Effect of surface attachment on synthesis of bacterial cellulose

Gluconacetobacter spp. synthesize a pure form of hydrophilic cellulose that has several industrial specialty applications. Literature reports have concentrated on intensive investigation of static and agitated culture in liquid media containing high nutrient concentrations optimized for maximal cellulose production rates. The behavior of these bacteria on semisolid and solid surfaces has not been specifically addressed. The species Gluconacetobacter hansenii was examined for cellulose synthesis and colony morphology on a range of solid supports, including cotton linters, and on media thickened with agar, methyl cellulose, or gellan. The concentration and chemical structure of the thickening agent were found to be directly related to the formation of contiguous cellulose pellicules. Viability of the bacteria following freezer storage was improved when the bacteria were frozen in their cellulose pellicules. This article was authored by a contractor of the US government under contract no. DEAC05-00OR22725. Accordingly, the US government retains a nonexclusive, royalty-free license to publish or reproduce the published form of this contribution, or allow others to do so, for US government purposes.     

Chemical force titrations of amine- and sulfonic acid-modified poly(dimethylsiloxane)

Chemical force titrations-measurements of the adhesive interaction between a pair of suitably chemically modified atomic force microscopy (AFM) tip and sample surfaces as a function of pH-have been carried out for various combinations of silanol, amine, carboxylic acid, and sulfonic acid functional groups on both tip and sample. The primary surface material studied was poly(dimethylsiloxane) (PDMS). Surface modification was carried out using a plasma oxidation process to form silanol sites; further modification with amine or sulfonic acid sites was carried out by reaction of the silanol sites with the appropriate trialkoxysilane derivative. AFM tips were also modified using trialkoxysilane compounds. In the cases of tip/sample combinations with the same functional group on each, surface pK(1/2) values could be determined. In several "mixed" tip/sample combinations, a peak appeared in the titration curve midway between the surface pK(1/2) values of the tip and sample, consistent with an ionic H-bonding model for the interactions. The amine/sulfonic acid pair showed more complex behavior; the amine-terminated tip/sulfonic acid-terminated PDMS surface force titration curve consisted of two peaks centered at pH 4 and pH 8. Reversing the tip/sample pair resulted in the peak positions being shifted upward by 1.0 pH unit. The peak appearing at lower pH is assigned to electrostatic interactions between the two oppositely charged surfaces, whereas the higher pH peak is believed to arise due to ionic H-bonding interactions. AFM images show the effects on surface patterning of amine- and sulfonic acid-modified PDMS surfaces that have undergone two different oxidation methods (air plasma oxidation and Tesla coil oxidation). The surface morphologies of freshly prepared and 24 h aged air plasma oxidized PDMS are also discussed in this study.     

Spectral and photophysical characterization of donor-pi-acceptor arylthienyl- and bithienyl-benzothiazole derivatives in solution and solid state

A comprehensive study has been made in solution at room temperature (293 K), low temperature (77 K), and in thin films (Zeonex matrixes) of the spectral and photophysical properties of six arylthienyl- and bithienyl-benzothiazole derivatives functionalized with different donor groups. Similar experiments have been carried out with two related precursors (containing the arylthienyl and aryl-bithienyl conjugated systems), and results are compared. Singlet-singlet and triplet-triplet absorption spectra, emission spectra together with lifetimes and quantum yields have been obtained, and from these data the rates for all the radiative and nonradiative processes determined, providing information on the dominant decay processes. The arylthienyl-benzothiazole derivatives show high fluorescence quantum yields (phi(F)) with negligible internal conversion (phi(IC)), whereas the bithienyl-benzothiazoles display lower but still significant phi(F) values, but now radiationless processes (phi(IC) and phi(ISC)) are competitive. A comparison with the analogous oligothiophenes is made. Singlet oxygen yields were also determined and the triplet energy transfer to (3)O2 to produce (1)O2 was found to be highly efficient with values of S(Delta)(= phi(Delta)/phi(T)) varying from 0.4 to 1.     

