Chemical deposition and characterization of thin polypyrrole films on glass plates: role of organosilane treatment

 Thin chloride-doped polypyrrole films (PPyCl) were deposited chemically onto untreated and silane-treated planar glass plates from aqueous solutions. The organosilanes used to treat the glass substrates were methyltriethoxysilane (Cl), propyltrimethoxysilane (C3), octyltrimethoxysilane (C8) and aminopropyltriethoxysilane (APS). The decreasing order of hydrophobic character of silane-treated glass slides, as measured by water contact angle measurements, was glass–APS ≅ glass–C8 > glass–C3 > glass–C1 > glass. X-ray photoelectron spectroscopy was used to determine the surface chemical composition of the glass plates before and following coating with the silane coupling agents and/or the PPy thin layer, respectively. The attenuation in intensity of the glass Na_{1 s} peak enabled the average thickness of the various organosilane overlayers to be estimated. Atomic force microscopy showed that the morphology of the organosilane overlayers was islandlike. The domains have a structure which depends upon the nature of the organosilane in question. Scanning electron microscope images showed that the morphology of the PPyCl thin films was homogeneous when coated onto glass–APS and glass–C8, but wrinkled at the surface of glass, glass–C1 and glass–C3 plates. Qualitative peel tests using 3M adhesive tape showed very good adhesion of PPyCl to the glass–APS substrate, whereas adhesion was fairly poor in the case of glass–PPy and PPy–alkylsilane–glass interfaces. The results of this multitechnique study suggest that hydrophobic interactions are important to obtain homogeneous and continuous thin PPy films, but Lewis acid–base interactions are the driving forces for strong and durable PPy–glass adhesion. Received: 3 January 2000/Accepted: 19 May 2000     

A short range many-body potential for modelling bcc metals

The problem considered is the fitting of a many-body interaction potential to bulk crystal data. A parameterisation of the potential is assumed which is based on physical considerations. The free parameters are determined by using global optimization to perform a least squares fit, to a large number of crystal properties. This has been achieved for body centered cubic (bcc) materials. The approach adopted here fits the bcc crystal structure, as the preferred minimum energy configuration for tungsten, and also fits the dimer energetics and the elastic properties of crystalline tungsten.     

Ion plated indium oxide : infrared and optical study

The high optical transparency of ion plated indium oxide combined with their mechanical hardness and good environmental stability have opened up numerous applications in the line of sophisticated optoelectronic devices. Indium is evaporated at a low oxygen pressure on to an ordinary glass substrate mounted under the cathode and biased by a r.f. generator at 13,6 M Hz. Infrared spectra are recorded in the range 5000–200 cm^?1 by A.T.R. and reflexion-absorption spectroscopy, and show between 800 and 200 cm^?1 bands due to stretching and bending modes predicted by a factor group analysis. A tentative assignment is made of the highest frequency. Last U.V. and visible spectra are discussed.     

Characterisation of cement pastes by inverse gas chromatography

Two cement pastes, commonly used in concrete formulations, were characterised by IGC at 35-80 degrees C before and after coating with an epoxy resin and a hardener. The cements are mixtures of hydrates in various proportions, such as calcium silicate hydrate (CaO-SiO2-H2O) and calcium hydroxide Ca(OH)2. Apolar and polar probes were used to determine the dispersive and acid-base characteristics of the cement pastes. These materials have high surface energy as judged from the dispersive contribution to the surface free energy (gamma(s)d) values lying in the 50-70 mJ/m2 range at 60-80 degrees C. Examination of the specific interactions permitted to show that the cement pastes are strongly amphoteric species with a substantial predominant Lewis basicity that is in line with the basic pH of their aqueous suspensions. Following coating with an epoxy resin (DGEBA) and a hardener (triethylene tetramine), the surface energy of the cements decreases substantially with the mass loading of the organic material. The surface thermodynamic properties were also correlated with the surface chemical composition as determined by X-ray photoelectron spectroscopy.     

Novel approach for metallic surface-initiated atom transfer radical polymerization using electrografted initiators based on aryl diazonium salts

This paper reports on the preparation of poly(methyl methacrylate) (PMMA), poly(n-butyl acrylate) (PBA), and polystyrene (PS) brushes at the surface of conducting materials that were modified by the electrochemical reduction of a brominated aryl diazonium salt BF4-, +N2-C6H4-CH(CH3)-Br (D1). The grafted organic species -C6H4-CH(CH3)-Br was found to be very effective in initiating atom transfer radical polymerization (ATRP) of vinyl monomers. This novel approach combining diazonium salts and ATRP allowed PMMA, PBA, and PS brushes to be grown from the surface of iron electrodes. The polymer films were characterized in terms of their chemical structure by infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy. Atomic force microscopy studies indicated that the polymer brushes are densely packed. Contact angle measurements of water drops on PS and PMMA brushes were 88.1 +/- 2.0 and 70.3 +/- 2.1 degrees, respectively, which is consistent with the published wettability data for the corresponding polymer sheets.     

