A brief review on structural concepts of novel supramolecular proton transfer compounds and their metal complexes

Our research group has been interested in synthesis of proton transfer compounds as new supramolecular synthons for the onepot preparation of self-assembled transition metal complex-organo-networks since 2000. We have focused on the proton delivery from acids, which are considered as suitable proton donors, to amines as proton acceptors. The results were production of several proton transfer ion pairs possessing some remaining donor sites applied for coordination to metallic centers in preparation of metal-organic structures. Some of the complexes showed contributions of both cationic and anionic fragments of the starting ion pair, while some others contained only one of these species as ligand. Much of the investigations on reviewed compounds focused on the concept of supramolecular systems, co-crystallization, stereochemically active lone pairs, coordination polyhedron and mainly on various interactions involve including van der Waals, ion pairing, hydrogen bondings, face to face π-π stackings and edge to face C-H...π, C-O...π, N-H...π, S-O...π, Ti...π and Hg-Cl...π interactions. The mentioned interactions are the most commonly used strategies in the extension of supramolecular structures.     

Synthesis and structure of nanocrystalline La0.50Ba0.50MnO3

Nanocrystalline manganite La_0.50Ba_0.50MnO₃ was synthesized by the soft-chemical method. For this purpose, the sol-gel method was modified and improved. A trihydric saturated alcohol, e.g., glycerol, was suggested as a new organic matrix. The crystal structure of the composite was studied by X-ray powder diffraction at room temperature. A La_0.50Ba_0.50MnO₃ powder annealed in air at T = 500°C is characterized by a perovskite-like cubic structure with the unit-cell parameter a = 3.869 Å. The chemical composition of the sample was studied by electron-probe X-ray microanalysis. The La: Ba: Mn cation ratio in the material was 1: 1: 2. The surface topography was examined with a scanning electron microscope. The crystallite size was ～30 nm. The dependence of the crystal structure and the surface topology on the annealing temperature was studied. The high-temperature treatment in air resulted in the growth of larger, micrometer-size, crystallites.     

Rheological properties of polyacrylates used as synthetic road binders

Most adhesives and binders, including bitumen for asphalt mixture production, are presently produced from petrochemicals after the refining of crude oil. The fact that crude oil reserves are a finite resource means that in the future, it may become necessary to produce these materials from alternative and probably renewable sources. Suitable resources of this kind may include polysaccharides, plant oils and proteins. This paper deals with the synthesis of polymer binders from monomers that could, in future, be derived from renewable resources. These binders consist of polyethyl acrylate (PEA) of different molecular weight, polymethyl acrylate (PMA) and polybutyl acrylate (PBA), which were synthesised from ethyl acrylate, methyl acrylate and butyl acrylate, respectively, by atom transfer radical polymerisation. The rheological properties of these binders were determined by means of oscillatory testing using a dynamic shear rheometer and combinations of stress/strain, temperature and frequency sweeps. The results indicate that PEA can be produced to have rheological properties similar to that of ‘soft’ 100/150 penetration grade bitumen, PMA with similar rheological properties to that of ‘hard’ 10/20 penetration grade bitumen, while PBA, due to its highly viscous nature and low dynamic moduli, cannot be used on its own as a binder. The synthetic polymers were found to be thermo-rheologically simple, and the shift factors, used to produce the dynamic moduli master curves, were found to fit an Arrhenius function.     

Rapid and accurate amperometric determination of acetaminophen in pharmaceutical preparations and spiked human blood serum samples at cadmium pentacyanonitrosylferrate modified glassy carbon electrode

The present work describes a rapid and accurate amperometric technique for the determination of acetaminophen (ACT) in pharmaceutical preparations and human blood serum, based on electrocatalytic oxidation of ACT at a glassy carbon electrode modified by cadmium pentacyanonitrosylferrate (CdPCNF) film. The electrocatalytic response of the modified GC electrode was linear over the concentration of 1.64-52.90 μM. The limit of detection was found to be 2.04 μM by amperometric technique. The method was successfully utilized for the determination of ACT in various pharmaceutical preparations and the results have been statistically compared with those obtained by the official method. The interference of some pharmaceutical and biological compounds was investigated. The results of interference study showed that the Nafion-coated CdPCNF|GC electrode can be utilized as a selective amperometric sensor for acetaminophen determination in human blood serum. The mean value of rate constant k for catalytic reaction, and the diffusion coefficient of ACT (D) in the phosphate buffer solution of pH 7.2 were found to be 4.27 × 10² M?¹ s?¹, and (4.25 ± 0.33) × 10^?6 cm² s^?1, respectively.     

