Effect of metal cations on polydiacetylene Langmuir films

Polydiacetylene (PDA) Langmuir films (LFs) are a unique class of materials that couple a highly aligned conjugated backbone with tailorable pendant side groups and terminal functionalities. The films exhibit chromatic transitions from monomer to blue polymer and finally to a red phase that can be activated optically, thermally, chemically, and mechanically. The properties of PDA LFs are strongly affected by the presence of metal cations in the aqueous subphase of the film due to their interaction with the carboxylic head groups of the polymer. In the present study the influence of divalent cadmium, barium, copper, and lead cations on the structural, morphological, and optical properties of PDA LFs was investigated by means of surface pressure-molecular area (π-A) isotherms, atomic force microscopy, optical absorbance, and Raman spectroscopy. The threshold concentrations for the influence of metal cations on the film structure, stability, and phase transformation were determined by π-A analyses. It was found that each of the investigated cations has a unique influence on the properties of PDA LFs. Cadmium cations induce moderate phase transition kinetics with reduced domain size and fragmented morphology. Barium cations contribute to stabilization of the PDA blue phase and enhanced linear strand morphology. On the other hand, copper cations enhance rapid formation of the PDA red phase and cause fragmented morphology of the film, while the presence of lead cations results in severe perturbation of the film with only a small area of the film able to be effectively polymerized. The influence of the metal cations is correlated with the solubility product (K(sp)), association strength, and ionic-covalent bond nature between the metal cations and the PDA carboxylic head groups.     

Comparative thermostability of whey protein and alginate hydrospheres complexed with divalent cations

Journal of Thermal Analysis and Calorimetry - Water retention and thermostability of powders and films of whey protein isolate (WPIp, dWPIf), sodium alginate (NaALGp, NaALGf), and their dry...     

Short peptides enhance single cell adhesion and viability on microarrays

Single cell patterning holds important implications for biology, biochemistry, biotechnology, medicine, and bioinformatics. The challenge for single cell patterning is to produce small islands hosting only single cells and retaining their viability for a prolonged period of time. This study demonstrated a surface engineering approach that uses a covalently bound short peptide as a mediator to pattern cells with improved single cell adhesion and prolonged cellular viability on gold patterned SiO2 substrates. The underlying hypothesis is that cell adhesion is regulated by the type, availability, and stability of effective cell adhesion peptides, and thus covalently bound short peptides would promote cell spreading and, thus, single cell adhesion and viability. The effectiveness of this approach and the underlying mechanism for the increased probability of single cell adhesion and prolonged cell viability by short peptides were studied by comparing cellular behavior of human umbilical cord vein endothelial cells on three model surfaces whose gold electrodes were immobilized with fibronectin, physically adsorbed Arg-Glu-Asp-Val-Tyr, and covalently bound Lys-Arg-Glu-Asp-Val-Tyr, respectively. The surface chemistry and binding properties were characterized by reflectance Fourier transform infrared spectroscopy. Both short peptides were superior to fibronectin in producing adhesion of only single cells, whereas the covalently bound peptide also reduced apoptosis and necrosis of adhered cells. Controlling cell spreading by peptide binding domains to regulate apoptosis and viability represents a fundamental mechanism in cell-materials interaction and provides an effective strategy in engineering arrays of single cells.     

Production of medium-chain-length polyhydroxyalkanoates by pseudomonas aeruginosa with fatty acids and alternative carbon sources

In this study, medium-chain-length polyhydroxyalkanoates (mcl-PHAs) were produced by Pseudomonas aeruginosa using different carbon sources. Decanoic acid induced the highest (9.71% [±0.7]) mcl-PHAs accumulation in bacterial cells at 47 h. The cells preferred to accumulate and degrade the poly-hydroxyoctanoate than polyhydroxydecanoate (PHD) during early stage and final stage, of the growth, respectively. The production cost of mcl-PHAs can be reduced by using edible oils as the carbon source. The bacteria accumulated 6% (±0.7) of mcl-PHAs in the presence of olive oil. Besides, reused oil was another potential carbon source for the reduction of the production cost of mcl-PHAs. Overall, PHD was the major constitutent in the accumulated mcl-PHAs.     

Molecular-orbital treatment of complex cations of magnesium and beryllium with acetonitrile

Semiempirical MO calculations of the self-consistent charge and configuration (SCCC ) method are reported for the acetonitrile–metal solvated species (CH₃CN)_xMⁿ⁺, where M = Be²⁺ and Mg²⁺. Comparison of the delocalization energies for various chemical structures x = 1, 2, 3, 4, 6 leads to an expectation of a tetrahedral structure for the Be²⁺ species and an octahedral structure for the Mg²⁺ species. The electronic nature of the donor–acceptor interaction is also discussed.     