Covalent modification of iron surfaces by electrochemical reduction of aryldiazonium salts.

Electrochemical reduction of aryldiazonium salts (in acetonitrile or acidic aqueous medium) on an iron or mild steel surface permits the strong bonding (which resists an ultrasonic cleaning) of aryl groups on these surfaces. Attachment of aryl groups was demonstrated by the combined used of electrochemistry, infrared spectroscopy and polarization modulation infrared reflection spectroscopy (PMIRRAS), Rutherford backscattering, X-ray photoelectron spectroscopy, and capacity measurements. The substituents of aryl groups, which can be widely varied, include NO2, I, COOH, and long alkyl chains. It is shown that the attachment of the aryl groups is to an iron and not to an oxygen atom and that the bond is covalent.     

Alcaloides steroidiques—LII Alcaloides du buxus balearica Willd.: Cycloprotobuxine-D, buxamine-E, buxaminol-E, N-isobutyryl-baleabuxidine-F, N-benzoyl-baleabuxidine-F, baleabuxoxazine-C, N-isobutyryl-baleabuxidienine-F, N-benzoyl-baleabuxidienine-F, N-isobutyryl-baleabuxaline-F

The following alkaloides have been extracted from the leaves of Buxus balearica Willd.: cyclomicrophylline-B, cycloprotobuxines A, C and D, baleabuxine (N-isobutyryl-baleabuxine-F), buxamine-E and buxaminol-E (already reported), N-isobutyryl- and N-benzoyl-baleabuxidine-F, baleabuxoxazine-C, N-isobutyryl- and N-benzoyl-baleabuxidienine-F, N-isobutyryl-baleabuxaline-F, the structures of which are proposed. The stereochemistry of baleabuxidines and baleabuxoxazines is established on the base of chemical correlations between these two groups and cyclomicrophyllines.     

Synthesis of Polysiloxane-Immobilized Monoamine,Diamine, and Triamine Ligand Systems in the Presence of CTAB and Their Applications

Abstract

Polysiloxane-immobilized monoamine, diamine, and triamine ligand systems of the general formula P-(CH₂)₃-X [where P represents a polysiloxane three-dimension silica like network, and X represents monoamine(-NH₂), diamine (-NH(CH₂)₂NH₂), or triamine (-NH(CH₂)₂NH(CH₂)₂NH₂) functional ligand groups] were prepared by hydrolytic polycondensation of the tetraethylorthosilicate (TEOS) and the appropriate amine silane coupling agent (RO)₃Si-(CH₂)₃X in the presence of cetyltrimethylammonium bromide (CTAB) as surfactant using the sol-gel method. The polysiloxane-immobilized amine ligand systems exhibit a higher potential for divalent metal ions (Cu²⁺, Ni²⁺, Co²⁺) when CTAB was used as surfactant than those of the corresponding polysiloxane ligand systems prepared without CTAB. X-ray Photoelectron Spectroscopy (XPS) analyses show a significant change in the surface composition as resulting from the incorporation of CTAB, which can be related to the increase in the uptake of metal ions.     

Diazonium salt-derived 4-(dimethylamino)phenyl groups as hydrogen donors in surface-confined radical photopolymerization for bioactive poly(2-hydroxyethyl methacrylate) grafts

In this paper we describe a novel methodology for grafting polymers via radical photopolymerization initiated on gold surfaces by aryl layers from diazonium salt precursors. The parent 4-(dimethylamino)benzenediazonium salt was electroreduced on a gold surface to provide 4-(dimethylamino)phenyl (DMA) hydrogen donor layers; free benzophenone in solution was used as a photosensitizer to strip hydrogen from the grafted DMA. This system permitted efficient surface initiation of photopolymerization of 2-hydroxyethyl methacrylate. The resulting poly(2-hydroxyethyl methacrylate) (PHEMA) grafts were found to be very adherent to the surface as they resist total failure after being soaked in the well-known paint stripper methyl ethyl ketone. The PHEMA grafts were reacted with 1,1'-carbonyldiimidazole to yield carbamate groups that are able to react readily with amino groups from proteins. The final surface consisted of protein-functionalized PHEMA grafts where bovine serum albumin (BSA) protein is specifically linked to the grafts by covalent bonds. We used X-ray photoelectron spectroscopy to monitor the chemical changes at the gold surface all along the process from the neat gold to the end-protein-functionalized polymer grafts: the PHEMA graft thickness ranged from 7 to 27 nm, and the activation by 1,1'-carbonyldiimidazole reached 37% of the OH groups, which was sufficient for 90% surface coverage of the grafts by BSA. This work conclusively provides a new approach for bridging reactive and functional polymers to surfaces via aryl diazonium salts in a simple, fast, and efficient approach of importance in biomedical and other applications.