A Polyaniline-Deposited Nonplatinum Metal as a Potentiometric Sensor—An Inexpensive Alternate to Conventional Platinum for Some Potentiometric Redox Reactions

For the purpose of employing an inexpensive alternative to conventional platinum for use by upper-division as well as graduate students, polyaniline (PANI)-deposited stainless steel (SS) and mild steel (MS) electrodes are described as indicator electrodes for potentiometry and potentiometric titrations of some redox reactions. PANI is deposited on the nonplatinum metal by electrochemical polymerization of aniline using cyclic voltammetric technique. Alternate methods to produce the PANI electrodes are also suggested. The electrodes respond to concentration changes of hydroquinone (H₂O), Fe²⁺/Fe³⁺, and [Fe(CN)₆]^4–/[Fe(CN)₆]^3– in HCL electrolytes, and the potential variation with concentration follows the Nernst relationship. Under identical experimental conditions, the response time of the PANI/SS, PANI/MS, and Pt electrodes for a change in concentration of Fe³⁺ in a mixed electrolyte of Fe²⁺ and Fe³⁺ is found to be about 20 s. Neutralization reaction of HC1 versus NaOH, redox reaction of Fe²⁺ and Ce⁴⁺, and redox reaction of Fe²⁺ and KMnO₄ in several concentrations in the range from 1 mM to 100 mM are carried out using the PANI/SS, PANI/MS, and Pt indicator electrodes. The performance of the PANI/SS and PANI/MS electrodes is as good as that of the Pt at all concentration levels of the titrations. The electrodes can be reused for several titrations by storing them in an acid electrolyte for a long period of time. Thus, the conventional inert Pt or Au can be substituted for by using a PANI-deposited nonplatinum reactive metal as a potentiometric sensor for redox titrations.     

Orthogonal surface-grafted polymer gradients: A versatile combinatorial platform

Orthogonal polymer brush gradients are assemblies of surface-anchored macromolecules, in which two material properties of the grafted chains (e.g., grafting density, molecular weight) vary independently in orthogonal directions. Here, we describe the formation and applications of two such orthogonal assemblies, involving: (1) molecular weight and grafting density (MW/σ) gradients of a given polymer and (2) molecular weight gradients (MW1/MW2), of two different polymers. Each point on orthogonal gradient substrate represents a unique combination of the two surface properties being varied, thus facilitating systematic investigation of a phenomenon that depends on the two said properties. We illustrate this point by employing orthogonal structures to study systematically: (1) formation of polymer brush-nanoparticle composite assemblies, (2) protein adsorption and cell adhesion, and (3) chain conformations in tethered diblock copolymers exposed to selective solvents. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3384–3394, 2005     

A new look at Theodorsen's method in aerofoil theory

Theodorsen's method for calculating the incompressible potential flow past an aerofoil is viewed afresh. It is found that some simple modifications to the computational process make the computations relatively faster, easier and more accurate. The new modifications are applicable to the analysis of conventional aerofoils with up to moderate thickness and camber ratios. Several examples are presented to show the effectiveness of the modifications.     

Head-group size or hydrophilicity of surfactants: the major regulator of lipase activity in cationic water-in-oil microemulsions

To determine the crucial role of surfactant head-group size in micellar enzymology, the activity of Chromobacterium Viscosum (CV) lipase was estimated in cationic water-in-oil (w/o) microemulsions of three different series of surfactants with varied head-group size and hydrophilicity. The different series were prepared by subsequent replacement of three methyl groups of cetyltrimethylammonium bromide (CTAB) with hydroxyethyl (1-3, series I), methoxyethyl (4-6, series II), and n-propyl (7-9, series III) groups. The hydrophilicity at the polar head was gradually reduced from series I to series III. Interestingly, the lipase activity was found to be markedly higher for series II surfactants relative to their more hydrophilic analogues in series I. Moreover, the activity remained almost comparable for complementary analogues of both series I and III, though the hydrophilicity was drastically different. Noticeably, the head-group area per surfactant is almost similar for comparable surfactants of both series I and III, but distinctly higher in case of series II surfactants. Thus the lipase activity was largely regulated by the surfactant head-group size, which plays the dominant role over the hydrophilicity. The increase in head-group size presumably allows the enzyme to attain a flexible conformation as well as increase in the local concentration of enzyme and substrate, leading to the higher efficiency of lipase. The lipase showed its best activity in the microemulsion of 6 probably because of its highest head-group size. Furthermore, the observed activity in 6 is 2-3-fold and 8-fold higher than sodium bis(2-ethyl-1-hexyl)sulfosuccinate (AOT) and CTAB-based microemulsions, respectively, and in fact highest ever in any w/o microemulsions.     