Effects of divalent cations on the formation and structure of solid supported lipid films

The interaction of glassy carbon-supported thin wetting films of lecithin with some divalent cations is investigated by impedimetry and voltammetry. The influence of Ca2+, Mg2+, and Mn2+ on the film structure is explored in two different cases--the divalent cations are added to the electrolyte either before or after the formation of the film. When the film has been previously formed, the addition of divalent cations in millimolar concentrations leads to changes in the passive electrical parameters and the blocking properties of the films. On the one hand the dielectric properties of the film measured in 0.1 M KCl seem to improve after the interaction with divalent cations--the film capacitance decreases, the resistance and resistivity of the film increase. On the other hand the increase of the redox current in the presence of 1 mM Fe(CN)6(3-/4-) in the electrolyte suggests the formation of some defects in the lipid structure of the film after the action of divalent cations. It is shown that the amount of these defects could be significantly decreased when the divalent cations are present in the electrolyte solution before the film formation. The effect of divalent cations on the film stability is tested by applying negative potential to the film. In 0.1 M KCl the films are not stable at potential of - 0.8 V (vs. Ag/AgCl) and are destroyed. The addition of divalent cations stabilizes the films and at certain millimolar concentrations the films remain intact after the action of the negative potential. The effect of Mn2+ is more pronounced, the Ca2+ and Mg2+ have smaller commensurate effect. It is proposed that the changes in the films' properties could be related with more tight packing of the lipid molecules with the divalent cations inserted in the film and that some defects could be opened during the rearrangement of the lipids when the film has been previously formed.     

Effect of divalent cations on the adhesion rate of cellular surfaces with ionizable groups

The adhesion rate of cells under charge regulation onto a rotating disc with constant potential is investigated theoretically in this paper. In particular, the effect of the presence of divalent carions in the suspension medium on adhesion rate of cells is discussed. By using sheep leucocytes as an illustrative example, it is shown that the presence of divalent cations in the suspension medium has the effect of decreasing the adhesion rate of cells. At a fixed level of ionic strength, the adhesion rate decreases with the increase of the concentration of divalent cations in the suspension medium for the various values of Peclet number andAd parameter given in this paper. For a fixed concentration of cations, the adhesion rate increases with the increase of ionic strength. At high ionic strength, the effect of increasing the concentration of cations on decreasing the adhesion rate of cells is not as high as that at low ionic strength. Applying the concept of Donnan potential, it is found that the magnitude of the electrostatic force between an ion-penetrable cell membrane and a solid surface is much smaller than that for the ion-impenetrable cell membrane.Nomenclature a cell radius (cm) - A Hamaker's constant (erg) - Ad A/kT - C dimensionless cell concentration - D cell diffusion coefficient (cm²/s) - e magnitude of electron charge (statcoul) - F dimensionless interaction force between cell and rotating disc pernkT - h minimum separation distance between cell surface and disc surface (cm) - H dimensionless separation distance between cell surface and disc surfaceh/a - [H ⁺] _r hydrogen ion concentration in the suspension medium (mole dm^–3) - [H ⁺] _s hydrogen ion concentration on the cell surface (mole dm^–3) - Boltzmann's constant (erg K^–1) - K _a dissociation equilibrium constant for acid groups on cell surface (mole dm^–3) - K _b dissociation equilibrium constant for base groups on cell surface (mole dm^–3) - n ionic strength in the suspension medium (ions cm^–3 - Pe Peclet number - q valence of cations - Sa the reciprocal of acidic density on the cell surface (cm²/group) - S _b the reciprocal of basic density on the cell surface (cm²/group) - Sh Sherwood number - T absolute temperature (K) - the fraction of cationic electrolyte in the suspension medium, 01 - reciprocal of Debye length, (cm^–1) - fluid kinematic viscosity (cm²/s) - ×a - l distance between two plate surfaces in Derjuguin's model (cm) - dimensionless total interaction energy between cell surface and disc surface - _vdw dimensionless unretarded van der Waals potential between cell surface and disc surface - _DL dimensionless double-layer interaction potential between cell surface and disc surface - dimensionless electrostatic potential between cell surface and disc surface - rotating speed of the disc (rad/s)     

