Syntheses and properties of mixed dinuclear copper(II) complexes with heterocyclic dithiocarbamates and a cyclic octadentate tertiary amine

Five new Cu^II complexes of general formula [Cu₂(Rdtc)tpmc](ClO₄)₃, (1)–(5), where tpmc and Rdtc ^– refer to N,N,N,N-tetrakis(2-pyridylmethyl)-1,4,8,11-teraazacyclotetradecane and piperidine- (Pipdtc), 4-morpholine- (Morphdtc), 4-thiomorpholine- (Timdtc), piperazine- (Pzdtc) or N-methylpiperazine- (N-Mepzdtc) dithiocarbamates, respectively, have been prepared. Elemental analyses, conductometric and magnetic measurements, u.v./vis, i.r., e.p.r. and mass spectroscopy have been employed to characterize them. The complexes adopt an exo coordination of Cu^II ions and tpmc. The dithiocarbamate ion joins both the sulphur and the copper atoms acting as a bridging ligand The presence of different heteroatoms in the piperidine ring influences the (C=N) and (C=S) vibrations which decrease in the order of the complexes: Pipdtc>N-Mepipdtc>Pzdtc>Morphdtc>Timdtc ligands. Attention has been paid to the detailed mechanism of the mass spectral fragmentation of the complexes. The g _eff factors of the complexes have been also estimated by e.p.r. spectra. Finally, the complexes obtained demonstrate microbiologycal activity against some bacteria.     

Spectral methods for the equations of classical density-functional theory: relaxation dynamics of microscopic films

We propose a numerical scheme based on the Chebyshev pseudo-spectral collocation method for solving the integral and integro-differential equations of the density-functional theory and its dynamic extension. We demonstrate the exponential convergence of our scheme, which typically requires much fewer discretization points to achieve the same accuracy compared to conventional methods. This discretization scheme can also incorporate the asymptotic behavior of the density, which can be of interest in the investigation of open systems. Our scheme is complemented with a numerical continuation algorithm and an appropriate time stepping algorithm, thus constituting a complete tool for an efficient and accurate calculation of phase diagrams and dynamic phenomena. To illustrate the numerical methodology, we consider an argon-like fluid adsorbed on a Lennard-Jones planar wall. First, we obtain a set of phase diagrams corresponding to the equilibrium adsorption and compare our results obtained from different approximations to the hard sphere part of the free energy functional. Using principles from the theory of sub-critical dynamic phase field models, we formulate the time-dependent equations which describe the evolution of the adsorbed film. Through dynamic considerations we interpret the phase diagrams in terms of their stability. Simulations of various wetting and drying scenarios allow us to rationalize the dynamic behavior of the system and its relation to the equilibrium properties of wetting and drying.     

Single enzyme studies reveal the existence of discrete functional states for monomeric enzymes and how they are "selected" upon allosteric regulation

Allosteric regulation of enzymatic activity forms the basis for controlling a plethora of vital cellular processes. While the mechanism underlying regulation of multimeric enzymes is generally well understood and proposed to primarily operate via conformational selection, the mechanism underlying allosteric regulation of monomeric enzymes is poorly understood. Here we monitored for the first time allosteric regulation of enzymatic activity at the single molecule level. We measured single stochastic catalytic turnovers of a monomeric metabolic enzyme (Thermomyces lanuginosus Lipase) while titrating its proximity to a lipid membrane that acts as an allosteric effector. The single molecule measurements revealed the existence of discrete binary functional states that could not be identified in macroscopic measurements due to ensemble averaging. The discrete functional states correlate with the enzyme's major conformational states and are redistributed in the presence of the regulatory effector. Thus, our data support allosteric regulation of monomeric enzymes to operate via selection of preexisting functional states and not via induction of new ones.     

Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide

Multiblock copolymers of ethylene oxide, with four and five different blocks, were synthesized by the sequential anionic polymerization of styrene, isoprene, 2-vinyl pyridine, t-butyl methacrylate, and ethylene oxide with benzyl potassium as an initiator. The monomer sequence was based on the relative nucleophilicity of the active centers. Characterization of the multiblock copolymers by size exclusion chromatography (with refractive-index and UV detectors), membrane osmometry, and NMR spectroscopy confirmed that benzyl potassium is an efficient initiator for the synthesis of well-defined multiblock multicomponent copolymers of ethylene oxide. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2166–2170, 2002     

Melt‐state polymer chain dimensions as a function of temperature

The unperturbed chain dimensions (〈R²〉_o/M) of cis/trans‐1,4‐polyisoprene, a near‐atactic poly(methyl methacrylate), and atactic polyolefins were measured as a function of temperature in the melt state via small‐angle neutron scattering (SANS). The polyolefinic materials were derived from polydienes or polystyrene via hydrogenation or deuteration and represent structures not encountered commercially. The parent polymers were prepared via lithium‐based anionic polymerizations in cyclohexane with, in some cases, a polymer microstructure modifier present. The polyolefins retained the near‐monodisperse molecular weight distributions exhibited by the precursor materials. The melt SANS‐based chain dimension data allowed the evaluation of the temperature coefficients [dln 〈R²〉_o/dT(κ)] for these polymers. The evaluated polymers obeyed the packing length (p)‐based expressions of the plateau modulus, G = kT/np³ (MPa), and the entanglement molecular weight, M_e = ρN_anp³ (g mol^?1), where n_t denotes the number (～21) of entanglement strands in a cube with the dimensions of the reptation tube diameter (d_t) and ρ is the chain density. The product np³ is the displaced volume (V_e) of an entanglement that is also expressible as pd or kT/G. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1768–1776, 2002     

Versatile organic (fullerene)-inorganic (CdTe nanoparticle) nanoensembles

Novel organic (positively charged fullerene)-inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor-acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states.     

