Surface Chemistry of Thiobacillus ferrooxidans Relevant to Adhesion on Mineral Surfaces

Thiobacillus ferrooxidans cells grown on sulfur, pyrite, and chalcopyrite exhibit greater hydrophobicity than ferrous ion-grown cells. The isoelectric points of sulfur-, pyrite-, and chalcopyrite-grown cells were observed to be at a pH higher than that for ferrous ion-grown cells. Microbe-mineral interactions result in change in the surface chemistry of the organism as well as that of the minerals with which it has interacted. Sulfur, pyrite, and chalcopyrite after interaction with T. ferrooxidans exhibited a significant shift in their isoelectric points from the initial values exhibited by uninteracted minerals. With antibodies raised against sulfur-grown T. ferrooxidans, pyrite- and chalcopyrite-grown cells showed immunoreactivity, whereas ferrous ion-grown cells failed to do so. Fourier transform infrared spectroscopy of sulfur-grown cells suggested that a proteinaceous new cell surface appendage synthesized in mineral-grown cells brings about adhesion to the solid mineral substrates. Such an appendage was found to be absent in ferrous ion-grown cells as it is not required during growth in liquid substrates.

3,12-dinitro-5,10,15,20-tetraphenylporphyrin- an example of a twisted intramolecular charge-transfer system

he porphyrin ring in the title compound, 10,19-dinitro-2,7,12,17-tetraphenyl-21,22,23,24-tetraazapenta-cyclo[16.2.1.1(3,6).1(8,11).1(13,16)]tetracosa-1,3,5,7,9,11(23),-12,14,16,18(21),19-undecaene 0.5-dichloromethane solvate, C44H28N6O4.0.5CH2Cl2, adopts a saddle conformation with neighbouring pyrrole rings tilted with respect to each other. The two nitro groups are situated on alternate pyrrole rings and have their planes angled away from those of the pyrrole rings, thereby indicating that interaction between the porphyrin and nitro groups is slight.

Flat connections, geometric invariants and the symplectic nature of the fundamental group of surfaces

In this paper we associate a new geometric invariant to the space of fiat connections on a G (= SU(2))-bundle on a compact Riemann surface M and relate it tcr the symplectic structure on the space Hom(pi(1)(M), G)/G consisting of representations of the fundamental group pi(1)(M) Of M into G module the conjugate action of G on representations.

Probing potential energy surfaces in confined systems: behavior of mean-square displacement in zeolites

Time evolution of mean-squared displacement based on molecular dynamics for a variety of adsorbate-zeolite systems is reported. Transition from ballistic to diffusive behavior is observed for all the systems. The transition times are found to be system dependent and show different types of dependence on temperature. Model calculations on a one-dimensional system are carried out which show that the characteristic length and transition times are dependent on the distance between the barriers, their heights, and temperature. In light of these findings, it is shown that it is possible to obtain valuable information about the average potential energy surface sampled under specific external conditions.

Surface-ray tracing on hybrid surfaces of revolution for UTD mutual coupling analysis

An angle invariance property based on Hertz's principle of particle dynamics is employed to facilitate the surface-ray tracing on nondevelopable hybrid quadric surfaces of revolution (h-QUASOR's). This property, when used in conjunction with a Geodesic Constant Method, yields analytical expressions for all the ray-parameters required in the UTD formulation. Differential geometrical considerations require that some of the ray-parameters (defined heuristically in the UTD for the canonical convex surfaces) be modified before the UTD can be applied to such hybrid surfaces. Mutual coupling results for finite-dimensional slots have been presented as an example on a satellite launch vehicle modeled by general paraboloid of revolution and right circular cylinder.

