Phosphonic acid derivatized polythiophene: A building block for metal phosphonate and polyelectrolyte multilayers

A water-soluble polythiophene with pendant phosphonic acid groups, poly(3-(3'-thienyloxy)propane-phosphonate) (P3TOPP), has been synthesized. Matrix-assisted laser desorption ionization (MALDI) measurements showed that P3TOPP is an oligomer with an average chain length of 10 monomer units. In aqueous solutions it could be electrochemically oxidized and displayed self-acid doping at pH below 13. P3TOPP was used to prepare polyelectrolyte multilayers with poly(diallyldimethylammonium chloride) (PDADMA) and metal phosphonate multilayers with Zr4+ ions by the sequential layer-by-layer technique. The films were characterized by electrochemistry, atomic force microscopy (AFM), UV-vis, IR, and X-ray photoelectron (XPS) spectroscopy. A regular layer-by-layer growth was observed with both types of multilayers. The nature of the films was probed with XPS, which showed that the observed binding energies were characteristic for metal phosphonates and polyelectrolyte multilayers in Zr/P3TOPP and P3T0PP/PDADMA films, respectively. In the former, the Zr:P ratio showed deviation from the theoretical stoichiometry, and the reasons for the nonstoichiometry are discussed. In the latter, the N:P ratio was consistent with the partial deprotonation of the phosphonate groups. The multilayers exhibited both electrochromism and pH-induced halochromism

Riesz and Wolff potentials and elliptic equations in variable exponent weak Lebesgue spaces

We prove optimal integrability results for solutions of the p(x)-Laplace equation in the scale of (weak) Lebesgue spaces. To obtain this, we show that variable exponent Riesz and Wolff potentials map L1 to variable exponent weak Lebesgue spaces

Photoelectron spectroscopy study of irradiation damage and metal-sulfur bonds of thiol on silver and copper surfaces

Self-assembled l-dodecanethiol monolayers (SAMs) on silver and copper surfaces have been characterized with X-ray photoelectron spectroscopy (XPS) using both the synchrotron radiation and conventional Mg Kalpha excitation. Irradiation-induced changes in thiolate SAMs on Cu and Ag were observed. The identification of the sulfur species has been done. Results obtained confirm earlier studies of n-alkanethiols on silver. On copper (C12S/Cu), the observed S 2p spectrum is quite broad but the use of different excitation energies enabled us to identify four sulfur species on the surface. A S 2P(3/2) component of copper thiolate is observed at 162.6 eV. Three more doublets (161.9 eV, 163.2 eV and 163.8 eV) have been observed to develop during irradiation and they are assigned to chemisorbed sulfur on copper, to different dialkylsulfides and to sulfur-sulfur bonding, (C) 2004 Elsevier B.V. All rights reserved

Preparation of multilayers containing conjugated thiophene-based polyelectrolytes. Layer-by-layer assembly and viscoelastic properties

We study the layer-by-layer assembly and properties of polyelectrolyte multilayers containing anionic and cationic poly(alkoxythiophene) derivatives, poly(3-(3'-thienyloxy)propanesulfonate) (P3TOPS) and poly(3-(3'-thienyloxy)propyltriethylammonium) (P3TOPA), together with poly(diallyldimethylammonum chloride) (PDADMA) or poly(styrenesulfonate) (PSS). These polythiophenes are rigid-rod-type polyelectrolytes which tend to aggregate in aqueous medium. Three types of multilayers have been prepared: (P3TOPS/P3TOPA)(n) (all-thiophene films), (P3TOPS/PDADMA)(n), and (PSS/P3TOPA)(n). The layer-by-layer adsorption of polythiophenes was followed by UV-vis spectroscopy and surface plasmon resonance (SPR). Adsorption of P3TOPS and P3TOPA took place within 10 min from dilute aqueous solution (1 mM with respect to monomers). The adsorption of anew polyion layer on top of polythiophene was always accompanied by a partial loss of the polythiophene layer. As the result, the amount of polythiophene in the film oscillated as a function of the number of layers. This behavior was attributed to the adsorption and partial desorption of aggregated polythiophene, supported by atomic force microscope (AFM) images of dry films. Per bilayer, the amount of polythiophene remaining in the film increased linearly and corresponded approximately to the formation of a thiophene monolayer. The viscoelastic properties of the film; also exhibited a marked terminal layer effect in cases where the length and hydrophobicity of the polyions were different. This effect was studied with (PSS/PDADMA) multilayers and was attributed to the formation of loops and tails, All multilayers studied appeared very soft, comparable to protein layers. This softness was attributed mainly to the film/solution interface with a hydrogel-like outer part of the films (zone III)

Intrinsic non-symbiotic and truncated haemoglobins and heterologous Vitreoscilla haemoglobin expression in plants