Novel diblock copolymer‐grafted multiwalled carbon nanotubes via a combination of living and controlled/living surface polymerizations

Diels–Alder cycloaddition reactions were used to functionalize multiwalled carbon nanotubes (MWNTs) with 1‐benzocylcobutene‐1′‐phenylethylene (BCB‐PE) or 4‐hydroxyethylbenzocyclobutene (BCB‐EO). The covalent functionalization of the nanotubes with these initiator precursors was verified by FTIR and thermogravimetric analysis (TGA). After appropriate transformations/additions, the functionalized MWNTs were used for surface initiated anionic and ring opening polymerizations of ethylene oxide and ε‐caprolactone (ε‐CL), respectively. The OH‐end groups were transformed to isopropylbromide groups by reaction with 2‐bromoisobutyryl bromide, for subsequent atom transfer radical polymerization of styrene or 2‐dimethylaminoethyl methacrylate to afford the final diblock copolymers. ¹H NMR, differential scanning calorimetry (DSC), TGA, and transmission electron microscopy (TEM) were used for the characterization of the nanocomposite materials. TEM images showed the presence of a polymer layer around the MWNTs as well as the dissociation of MWNT bundles. Consequently, this general methodology, employing combinations of different polymerization techniques, increases the diversity of diblocks that can be grafted from MWNTs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1104–1112, 2010     

Crystallization and Physical Ageing of Poly (2-vinyl pyridine)-b-poly(ethylene oxide) Diblock Copolymers

Summary: A set of melt miscible Poly(2-vinyl pyridine)-b-Poly(ethylene oxide) (P2VP-b-PEO) block copolymers of different compositions were studied. Transmission electron microscopy shows phase separation in the materials during the crystallization process of the PEO block as crystalline lamellae are observed for all compositions evaluated. The isothermal crystallization kinetics of PEO is progressively retarded as the P2VP content in the copolymer increases, since P2VP hinders molecular mobility in the miscible amorphous phase. Polarized light optical microscopy demonstrated that the glassy P2VP block has a negative effect on the secondary nucleation of the PEO. Finally, physical ageing experiments performed in the glassy state of the amorphous mixed phase, at different ageing times, demonstrated that a nucleating effect can be induced in the glassy state as a consequence of the reorganization of the amorphous regions. This nucleating effect significantly alters the cold crystallization rate upon subsequent heating above the glass transition temperature.     

Thin film pyrolytic carbon electrodes: A new class of carbon electrode for electroanalytical sensing applications

This communication describes the electrochemical properties of thin pyrolytic carbon (PyC) films created using a reliable, non-catalytic chemical vapour deposition (CVD) process. After deposition, the electron transfer characteristics of the films are optimised using a simple oxygen plasma treatment. The redox probes Ru(NH₃)₆^3+/2+, Fe(CN)₆^3?/4? and Fe^3+/2+ are employed to demonstrate that the resulting material is endowed with a large electrochemical surface area and outstanding electron transfer properties. Atomic force microscopy (AFM), Raman and X-ray photoelectron spectroscopy (XPS) are used to elucidate the morphology and chemical composition of the electrode surfaces. This material represents a new class of carbon electrode, and its large densities of edge-plane sites and oxygenated functionalities make it an ideal candidate for electrochemical sensor applications.     

Electrochemical Impedance Spectroscopy and Cyclic Voltammetry of <Emphasis Type="Italic">cis</Emphasis>-[Cr(bipy)<Subscript>2</Subscript>(SCN)<Subscript>2</Subscript>]I (where bipy: 2,2′-Bipyridine) in Polar Solvents

Cyclic voltammetric studies (CV) on the complex cis-bis(2,2′-bipyridine)bis(thiocyanate)chromium(III) iodide [Cr(bipy)₂(SCN)₂]I (where bipy: 2,2′-bipyridine, C₁₀H₈N₂) were recorded on platinum (Pt) and glassy carbon (GC) electrodes in either acetonitrile (ACN) or acetone (ACE) solvent media including n-tetrabutylammonium hexafluorophosphate (NBu₄PF₆) as supporting electrolyte, at scan rates (v) ranging from 0.05 to 0.12 V⋅s⁻¹. In addition, electrochemical impedance spectroscopic (EIS) measurements in the frequency (f) range from 0.1 Hz to 50 kHz were carried out on GC and Pt electrodes. The half-wave potential (E _1/2) of the redox couple Cr(III)/Cr(II) was determined as −0.84 V and −0.79 V (versus Ag/AgCl) in ACN and ACE, respectively. The heterogeneous electron transfer rate constant (k _s) corresponding to the couple Cr(III)/Cr(II) was found to be greater on GC compared to the Pt electrode. The nature of the solvent medium also affects the kinetics of the investigated couple, to be exact, k _s increases remarkably upon replacement of ACE by ACN. The EIS results indicate that the GC electrode is a better capacitor and provides the smaller charge transfer resistance in ACN.