Globally anisotropic high porosity silica aerogels

We discuss two methods by which high porosity silica aerogels can be engineered to exhibit global anisotropy. First, anisotropy can be introduced with axial strain (i.e. axial compression). In addition, intrinsic anisotropy can result during growth and drying stages and, suitably controlled, it can be correlated with preferential radial shrinkage in cylindrical samples. We have performed small angle X-ray scattering (SAXS) to characterize these two types of anisotropy. We show that global anisotropy originating from either strain or shrinkage leads to optical birefringence and that optical cross-polarization studies are a useful characterization of the uniformity of the imposed global anisotropy.     

Time-resolved cavity ringdown spectroscopy on nanoparticle generation in a SiH4–H2 VHF plasma

Time-resolved cavity ringdown (τ-CRD) spectroscopy has been applied to monitor the silyl (SiH₃) radicals and nanoparticles in a pulsed very high frequency (VHF) silane-hydrogen plasma under microcrystalline silicon (μc-Si:H) deposition conditions. The measured cavity loss reveals four time intervals (I up to VI) in the first 4 s of the plasma pulse. By variation of the laser wavelength, it is demonstrated that the small cavity loss at 220 nm reflects the SiH₃ absorption in interval I. In intervals II and III, an additional cavity loss appears. This additional cavity loss corresponds to Rayleigh and Mie scattering by growing nanoparticles. Interval IV reflects the loss of nanoparticles between the electrodes during the afterglow of the plasma pulse. The evolution of the nanoparticle generation determined from the τ-CRD measurements are further confirmed by additional scanning electron microscopy analyses on the nanoparticles created in the plasma pulse.     

Indentation responses of piezoelectric films

Frictionless indentation responses of transversely isotropic piezoelectric film/rigid substrate systems under circular cylindrical indenter (i.e., punch), conical indenter (i.e., cone), and spherical indenter (i.e., sphere) are investigated. Both insulating and conducting indenters are considered. The technique of Hankel transformation is employed to derive the corresponding dual integral equations for the mixed boundary value indentation problems. For the two limiting cases of infinitely thick and infinitely thin piezoelectric films, closed-form solutions are obtained. For piezoelectric films of finite thickness, a numerical method is constructed to solve the dual integral equations and semi-empirical models having only two unknown parameters are proposed for the responses of indentation force, electric charge and electric potential, and contact radius. With the two parameters inferred from the numerical results, the semi-empirical formulae are found to provide good estimates of the indentation responses for the two limiting cases of infinitely thick and thin piezoelectric films, as well as those in between. The inferred parameters in the proposed semi-empirical formulae for normalized indentation force and electric charge are checked against four different piezoelectric materials and are found to be insensitive to the selection of piezoelectric materials. It is believed that the proposed semi-empirical indentation formulae are useful in developing experimental indentation techniques to extract the material properties of piezoelectric films.     

Synthesis and characterization of novel polyimides with 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein‐3′,5′‐bis(trifluoromethyl)anilide

2,2‐Bis[4(4‐aminophenoxy)phenyl]phthalein‐3′,5′‐bis(trifluoromethyl)anilide (6FADAP), containing fluorine and phthalimide moieties, was synthesized via the Williamson ether condensation reaction from 1‐chloro‐4‐nitrobenzene and phenolphthalein‐3′,5′‐bis(trifluoromethyl)anilide, which was followed by hydrogenation. Monomers such as 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein‐anilide containing phthalimide groups and 2,2‐bis[4(4‐aminophenoxy)phenyl]phthalein containing only phthalein moieties were also synthesized for comparison. The monomers were first characterized by Fourier transform infrared (FTIR), ¹H NMR, ¹⁹F NMR, elemental analysis, and titration and were then used to prepare polyimides with 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride. The polyimides were designed to have molecular weights of 20,000 g/mol via off‐stoichiometry and were characterized by FTIR, NMR, gel permeation chromatography (GPC), differential scanning calorimetry, and thermogravimetric analysis. Their solubility, water absorption, dielectric constant, and refractive index were also evaluated. The polyimides prepared with 6FADAP, containing fluorine and phthalimide moieties, had excellent solubility in N‐methylpyrrolidinone, N,N‐dimethylacetamide, tetrahydrofuran, CHCl₃, tetrachloroethane, and acetone, and GPC analysis showed a molecular weight of 18,700 g/mol. The polyimides also exhibited a high glass‐transition temperature (290 °C), good thermal stability (～500 °C in air), low water absorption (1.9 wt %), a low dielectric constant (2.81), a low refractive index, and low birefringence (0.0041). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3361–3374, 2003     

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