()‐3‐Ethyl‐2‐methyl‐4‐oxo­cyclo­hexane­carboxyl­ic acid: catemeric hydrogen bonding in a cyclic δ‐keto acid

In the title compound, C₁₀H₁₆O₃, the two mol­ecules of the asymmetric unit form acid‐to‐ketone hydrogen‐bonded chains. The two species differ only very slightly and are related by a pseudo‐center, so that the apparent translational relationship among the units of the hydrogen‐bonded chain is actually a pseudo‐translation, with the mol­ecules alternating in type. Two counterdirectional pairs of chains proceed through each cell [O⋯O = 2.743 (2) and 2.683 (2) Å, and O—H⋯O = 171 (3) and 157 (3)°]. Three intermolecular C—H⋯O close contacts were found, involving all three O atoms of one of the mol­ecules.     

Characterization of the triplet state of tris(8-hydroxyquinoline)aluminium(III) in benzene solution

The lowest triplet state of tris(8-hydroxyquinoline)aluminium(III) (Alq3) has been prepared by pulse radiolysis/energy transfer from appropriate donors in benzene solutions and has an absorption maximum around 510 nm with a lifetime of about 50 mus. It is quenched by molecular oxygen, leading to singlet oxygen formation. From flash photolysis and singlet oxygen formation measurements, a quantum yield of triplet formation of 0.24 was determined for direct photolysis of the complex. A value of 2.10 +/- 0.10 eV was determined for the energy of the lowest triplet state by energy transfer studies and was confirmed by phosphorescence measurements on Alq3, either in the heavy atom solvent ethyl iodide or photosensitized by benzophenone in benzene. Dexter (exchange) energy transfer was observed from triplet Alq3 to platinum(II) octaethylporphyrin.     

X-ray absorption and EPR spectroscopic studies of the biotransformations of chromium(VI) in mammalian cells. Is chromodulin an artifact of isolation methods?

Very different biological activities are usually ascribed to Cr(VI) (a toxin and carcinogen) and Cr(III) (an antidiabetic agent), although recent evidence suggests that both these types of actions are likely to arise from cellular uptake of varying concentrations of Cr(VI). The first systematic study of XANES spectra of Cr(III) complexes formed in Cr(VI)-treated mammalian cells (A549, HepG2, V79, and C2C12 cell lines), and in subcellular fractions of A549 cells, has been performed using a library of XANES spectra of model Cr(III) complexes. The results of multiple linear regression analyses of XANES spectra, in combination with multiple-scattering fits of XAFS spectra, indicate that Cr(III) formed in Cr(VI)-treated cells is most likely to bind to carboxylato, amine, and imidazole residues of amino acids, and to a lesser extent to hydroxo or aqua ligands. A combination of XANES and EPR spectroscopic data for Cr(VI)-treated cells indicates that the main component of Cr(III) formed in such cells is bound to high-molecular-mass ligands (>30 kDa, probably proteins), but significant redistribution of Cr(III) occurs during the cell lysis, which leads to the formation of a low-molecular-mass (<30 kDa) Cr(III)-containing fraction. The spectroscopic (XANES, XAFS, and EPR) properties of this fraction were strikingly similar to those of the purported natural Cr(III)-containing factor, chromodulin, that was reported to be isolated from the reaction of Cr(VI) with liver. These data support the hypothesis that a chromodulin-like species, which is formed from such a reaction, is an artifact of the reported isolation procedure.     

Controlling interfacial curvature in nanoporous silica films formed by evaporation-induced self-assembly from nonionic surfactants. II. Effect of processing parameters on film structure

The double-gyroid phase of nanoporous silica films has been shown to possess facile mass-transport properties and may be used as a mold to fabricate a variety of highly ordered inverse double-gyroid metal and semiconductor films. This phase exists only over a very small region of the binary phase diagram for most surfactants, and it has been very difficult to synthesize metal oxide films with this structure by evaporation-induced self-assembly (EISA). Here, we show the interplay of the key parameters needed to synthesize these structures reproducibly and show that the interfacial curvature may be systematically controlled. Grazing angle of incidence small-angle X-ray scattering (GISAXS) is used to determine the structure and orientation of nanostructured silica films formed by EISA from dilute silica/(poly(ethylene oxide)-b-poly(propylene oxide)-b-alkyl) surfactant solutions. Four different highly ordered film structures are observed by changing only the concentration of the surfactant, the relative humidity during dip-coating, and the aging time of the solution prior to coating. The highly ordered films progress from rhombohedral (Rm) to 2D rectangular (c2m) to double-gyroid (distorted Iad) to lamellar systematically as interfacial curvature decreases. Under all experimental conditions investigated, increasing the aging time of the coating solution was found to decrease the interfacial curvature. In particular, this parameter was critical to being able to synthesize highly ordered, pure-phase double-gyroid films. The key role of the aging time is shown via processing diagrams that map out the interplay between the aging time, composition, and relative humidity. 29Si nuclear magnetic resonance (NMR) spectroscopy and solution-phase small-angle X-ray scattering (SAXS) of the aged coating solutions presented in part I of this series are then used to interpret the effects of aging prior to dip-coating. Specifically, it was found that a predictive model based on volume fractions and the silica cluster stoichiometry obtained from 29Si NMR qualitatively explains the trends observed with composition and aging. However, apart from the effects of relative humidity, a quantitative comparison of the predicted phase with the experimental processing diagram suggests that less-condensed silica clusters are more effective at swelling the EO blocks at early aging times. This enhanced swelling decreases with aging time and results in lower-curvature nanostructures such as the double-gyroid. The decrease in swelling is attributed to the decreased thermodynamic driving force for the more-condensed silica clusters to mix with the EO block of the surfactant.     