Applicability of Butler's equation in interpreting the thermodynamic behavior of surfaces and adsorption in Fe-S-O melts

Expressions for various second-order derivatives of surface tension with respect to composition at infinite dilution in terms of the interaction parameters of the surface and those of the bulk phases of dilute ternary melts have been presented. A method of deducing the parameters, which consists of repeated differentiation of Butler's equations with subsequent application of the appropriate boundary conditions, has been developed. The present investigation calculates the surface tension and adsorption functions of the Fe-S-O melts at 1873 and 1923 K using the modified form of Butler's equations and the derived values for the surface interaction parameters of the system. The calculated values are found to be in good agreement with those of the experimental data of the system. The present analysis indicates that the energetics of the surface phase are considerably different from those of the bulk phase. The present research investigates a critical compositional range beyond which the surface tension increases with temperature. The observed increase in adsorption of sulfur with consequent desorption of oxygen as a function of temperature above the critical compositional range has been ascribed to the increase of activity ratios of oxygen to sulfur in the surface relative to those in the bulk phase of the system.

Inter And Intramolecular Interactions Of Porphyrins With 5,5′-Dithiobis(2-Nitrobenzoic Acid)

meso-Tetraphenylporphyrin and its metal [zinc(II) and copper(II)] derivatives form both inter and intramolecular complexes with 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB). The nature of interaction is predominantly charge transfer (CT) in origin, with the porphyrin functioning as a II-donor and DTNB as an acceptor. Among the covalently linked intramolecular systems, the magnitude of CT interaction varies with the position (of one of the aryl groups of the porphyrin) to which DTNB is attached as ortho meta > para. Steady-state and time-resolved fluorescence studies revealed electron transfer to be the dominant pathway for the fluorescence quenching in these systems. Steady-state photolysis experiments probed using EPR and optical absorption studies have shown that electron transfer (from the excited singlet state of the porphyrin) to DTNB results in the formation of thiyl radical and production of free thiolate anion. It is found that the products of electrochemical reduction of covalently linked porphyrin-DTNB systems are different from those observed for the photochemical studies.

Local polynomial convexity of the union of two totally-real surfaces at their intersection

We consider the following question: Let S (1) and S (2) be two smooth, totally-real surfaces in C-2 that contain the origin. If the union of their tangent planes is locally polynomially convex at the origin, then is S-1 boolean OR S-2 locally polynomially convex at the origin? If T (0) S (1) a (c) T (0) S (2) = {0}, then it is a folk result that the answer is yes. We discuss an obstruction to the presumed proof, and provide a different approach. When dim(R)(T0S1 boolean AND T0S2) = 1, we present a geometric condition under which no consistent answer to the above question exists. We then discuss conditions under which we can expect local polynomial convexity.

Photochemical intramolecular gamma-hydrogen abstraction in a ketone and an alkene and the role of tunneling of hydrogen

Intramolecular gamma-hydrogen abstraction reactions were examined in pentane-2-one and 2-methyl-1-pentene in their lowest triplet states using the AM1 semi-empirical molecular orbital method with the complete geometry optimization in the unrestricted Hartree-Fock frame. The results reveal that the oxygen atom of the carbonyl group and the end carbon atom of the olefinic bond acquire high free valence and spin density indices in their respective lowest triplet states, leading to abstraction of hydrogen from the gamma-position relative to the carbonyl and olefinic bonds. The theoretical energy profiles fit with a polynomial and the probability of tunneling of hydrogen was estimated by the WKB (Wentzel, Kramer and Brillouin) method. The results, after thermal averaging of the rate constants, reveal that tunneling of hydrogen is significant at room temperature.

Synthesis of chiral bicyclo[2.2.2]oct-5-en-2-ones via an intramolecular alkylation reaction

Generation of the thermodynamic dienolate of 9-bromocarvone derivatives 5, 7 and 11 furnished the chiral bicycle[2.2.2] octenones 6, 8 and 9 and 12 and 13 containing a bridgehead methyl group via an intramolecular alkylation reaction. In an analogous manner intramolecular alkylation reaction of the bromo enones 15a-e, obtained from carvone 2 by 1,3-alkylative enone transposition (-->14) followed by a regiospecific bromoetherification reaction, furnished the bicyclo[2.2.2]oct-5-en-2-ones 16a-e and 17a-e.

Flat connections, geometric invariants and energy of harmonic functions on compact Riemann surfaces

A geometric invariant is associated to the space of fiat connections on a G-bundle over a compact Riemann surface and is related to the energy of harmonic functions.