Zwitterionic and charge-balanced polyampholyte copolymer hydrogels

Zwitterionic copolymers were synthesised from N,N-dimethyl-N-(2- acryloylethyl)-N-(3-sulfopropyl) ammonium betaine (SPDA) and 2-hydroxyethyl methacrylate (HEMA) produce a series of polyzwitterion hydrogels. For the synthesis of the charge-balanced copolymer hydrogels, two cationic monomers were selected: 2-(diethylamino) ethyl methacrylate (DMAEMA) and 3-(dimethylamino) propyl methacrylamide (DMAPMA), and an anionic monomer; 2-acrylamido-2- methylpropane sulphonic acid (AMPS). Two series of charge-balanced copolymers were synthesized from stoichiometrically equivalent ratios of DMAEMA or DMAPMA and AMPS with HEMA as a termonomer. All synthesized copolymers produced clear and cohesive hydrogels. The zwitterionic and charge-balanced copolymers displayed similar equilibrium water contents together with similar mechanical and surface energy properties. The swelling of the zwitterionic and the charge-balanced copolymers shows some features of antipolyelectrolyte behavior.

Interplay between the charge transport phenomena and the charge-transfer phase transition in RbxMn[Fe(CN)6]y.zH2O

Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y·zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < 220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis.

Liposomal cationic charge and antigen adsorption are important properties for the efficient deposition of antigen at the injection site and ability of the vaccine to induce a CMI response

With respect to liposomes as delivery vehicles and adjuvants for vaccine antigens, the role of vesicle surface charge remains disputed. In the present study we investigate the influence of liposome surface charge and antigen-liposome interaction on the antigen depot effect at the site of injection (SOI). The presence of liposome and antigen in tissue at the SOI as well as the draining lymphatic tissue was quantified to analyse the lymphatic draining of the vaccine components. Furthermore investigations detailing cytokine production and T-cell antigen specificity were undertaken to investigate the relationship between depot effect and the ability of the vaccine to induce an immune response. Our results suggest that cationic charge is an important factor for the retention of the liposomal component at the SOI, and a moderate to high (>50%) level of antigen adsorption to the cationic vesicle surface was required for efficient antigen retention in the same tissue. Furthermore, neutral liposomes expressing poor levels of antigen retention were limited in their ability to mediate long term (14 days) antigen presentation to circulating antigen specific T-cells and to induce the Th1 and Th17 arms of the immune system, as compared to antigen adsorbing cationic liposomes. The neutral liposomes did however induce the production of IL-5 at levels comparable to those induced by cationic liposomes, indicating that neutral liposomes can induce a weak Th2 response.

Fundamental characteristics of space-charge waves in photorefractive sillenite crystals

We investigate experimentally the fundamental characteristics of space-charge waves excited in a photorefractive crystal of Bi12SiO20. Features such as their transient rise and decay as well as their steady-state frequency response are investigated. Based on this, we find the dependence of the space-charge waves' quality factor on spatial frequency and electric-field biasing. The experimental findings are compared with the linear space-charge wave theory developed previously by Sturman et al. [J. Opt. Sec. Am. B 10, 1919 (1993)].

Hydrophobicity and surface electrostatic charge of conidia of the mycoparasite Coniothyrium minitans

The effect of increasing culture age on cell surface hydrophobicity (CSH) and cell surface electrostatic charge (measured as zeta potential) of conidia from five isolates of Coniothyrium minitans representing three different morphological types was examined. Conidial CSH of three isolates (A2 960/1, CH1 and CH2) decreased with culture age, whereas CSH of two others (B 1300/2 and IMI 134523) remained high for the whole 42 day experimental period. In contrast, cell surface electrostatic charge decreased uniformly in conidia of all five isolates for the first 34 d and then rose slightly at 42 d. The variation in cell surface electrostatic charge (spectrum width) of the sampled conidia decreased with age for all five isolates. In all five isolates cell surface electrostatic charge of conidia became increasingly negative as the pH of the buffer used to suspend conidia was increased from pH 3.0 to 9.0. No relationship between colony morphology of C. minitans and conidial CSH and cell surface electrostatic charge was found.

