Characterization of electrochemically visualized latent fingerprints on the steel substrates

Journal of Solid State Electrochemistry - The characterization of electrochemically visualized latent fingerprints on steel surfaces is demonstrated. Optimization of electrochemical conditions of...     

RAFT of sulfobetaine for modifying poly(glycidyl methacrylate) microspheres to reduce nonspecific protein adsorption

The minimization of nonspecific protein adsorption is a crucial step in the development of bioseparation processes, immunoassays, and affinity diagnostics. Among the numerous biomaterials, polyzwitterions are known to effectively suppress protein and cell adhesion. This article describes the formation of monodisperse polymer microspheres coated with polysulfobetaine with the aim to limit nonspecific adsorption of bovine serum albumin (BSA) as a model protein. In this process, 2‐μm poly(glycidyl methacrylate) (PGMA) microspheres were prepared by dispersion polymerization. To render the microspheres hydrophilic and biocompatible, [3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide (MPDSAH) was grafted from the surface by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Elemental analysis of the modified microspheres revealed up to 20 wt % of poly{[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonimum hydroxide} (PMPDSAH). The microspheres were characterized in terms of particle size, morphology, and zeta potential. The amount of BSA nonspecifically adsorbed on the PMPDSAH‐modified microspheres decreased to half of that captured on the unmodified PGMA microspheres. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2273–2284     

Self‐Assembly of Aniline Oligomers

A great number of nano/microscaled morphologies have recently been prepared during the oxidation of aniline. At the early stage of oxidation, aniline oligomers are obtained, often in spectacular morphologies depending on reaction conditions. Herein, the flower‐like hierarchical architectures assembled from aniline oligomers by a template‐free method are reported. Their formation process is ascribed to the self‐assembly of oligoanilines through non‐covalent interactions, such as hydrogen bonding, hydrophobic forces, and π–π stacking. The model of directional growth is offered to explain the formation of petal‐like objects and, subsequently, flowers. In order to investigate the chemical structure of the oligomers, a series of characterizations have been carried out, such as matrix‐assisted laser desorption ionization, time‐of‐flight mass spectrometry, gas chromatography coupled with mass spectrometry analysis, X‐ray diffraction, and UV/Vis, Fourier‐transform infrared, and Raman spectroscopies. Based on the results of characterization methods, a formation mechanism for aniline oligomers and their self‐assembly is proposed.     

Nanostructural composites of phthalocyanine and metals

Thin composite films of metal nanoparticles incorporated into a phthalocyanine matrix were prepared by simultaneous vacuum deposition of copper and phthalocyanine from two evaporation sources. Absorption spectra in both the IR and UV/VIS regions were measured in order to study changes of structure and properties with different volume fractions of copper in the films. The effective medium theory (EMT) approach was used to model optical spectra. A pronounced aging of composite layers was observed after the deposition.     

Intercalates of Vanadyl Phosphate with Aliphatic Nitriles

Intercalates of vanadyl phosphate with aliphatic nitriles (acetonitrile, propionitrile, butyronitrile, valeronitrile and hexanenitrile) were prepared and characterized by X-ray powder diffraction, thermogravimetric analysis, IR and Raman spectroscopies. The basal spacings of all the intercalates prepared are practically identical. The nitrile intercalates (except acetonitrile) contain one nitrile molecule per formula unit. The nitrile molecules are anchored to the host layers by an N–V donor-acceptor bond and their aliphatic chains are parallel to the host layers. The acetonitrile intercalate contains two guest molecules per formula unit. Only half of them can be bonded to the vanadium atom, the second half is probably anchored by van der Waals interaction. The intercalates prepared are moisture-sensitive and the guest molecules are easily replaced by water molecules.     