Synthesis of aligned hematite nanoparticles on chitosan–alginate films

Iron oxide nanoparticles are being viewed with interest owing to the great potential they have in the biomedical applications like MRI contrast enhancement, targeted drug delivery, hyperthermia and recently in magnetic separation of cancer cells from the body. Templated synthesis has been considered ideal for synthesis of iron oxide nanoparticles as particles are attracted magnetically, in addition to usual flocculation through van der Waals attraction. Biological templates are attractive owing to their biocompatibility and the attractive porosity and surface chemistry that nature provides. Polysaccharides like chitosan and alginate have been employed in the synthesis of a polyion complex, which provided the active-binding sites for iron(II) ions in solution to bind. The natural organization of chitosan and alginate into a porous film has been exploited to synthesize spherical iron oxide nanoparticles through careful calcination of the iron(II) conjugate film. Our experiments indicate that the formed nanoparticles are highly crystalline, confirm to the hematite structure and have a superparamagnetic response with a low coercivity of 116 Oe. Particles thus synthesized were highly monodisperse with hydrodynamic diameter of 1.8 nm. The symmetric porosity of the film translates into the synthesis of well-aligned nanoparticles of iron oxide. Compared to synthesis in solution, the film-assisted synthesis offered a greater degree of control over the particle size distribution pattern, with the chitosan–alginate template providing the needed spatial separation to prevent the aggregation due to magnetostatic coupling. Such hematite nanoparticles can either be used directly or converted to paramagnetic magnetite by reduction. Zeta potential measurements indicate highly stable nanoparticles, which can therefore be conjugated to cationic liposomes carrying drugs and magnetically guided to target sites.     

Calcium and magnesium chlorides-catalyzed oxidative esterification of aromatic aldehydes

An interesting procedure for the oxidative esterification of aromatic aldehydes has been developed. By using catalytic amount of CaCl₂ or MgCl₂, various methyl benzoates were isolated in good yields with hydrogen peroxide as the terminal oxidant.     

Equivalence of Visual Immunoprecipitate Assay (VIP) for Salmonella for the detection of motile and nonmotile Salmonella in all foods to AOAC culture method: collaborative study

Six foods representative of a wide variety of processed, dried powder processed, and raw food types were analyzed by the Visual Immunoprecipitate Assay (VIP) for Salmonella and AOAC INTERNATIONAL culture method. Paired samples of each food type were simultaneously analyzed; one sample by the VIP method and one by the AOAC culture method. A total of 24 laboratories representing federal government agencies and private industry, in the United States and Canada, participated in this collaborative study. Food types were inoculated with species of Salmonella with the exception of raw ground chicken, which was naturally contaminated. No statistical differences (p < 0.05) were observed between VIP for Salmonella interpretation and the AOAC culture method for any inoculation level of any food type or naturally contaminated food. The method was adopted Official First Action status by AOAC INTERNATIONAL.     

Effect of electrolyte cations on the charge transfer in films of prussian blue

Charge transfer in films of Prussian blue is studied by cyclic voltammetry and chronoamperometry at potentials of first (PB/PW) and second (PB/PY) redox processes in solutions of potassium, cesium, and ammonium nitrates (pH 4.0). The current relaxation following a film perturbation by a small-amplitude voltage pulse is analyzed with theoretical relationships obtained earlier for the charge transfer in redox polymers. Parameters, characterizing the charge transfer rate (formal diffusion coefficient, instantaneous current), are calculated and analyzed as a function of the film oxidation state and the supporting-electrolyte nature     

Adhesion of nonmotile Pseudomonas aeruginosa on "soft" polyelectrolyte layer in a radial stagnation point flow system: measurements and model predictions

Prediction of bacterial deposition rates onto substrates in natural aquatic systems is quite challenging because of the inherent complexity of such systems. In this study, we compare experimental deposition kinetics of nonmotile bacteria (Pseudomonas aeruginosa) on an alginate-coated substrate in a radial stagnation point flow (RSPF) system to predictions based on DLVO theory. The "softness" of the surface layer of the bacteria and alginate-coated substrate was considered in the calculations of their electrokinetic surface properties, and the relevance of both the classical zeta potential and the outer surface potential as surrogates for surface potential was investigated. Independent of the used electrical potentials, we showed that significant discrepancies exist between theory and experiments. Analysis of microscopic images in the RSPF system has demonstrated, for the first time, that irreversible deposition of particles or cells entrapped in the secondary energy minimum can occur on the alginate layer, despite the hydrodynamic forces resulting from the radial flow in the RSPF system. It is suggested that polymeric structures associated with the surface of the particle/cell and the alginate-coated substrate are responsible for the transition between the secondary minimum and primary energy well. This mode of deposition is likely to be important in the deposition of microorganisms in complex aquatic systems.     

