Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

A tunable microwave notch absorber filter

A magnetized plasma column is found to be a notch absorber of microwave radiation propagating in the extraordinary mode. Based on this fact, a compact tunable microwave filter is designed and tested successfully. The center frequency of the absorbed band can be varied by adjusting the background magnetic field stength. The 3dB bandwidth and amount of attenuation are functions of the plasma current. These characteristics offer a great tunability, often sought after in microwave devices. This filter can find applications in microwave measurement systems where filtering of unwanted harmonics and spurious signals can directly affect the accuracy and resolution of the measurements.     

Solid state NMR characterization of formation of poly(ϵ‐caprolactone)/maghnite nanocomposites by in situ polymerization

Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. ¹H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. ²⁷Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the ²⁹Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007     

Pinacol-Pinacolone Rearrangement of 1, 2-Di-(p-methoxyphenyl)-ethane-1, 2-diol and Bis-(4-methoxyphenyl)-acetaldehyde in Acid Media

1, 2-Di-(p-methoxyphenyl)-ethane-1, 2-diol gave in acid media bis-(4-methoxy-phenyl)-acetaldehyde, 4-4′-dimethoxy-deoxybenzoin, and 1, 2-di-(p-methoxyphenyl)-ethylene oxide; their respective yields being influenced by at least 3 factors: (i) the acid, (ii) its concentration, and (iii) the reaction period. Bis-(4-methoxyphenyl)-acetaldehyde rearranged to the deoxybenzoin in boiling sulfuric (50%) or phosphoric (75%) acids (w/w), and to two isomeric 1, 2-diacetoxy-1, 2-di-(p-methoxyphenyl) ethanes when it was heated with acetic anhydride. The mechanisms of these reactions are discussed.     

Hygrometric Determination of Water Activities and Osmotic and Activity Coefficients of NH4Cl–LiCl–H2O at 25°C

The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg^{– 1} for different ionic-strength fractions y of NH₄Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions.     

Amperometric biosensors for glucose based on carbon paste modified electrodes

The modification of carbon-paste electrodes by incorporation of the enzyme glucose oxidase (GOD) is described. The resulting probes can be operated as amperometric glucose sensors in the presence or absence of a mediator (1,1'-dimethylferrocene) mixed into the paste. Extended linear calibration ranges have been obtained up to 90 and 5OmM glucose respectively. The electrode responses were rapid, reaching steady-state values within 30-40 sec. Advantages of using a GOD-paste formulation are suggested. Plasma glucose assays were correlated with spectrophotometric determinations based on glucose oxidase (y = 1.07x - 0.16, r = 0.973, n = 17).     

Scattering of electromagnetic waves by a layer of air plasma surrounding a conducting cylinder

In this paper, the total scattering and back-scattering cross-sections (respectively represented by and _b) of an air plasma layer surrounding a conducting cylinder are studied. The plasma layer can be turned ON and OFF to allow for a comparison between the scattering cross-section of the bare cylinder and the plasma covered cylinder. The plasma layer is generated at atmospheric pressure, which results in a very highly collisional case. The scattered fields are calculated using a cylindrical expansion, with coefficients satisfying the appropriate boundary conditions, and which are a function of the refractive index of the air plasma. The results of our study are presented as plots of the total scattering cross-section, , and back-scattering cross-section, _b, versus frequency. The scattering cross-section gives an average characteristic of the scattering process from obstacles. Once the scattering cross-section is known, the actual scattered energy per unit length per second can be calculated by multiplying by the incident energy per unit area per second.     

Physical,chemical and biological studies on transition metal complexes of chelating tridentate ligand

Summary The interaction of 1-benzoin-4-phenylthiosemicarbazone (H₂ BPS) with some transition metal ions has been investigated. The ligand can function as a tridentate chelating agent, giving M(HBPS)₂ and M(BPS). Potentiometric studies proved that the mechanism of chelation is based on hydrogen ion liberation. Spectral studies in solution show that the ligand could be used for the microdetermination of Cu^IIions. On the basis of magnetic and spectral data, an octahedral structure is proposed for the Co^II and Ni^II complexes and a square-planar structure for the Cu^II complex. The corrosion inhibition of aluminium in Cl₃CCO₂H using H₂BPS is studied. The electrical conductivity of H₂BPS and of its complexes have been measured. The ligand shows an activation energy in the range of semiconducting materials. The antimicrobial activity of all compounds has also been demonstrated.     

Photochemically induced fluorescence investigation of aβ-cyclodextrin: Azure A inclusion complex and determination of analytical parameters

The photooxidation of Azure A and fluorescence properties of Azure A and its photoproduct have been investigated in aqueous media and in the presence of-cyclodextrin (-CD). The fluorescence intensity of the complex formed between the photoproduct and -CD was found to be three times higher than that of the uncomplexed Azure A photoproduct. A complex formation constant of 110±40 M^–1 was calculated using the Benesi-Hildebrand treatment of the fluorescence emission data. Although the stoichiometry of the Azure A photoproduct: -CD complex was found to be 1: 1, it seems that the Azure A structure is only partially included. Calibration graphs were plotted for the free Azure A photoproduct and the photogenerated product included in -CD. The analytical parameters and quantification limits were determined.     

Hygrometric Determination of Water Activities, Osmotic and Activity Coefficients, and Excess Gibbs Energy of the System MgSO4–K2SO4–H2O

Ternary aqueous solutions of MgSO₄ and K₂SO₄ have been studied by the hygrometric method at 25°C. The relative humidity of this system is measured at total molalities from 0.35 mol-kg^–1 to about saturation for three ionic-strength fractions (y = 0.25, 0.50, and 0.80 of MgSO₄. The data allow calculation of water activities and osmotic coefficients. From these measurements, the Pitzer ionic mixing parameters are determined and used to predict the solute activity coefficients in the mixture. The results are used to calculate the excess Gibbs energy at total molalities for ionic-strength fraction y.