dielectric constant suggested that these compounds exhibit semiconductor behavior. The activation energy values were calculated from the Arrhenius plots at different frequencies. A distinct transition in these plots indicated the activation of ionic conductivity at higher temperatures.     

On the Coupling Time of the Heat-Bath Process for the Fortuin–Kasteleyn Random–Cluster Model

We consider the coupling from the past implementation of the random–cluster heat-bath process, and study its random running time, or coupling time. We focus on hypercubic lattices embedded on tori, in dimensions one to three, with cluster fugacity at least one. We make a number of conjectures regarding the asymptotic behaviour of the coupling time, motivated by rigorous results in one dimension and Monte Carlo simulations in dimensions two and three. Amongst our findings, we observe that, for generic parameter values, the distribution of the appropriately standardized coupling time converges to a Gumbel distribution, and that the standard deviation of the coupling time is asymptotic to an explicit universal constant multiple of the relaxation time. Perhaps surprisingly, we observe these results to hold both off criticality, where the coupling time closely mimics the coupon collector’s problem, and also at the critical point, provided the cluster fugacity is below the value at which the transition becomes discontinuous. Finally, we consider analogous questions for the single-spin Ising heat-bath process.     

Carbon Nanoparticles in Nematic Liquid Crystals

Fullerene C60, C7o, single-walled and multi-walled carbon nanotubes and graphene sheets are doped to nematic liquid crystal （LC） host in the same percentage. Planar samples of these mixtures are prepared and our measurements constitute an optimization basis for possible applications. Fullerene balls are found to be the best compatible material for optical aims and reorientation of LC molecules, while the carbon nanotubes experience some reorientation possibility in LC media and graphene layers are good barriers to preserve reorientation.     

Vibration control for plate-like structures using strategic cut-outs

Cut-outs are widely used in plates and shells to facilitate heat dissipation, and to provide access to different components. Because of the presence of the cut-outs, it is expected that the dynamic behavior will deteriorate, and vibration magnitudes will be exaggerated as compared to those of the case without a cut-out. Summary of an investigation is presented in this paper to explore the possibility of making a rectangular cut-out in a plate for the purposes of employing this cut-out as a dynamic vibration absorber.The process involves numerical modeling using standard finite elements. The numerical predictions are presented in the form of design charts to indicate the conditions under which vibration control may be possible. Then, two variations are presented for comparison purposes, namely a lumped-parameter tuned vibration absorber and an auxiliary flap, instead of an integral cut-out. Finally, simple experiments are described to test the validity of the numerical predictions.