Preparation and adhesion of ultrathin polyimide films on polycrystalline silver

4.4-oxydianiline (ODA) and 1,2,3,5-benzenetetracarboxylic anhydride (PMDA) were deposited from the vapor phase onto a polycrystalline silver substrate and polymerization of the two components to form ultrathin polyimide films (d≈ 11 Å) was followed by X-ray photoelectron spectroscopy. Both PMDA and ODA chemisorb on the clean surface under partial fragmentation. Co-deposition of ODA and PMDA followed by heating of the substrate led to formation of thermally stable (T<450°C) polyimide films. Our data indicate that adhesion of the polyimide film to the surface involves chemical bonding to fragmented PMDA and/or ODA chemisorbed on the substrate. Our experiments show that polyimide films can be prepared sufficiently thin to allow the application of surface sensitive techniques to probe the substrate-polymer interface and to study the basic physics and chemistry of adhesion.     

Calcium and magnesium ATPases of the spectrin fraction of human erythrocytes.

Using a rapid method of preparation, spectrin has been isolated from human erythrocytes and its ATPase activity investigated. The ATPase activity with calcium has two distinct components, one with optimal activity when calcium and ATP are of equal concentration (low-Ca-ATPase) and another which is activated above 1 mM CaCl2 and is maximal at 100 mM CaCl2. There is also a Mg-ATPase with maximal activity at 10 mM MgCl2. The high-Ca-ATPase of spectrin, but not the low-Ca-ATPase, is inhibited by magnesium, while the Mg-ATPase is inhibited by Ca in excess of ATP. None of these activities exhibits the calcium-stimulated magnesium-dependent activity characteristic of the red cell calcium pump.     

Equivalence of assurance Gold Enzyme Immunoassay for visual or instrumental detection of motile and nonmotile Salmonella in all foods to AOAC culture method: collaborative study

Six foods representative of a wide variety of processed, dried powder processed, and raw food types were analyzed by the Assurance Gold Salmonella Enzyme Immunoassay (EIA) and AOAC INTERNATIONAL culture method. Paired samples of each food type were simultaneously analyzed; one sample by the Assurance method and one by the AOAC culture method. The results for Assurance method were read visually and instrumentally with a microplate reader. A total of 24 laboratories representing federal government agencies and private industry, in the United States and Canada, participated in this collaborative study. Food types were inoculated with species of Salmonella with the exception of raw ground chicken, which was naturally contaminated. No statistical differences (p < 0.05) were observed between Assurance Gold Salmonella EIA with either visual or instrumental interpretation and the AOAC culture method for any inoculation level of any food type or naturally contaminated food. The Assurance visual and instrumental options of reading sample reactions produced the same results for 1277 of the 1296 sample and controls analyzed.     

High-performance liquid chromatography method for the characterization of rhamnolipid mixtures produced by pseudomonas aeruginosa UG2 on corn oil

A HPLC method was developed to quantify rhamnolipid species in a bacterial biosurfactant mixture. The biosurfactant mixtures containing mainly 3-[3'-(L-rhamnopyranosyl-oxy)decanoyloxy]decanoic acid (RhC10C10), 3-[3'-(2'-O-alpha-L-rhamnopyranosyl-oxy)decanoyloxy]decanoic acid (Rh2C10C10), 3-[3'-(2'-O-alpha-L-rhamnopyranosyl-oxy)decanoyloxy]dodecanoic acid (Rh2C10C12), and a dehydrogenated variety of the latter, 3-[3'-(2'-O-alpha-L-rhamnopyranosyl-oxy)decanoyloxy]dodecenoic acid (Rh2C10C12-H2), were isolated from Pseudomonas aeruginosa UG2 cultures grown on corn oil as sole carbon. The rhamnolipid species were identified and quantified after their derivatization to the corresponding phenacyl esters. To confirm the reliability of the HPLC method, the biosurfactant mixtures and the HPLC isolated species were further analyzed. Mass spectroscopy (electrospray ionization and atmospheric pressure chemical ionization techniques) was used to confirm their molecular mass, gas chromatography to verify their fatty acid content, and a colorimetric assay to quantify the rhamnose content.     

The influence of monovalent cations on the stability of electrochemically formed nickel fluoride films

The stability of electrochemically formed NiF₂ film in 1.0 M perchloric acid containing monovalent fluorides namely, NH₄F, HF, NaF, KF and LiF, is investigated using cyclic voltammetry, chronoamperometry, atomic absorption spectroscopy and scanning electron microscopy. In addition to direct dissolution of nickel and dissolution through the oxide layer, a new mode of dissolution of NiF₂ film as NiF₃ ⁻ and NiF₄ ²⁻ through complex formation is proposed. This process is significantly influenced by the alkali metal fluorides. On a comparative basis the stability of NiF₂ decreases in the order NH₄F > HF > KF > LiF. Received: 29 July 1998 / Accepted: 3 November 1998     

Correction to: Comparative thermostability of whey protein and alginate hydrospheres complexed with divalent cations

Journal of Thermal Analysis and Calorimetry -