Fundamental characteristics of space-charge waves in photorefractive sillenite crystals

We investigate experimentally the fundamental characteristics of space-charge waves excited in a photorefractive crystal of Bi12SiO20. Features such as their transient rise and decay as well as their steady-state frequency response are investigated. Based on this, we find the dependence of the space-charge waves' quality factor on spatial frequency and electric-field biasing. The experimental findings are compared with the linear space-charge wave theory developed previously by Sturman et al. [J. Opt. Sec. Am. B 10, 1919 (1993)].

Tuning of the charge in octahedral ferric complexes based on pyridoxal-N substituted thiosemicarbazone ligands

Four novel mononuclear coordination compounds namely: [Fe(Hthpy)2](SO4)1/2·3.5H2O 1, [Fe(Hthpy)2]NO3·3H2O 2, [Fe(H2mthpy)2](CH3C6H4SO3)3·CH3CH2OH 3 and [Fe(Hethpy)(ethpy)]·8H2O 4, (H2thpy = pyridoxalthiosemicarbazone, H2mthpy = pyridoxal-4-methylthiosemicarbazone, H2ethpy = pyridoxal-4-ethylthiosemicarbazone), were synthesized in the absence or presence of organic base, Et3N and NH3. Compounds 1 and 2 are monocationic, and were prepared using the singly deprotonated form of pyridoxalthiosemicarbazone. Both compounds crystallise in the monoclinic system, C2/c and P21/c space group for 1 and 2, respectively. Complex 3 is tricationic, it is formed with neutral bis(ligand) complex and possesses an interesting 3D channel architecture, the unit cell is triclinic, P1 space group. For complex 4, the pH value plays an important role during its synthesis; 4 is neutral and crystallises with two inequivalent forms of the ligand: the singly and the doubly deprotonated chelate of H2ethpy, the unit cell is monoclinic, C2/c space group. Notably, in 1 and 4, there is an attractive infinite three dimensional hydrogen bonding network in the crystal lattice. Magnetic measurements of 1 and 4 revealed that a rather steep spin transition from the low spin to high spin Fe(III) states occurs above 300 K in the first heating step. This transition is accompanied by the elimination of solvate molecules and thus, stabilizes the high spin form due to the breaking of hydrogen bonding networks; compared to 2 and 3, which keep their low spin state up to 400 K.

Application of space-charge electrostatic precipitator for collection of oil mist from pyrolysis gases

A novel electrostatic precipitator CAROLA® is developed for collection of fine oil mists. It operates on the principle of unipolar particle charging in the corona discharge and particle precipitation under the field of space charge. The pilot precipitator was tested at different gas temperatures. It is shown that the increase of gas temperature changes the characteristics of the corona discharge and particle size distribution, especially for droplets sub-micron droplets. The CAROLA® precipitator was used for collection of oil mist from pyrolysis gases at the HALOCLEAN® plant. The flow rate of biomass in the HALOCLEAN® plant was 15-30 kg/h. The particle mass concentration in the raw gas was over 100 g/Nm. The operation voltage of the precipitator was 10-12 kV and corona current up to 0,1 mA. Single stage electrostatic precipitator ensured mass collection efficiency 97-99,5% for pyrolysis oil mist.