Non Existence of Triangle Free Quasi-symmetric Designs

The following two results are proved. Let D be a triangle free quasi-symmetric design with k=2y−x and x≥ 1 then D is a trivial design with v=5 and k=3. There do no exist triangle free quasi-symmetric designs with x≥ 1 and λ=y or λ=y−1.Communicated by: P. Wild     

Preparation and characterization of some stereochemically rigid seven-coordinate η-cyclopentadienyltris(N,N-dialkyldithiocarbamato)hafnium(IV) complexes

Summary N,N-Dialkyldithiocarbametohafnium(IV) complexes of the type -CpHf(S₂CNR₂)₃, (R = Me or Et) have been prepared in nonaqueous media by reacting dichlorodicyclopentadienylhafnium(IV) with sodium salts of substituted dithiocarbamic acids. Conductance and i.r. studies show that these complexes are nonelectrolytes in which all of the dithiocarbamate ligands are bidentate. A coordination number of seven may be assigned to hafnium(IV) in these complexes, 'H n.m.r. spectra of the complexes in CDCI₃ at ambient temperature (30°) indicate that the metal centered rearrangement and the S₂C N bond rotation are both slow on the n.m.r. time scale. A capped octahedron configuration is suggested for these complexes.Author to whore all correspondence should be addressed.     

Electron transport and redox reactions in carbon-based molecular electronic junctions

A unique molecular junction design is described, consisting of a molecular mono- or multilayer oriented between a conducting carbon substrate and a metallic top contact. The sp2 hybridized graphitic carbon substrate (pyrolyzed photoresist film, PPF) is flat on the scale of the molecular dimensions, and the molecular layer is bonded to the substrate via diazonium ion reduction to yield a strong, conjugated C-C bond. Molecular junctions were completed by electron-beam deposition of copper, titanium oxide, or aluminium oxide followed by a final conducting layer of gold. Vibrational spectroscopy and XPS of completed junctions showed minimal damage to the molecular layer by metal deposition, although some electron transfer to the molecular layer resulted in partial reduction in some cases. Device yield was high (>80%), and the standard deviations of junction electronic properties such as low voltage resistance were typically in the range of 10-20%. The resistance of PPF/molecule/Cu/Au junctions exhibited a strong dependence on the structure and thickness of the molecular layer, ranging from 0.13 ohms cm2 for a nitrobiphenyl monolayer, to 4.46 ohms cm2 for a biphenyl monolayer, and 160 ohms cm2 for a 4.3 nm thick nitrobiphenyl multilayer. Junctions containing titanium or aluminium oxide had dramatically lower conductance than their PPF/molecule/Cu counterparts, with aluminium oxide junctions exhibiting essentially insulating behavior. However, in situ Raman spectroscopy of PPF/nitroazobenzene/AlO(x)/Au junctions with partially transparent metal contacts revealed that redox reactions occurred under bias, with nitroazobenzene (NAB) reduction occurring when the PPF was biased negative relative to the Au. Similar redox reactions were observed in PPF/NAB/TiO(x)/Au molecular junctions, but they were accompanied by major effects on electronic behavior, such as rectification and persistent conductance switching. Such switching was evident following polarization of PPF/molecule/TiO2/Au junctions by positive or negative potential pulses, and the resulting conductance changes persisted for several minutes at room temperature. The "memory" effect implied by these observations is attributed to a combination of the molecular layer and the TiO2 properties, namely metastable "trapping" of electrons in the TiO2 when the Au is negatively biased.     

Mesoporous materials with zeolite framework: remarkable effect of the hierarchical structure for retardation of catalyst deactivation

Hierarchical MFI zeolite was synthesized following a synthesis route using organic-inorganic hybrid surfactants; the resultant zeolite with mesoporous/microporous hierarchical structure exhibited remarkably high resistance to deactivation in catalytic activity of various reactions such as isomerization of 1,2,4-trimethylbenzene, cumene cracking, and esterification of benzyl alcohol with hexanoic acid, as compared with conventional MFI and mesoporous aluminosilicate MCM-41.     

Organosilane surfactant-directed synthesis of mesoporous aluminophosphates constructed with crystalline microporous frameworks

A direct hydrothermal assembly process was developed to synthesize mesoporous aluminophosphates that are constructed with crystalline microporous frameworks, by the addition of organosilane surfactants into the conventional synthesis composition for crystalline microporous aluminophosphates.