S1P1-selective in vivo-active agonists from high-throughput screening: off-the-shelf chemical probes of receptor interactions, signaling, and fate

The essential role of the sphingosine 1-phosphate (S1P) receptor S1P(1) in regulating lymphocyte trafficking was demonstrated with the S1P(1)-selective nanomolar agonist, SEW2871. Despite its lack of charged headgroup, the tetraaromatic compound SEW2871 binds and activates S1P(1) through a combination of hydrophobic and ion-dipole interactions. Both S1P and SEW2871 activated ERK, Akt, and Rac signaling pathways and induced S1P(1) internalization and recycling, unlike FTY720-phosphate, which induces receptor degradation. Agonism with receptor recycling is sufficient for alteration of lymphocyte trafficking by S1P and SEW2871. S1P(1) modeling and mutagenesis studies revealed that residues binding the S1P headgroup are required for kinase activation by both S1P and SEW2871. Therefore, SEW2871 recapitulates the action of S1P in all the signaling pathways examined and overlaps in interactions with key headgroup binding receptor residues, presumably replacing salt-bridge interactions with ion-dipole interactions.     

New prodrugs derived from 6-aminodopamine and 4-aminophenol as candidates for melanocyte-directed enzyme prodrug therapy (MDEPT)

Two novel tyrosinase mediated drug delivery pathways have been investigated for the selective delivery of cytotoxic units to melanocytes from urea and thiourea prodrugs. The synthesis of these prodrugs is reported, as well as oximetry data that illustrate that the targets are substrates for tyrosinase. The stability of each of the prodrugs in (i) phosphate buffer and (ii) bovine serum is discussed, and the urea prodrugs are identified as lead candidates for further studies. Finally, HPLC studies and preliminary cytotoxicity studies in a melanotic and an amelanotic cell line, that illustrate the feasibility of the approach, are presented.     

Interactions of benzoic acid and phosphates with iron oxide colloids using chemical force titration

Colloidal iron oxides are an important component in soil systems and in water treatment processes. Humic-based organic compounds, containing both phenol and benzoate functional groups, are often present in these systems and compete strongly with phosphate species for binding sites on the iron oxide surfaces. Here, we examine the interaction of benzoate and phenolic groups with various iron oxide colloids using atomic force microscopy (AFM) chemical force titration measurements. Self-assembled monolayers (SAMs) of 4-(12-mercaptododecyloxy)benzoic acid and 4-(12-mercaptododecyloxy)phenol were used to prepare chemically modified Au-coated AFM tips, and these were used to probe the surface chemistry of a series of iron oxide colloids. The SAMs formed were also characterized using scanning tunneling microscopy, reflection-absorption infrared spectroscopy, and X-ray photoelectron spectroscopy. The surface pK(a) of 4-(12- mercaptododecyloxy)benzoic acid has been determined to be 4.0 +/- 0.5, and the interaction between the tip and the sample coated with a SAM of this species is dominated by hydrogen bonding. The chemical force titraton profile for an AFM probe coated with 4-(12- mercaptododecyloxy)benzoic acid and a bare iron oxide colloid demonstrates that the benzoic acid function group interacts with all three types of iron oxide sites present on the colloid surface over a wide pH range. Similar experiments were carried out on colloids precipitated in the presence of phosphoric, gallic, and tannic acids. The results are discussed in the context of the competitive binding interactions of solution species present in soils or in water treatment processes.