To date, haemoglobins (Hbs) have been shown to exist in all kingdoms of life. The least studied and understood groups are plant non-symbiotic haemoglobins (nsHbs) and the recently found plant truncated Hbs (trHbs). From a biotechnological point of view, the best characterized and almost exclusively applied Hb is the bacterial Vitreoscilla haemoglobin (VHb). In this review, the present state of knowledge of structural features and ligand binding kinetics of plant nsHbs and trHbs and their proposed roles as oxygen carriers, oxygen sensors, and for oxygen storage, in nitric oxide (NO) detoxification, and in peroxidase activity are described. Furthermore, in order to predict the functioning of plant Hbs, their characteristics will be compared with those of the better known bacterial globins. In this context, the effects of heterologous applications of VHb on plants are reviewed. Finally, the challenging future of plant Hb research is discusse

Chemisorption of alkyl thiols and S-alkyl thiosulfates on Pt(111) and polycrystalline platinum surfaces

The self-assembled monolayers prepared from 1-dodecanethiol (C12SH) or S-dodecylthio sulfate (Bunte salt, C12SSO3Na) have been characterised on polycrystalline gold and platinum surfaces and on Pt(111). Contact angle and impedance measurements show that the film quality decreases in the order Au/C12SH > Pt/C12SH similar to Au/C12SSO3-Na > Pt/C12S SO3Na. XPS measurements show that the S-SO3 bond of organic thiosulfates is broken on platinum surfaces and the state of the surface-bound sulfur is indistinguishable from that of thiolate. On platinum three sulfur species are formed upon SAM formation and we suggest that the catalytic activity of platinum is responsible for their existence in pristine monolayers. (c) 2005 Elsevier B.V. All rights reserved

Water-soluble full-length single-wall carbon nanotube polyelectrolytes: Preparation and characterization

HiPco single-wall carbon nanotubes (SWNTs) have been noncovalently modified with ionic pyrene and naphthalene derivatives to prepare water-soluble SWNT polyelectrolytes (SWNT-PEs), which are analogous to polyanions and polycations. The modified nanotubes have been characterized with UV-vis-NIR, fluorescence, Raman and X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The nanotube-adsorbate interactions consist of π-π stacking interactions between the aromatic core of the adsorbate and the nanotube surface and specific contributions because of the substituents. The interaction between nanotubes and adsorbates also involves charge transfer from adsorbates to SWNTs, and with naphthalene sulfonates the role of a free amino group was important. The ionic surface charge density of the modified SWNTs is constant and probably controlled by electrostatic repulsion between like charges. The linear ionic charge density of the modified SWNTs is similar to that of common highly charged polyelectrolytes

New insights on the interaction between thiophene derivatives and Au surfaces: the case of 3,4-ethylenedioxythiophene and the relevant polymer.

The nature of the interface between electrogenerated poly(3,4-ethylenedioxythiophene) and the Au substrate is studied in detail. In particular, the adsorption of the relevant monomer, namely, 3,4-ethylenedioxythiophene, is investigated and compared with that of other thiophene derivatives. Different deposition procedures have been adopted: very thin films of the thiophene derivatives have been obtained through chemisorption processes from vapor and liquid phases, on Au polycrystalline substrates, Au nano particles possessing different size, and a Au(111) single crystal. Different techniques, operating both in situ and ex situ, have been employed for the characterization of these deposits, that is, X-ray photoemission and surface enhanced Raman spectroscopy. The results show that the poly(3,4-ethylenedioxythiophene)/metal interface is far from being simply constituted by unreacted molecules in contact with the substrate; rather, the formation of oligothiophene species and sulfur atoms at the interface has been ascertained

Polydopamine Nanoparticles Prepared Using Redox-Active Transition Metals

Autoxidation of dopamine to polydopamine by dissolved oxygen is a slow process that requires highly alkaline conditions. Polydopamine can be formed rapidly also in mildly acidic and neutral solutions by using redox-active transition-metal ions. We present a comparative study of polydopamine nanoparticles formed by autoxidation and aerobic or anaerobic oxidation in the presence of Ce(IV), Fe(III), Cu(II), and Mn(VII). The UV-vis spectra of the purified nanoparticles are similar, and dopaminechrome is an early intermediate species. At low pH, Cu(II) requires the presence of oxygen and chloride ions to produce polydopamine at a reasonable rate. The changes in dispersibility and surface charge take place at around pH 4, which indicates the presence of ionizable groups, especially carboxylic acids, on their surface. X-ray photoelectron spectroscopy shows the presence of three different classes of carbons, and the carbonyl/carboxylate carbons amount to 5-15 atom %. The N 1s spectra show the presence of protonated free amino groups, suggesting that these groups may interact with the pi-electrons of the intact aromatic dihydroxyindole moieties, especially in the metal-induced samples. The autoxidized and Mn(VII)-induced samples do not contain metals, but the metal content is 1-2 atom % in samples prepared with Ce(IV) or Cu(II), and ca. 20 atom % in polydopamine prepared in the presence of Fe(III). These differences in the metal content can be explained by the oxidation and complexation properties of the metals using the general model developed. In addition, the nitrogen content is lower in the metal-induced samples. All of the metal oxidants studied can be used to rapidly prepare polydopamine at room temperature, but the possible influence of the metal content and nitrogen loss should be taken into account