Polymerization of aniline on polyaniline membranes

When solutions of aniline hydrochloride and ammonium peroxydisulfate were separated by a semipermeable cellulose membrane, the reactants met at the membrane and produced a polyaniline (PANI) membrane at the interface. The oxidative polymerization of aniline then proceeded in situ on the PANI-cellulose composite membrane. PANI was produced entirely at the monomer side of the membrane; about 80% conversion of aniline to PANI was observed after 24 h. The oxidation of aniline with peroxydisulfate consists in the transfer of electrons from aniline to the oxidant; it is proposed that electrons pass through the PANI membrane, which is conducting, and electroneutrality is maintained by the simultaneous transfer of protons. The reaction between aniline and peroxydisulfate thus takes place without the need for both reactant molecules to be in physical contact. The residual aniline is located only at its original side of the membrane, but the product of ammonium peroxydisulfate conversion, ammonium hydrogen sulfate, was found on both sides of the membrane. Fourier-transform infrared spectroscopy has been used to analyze PANI, the reaction residues and byproducts, and to prove that PANI is protonated with counter-ions of the sulfate type. Using this technique, we have detected only small differences in the molecular structure of PANI prepared with the membrane-separated reactants and in the polymerization when reactants were mixed; also, the molecular weights differed only marginally. The conductivity of both types of PANI was about the same. The repeated polymerization of aniline on the earlier prepared PANI-cellulose membrane yielded similar results, thus confirming the proposed concept of coupled electron- and proton-transfer through the PANI membrane.     

Cerium(IV) phenylphosphonates and para-substituted phenylphosphonates: preparation and characterization

Cerium(IV) phenylphosphonates and 4-substituted phenylphosphonates were prepared by reaction of a cerium(IV) salt with corresponding acids (phenylphosphonic, 4-carboxyphenylphosphonic, 4-sulfamoylphenylphosphonic, 1,4-benzenediphosphonic, 1,4-biphenyldiphosphonic and 4-sulfophenylphosphonic acid) and characterized by elemental analysis, energy-dispersive X-ray analysis, TGA, powder X-ray diffraction and infrared spectroscopy. Three different cerium phenylphosphonates can be prepared in dependence on the reaction conditions. On the other hand, only one compound is formed in each 4-substituted phosphonate system regardless the variation of the reaction conditions. All three phenylphosphonates, 4-carboxyphenylphosphonate and 4-sulfamoylphenylphosphonate are layered with the organic parts pointed below and above the plane of the metal phosphonate layers, with the functional groups placed at the end of the organic part. 4-Sulfophenylphosphonate, 1,4-benzenediphosphonate and 4,4′-biphenyldiphosphonate form pillared structures. Cerium 4-carboxyphenylphosphonate is able to intercalate aliphatic amines due to the presence of the free carboxylic groups in its interlayer space.     

Temperature- and humidity-related degradation of conducting polyaniline films

The time dependence of dc conductivity of conducting polyaniline films was measured in relation to temperature and relative humidity of the environment. Optical and structural properties of the samples were checked using Fourier transform infrared (FTIR) spectroscopy.     

Explosive hazards in polyaniline chemistry

Polyaniline, a conducting polymer, is prepared by the oxidation of aniline with various oxidants. When using ammonium peroxydisulfate or hydrogen peroxide at high concentrations, the temperature may exceed boiling point of reaction mixture, which then explodes. This represents a safety hazard in the synthesis of polyaniline. Also polyaniline samples prepared in the solutions of nitric acid may spontaneously ignite or decompose during the characterization. The synthesis using the recommended protocol is safe.     

Chemical oxidative polymerization of aminodiphenylamines

The course of oxidation of 4-aminodiphenylamine with ammonium peroxydisulfate in an acidic aqueous ethanol solution as well as the properties of the oxidation products were compared with those of 2-aminodiphenylamine. Semiconducting oligomers of 4-aminodiphenylamine and nonconducting oligomers of 2-aminodiphenylamine of weight-average molecular weights 3700 and 1900, respectively, were prepared by using an oxidant to monomer molar ratio of 1.25. When this ratio was changed from 0.5 to 2.5, the highest conductivity of oxidation products of 4-aminodiphenylamine, 2.5 x 10 (-4) S cm (-1), was reached at the molar ratio [oxidant]/[monomer] = 1.5. The mechanism of the oxidative polymerization of aminodiphenylamines has been theoretically studied by the AM1 and MNDO-PM3 semiempirical quantum chemical methods combined with the MM2 molecular mechanics force-field method and conductor-like screening model of solvation. Molecular orbital calculations revealed the prevalence of N prim-C10 coupling reaction of 4-aminodiphenylamine, while N prim-C5 is the main coupling mode between 2-aminodiphenylamine units. FTIR and Raman spectroscopic studies confirm the prevalent formation of linear N prim-C10 coupled oligomers of 4-aminodiphenylamine and suggest branching and formation of phenazine structural units in the oligomers of 2-aminodiphenylamine. The results are discussed with respect to the oxidation of aniline with ammonium peroxydisulfate, leading to polyaniline, in which 4-aminodiphenylamine is the major dimer and 2-aminodiphenylamine is the most important dimeric intermediate byproduct.