Zwitterionic and charge-balanced (polyampholyte) copolymer hydrogels

Zwitterionic compounds, or zwitterions, are electrically neutral compounds having an equal number of formal unit charges of opposite sign. In common polyzwitterions the zwitterionic groups are usually located in pendent groups rather than the backbone of the macromolecule. Polyzwitterions contain both the anion and cation in the same monomeric unit, unlike polyampholytes which can contain the anion and cation in different monomeric units. The use of cationic and anionic monomers (or monomers capable of becoming charged) in stoichiometric equivalent proportions produces charge-balanced polyampholyte copolymers. Hydrogel materials produced from zwitterionic monomers have been proposed for use and are used in many biomaterial applications but synthetic charge-balanced polyampholyte are less common. Certain properties of hydrogels which are important for their successful use as biomaterials, these include the equilibrium water content, mechanical, surface energy, oxygen permeability, swelling and the coefficient of friction. The zwitterionic monomer N,N-dimethyl-N-(2-acryloylethyl)-N-(3-sulfopropyl) ammonium betaine (SPDA) was synthesized with 2-hydroxyethly acrylate (HEMA) as the comonomer to produce a series of polyzwitterion hydrogels. To produce charged-balanced copolymer hydrogels two “cationic” monomers were selected; 2-(diethylamino) ethyl methacrylate (DMAEMA) and 3-(dimethylamino) propyl methacrylamide (DMAPMA) and an anionic monomer; 2-acrylamido 2,2 methylpropane sulphonic acid (AMPS). Two series’ of charge-balanced copolymers were synthesized from stoichiometric equivalent ratios of DMAEMA or DMAPMA and AMPS with HEMA as a terpolymer. The zwitterionic copolymer and both charge-balanced copolymers produced clear, cohesive hydrogels. The zwitterionic and charge-balanced copolymers displayed similar EWC’s along with similar mechanical and surface energy properties. The swelling of the zwitterionic copolymer displayed antipolyelectrolyte behavior whereas the charge-balanced copolymers displayed behaviour somewhere between this and a typical polyelectrolyte. This work describes some aspects of the polymerisation and properties of SPDA copolymers and charge-balanced (polyampholyte) copolymers relevant to their potential as biomedical / bioresponsive materials. The biomimetic nature of SPDA together with its compatibility with other monomers makes it a useful and complimentary addition to the building blocks of biomaterials.

Osmotic flow in porous membranes:effects of electric charge

The electrostatic model for osmotic flow across a porous membrane in our previous study (Akinaga et al. 2008)" was extended to include the streaming potential, for solutes and pores of like charge and fixed surface charge densities. The magnitude of the streaming potential was determined to satisfy zero current condition along the pore axis. It was found that the streaming potential affects the velocity profiles of the pressure driven flow as well as the osmotic flow through the pore, and decreases their flow rates, particularly in the case of large Debye length relative to the pore radius, whereas it has little effect on the reflection coefficients of spherical solutes through cylindrical pores.

Charge-balanced copolymer hydrogels:potential as biomedical materials

Polyzwitterionic-containing hydrogel materials been proposed for use in biomaterial applications. Polyzwitterions contain anions and cations in the same monomeric unit, unlike polyampholytes which contain them in different monomeric units. The use of cationic and anionic monomers in stoichiometrically equivalent proportions produces charge-balanced polyampholytes (PA) copolymers. Membranes prepared using either betaine-containing (BT) polyzwitterionic copolymers or PA copolymers can share similar properties, but the range of EWCs offered by membranes incorporating BT and PA monomers is greater than that for conventional neutral hydrogels and methacrylic acid-based systems. Here we compare properties of BT-containing and PA-containing copolymer membranes, relevant to their potential as biomedical materials. Membranes of the copolymers were prepared as previously described. Surface energy was determined using a GBX Digidrop (GBX Scientific Instruments), with diidomethane and water as probes. The absorption of proteins was determined by soaking the membranes in 1mg/ml protein solutions for a predetermined time, and measuring UV absorption of the membranes at certain wavelengths. The BT and PA copolymer membranes displayed similar values for the polar components and dispersive components of total surface free energy. This was perhaps not surprising when the structures of the monomers were considered. The BT and PA copolymer membranes displayed differences in their protein absorption over time, with the PA demonstrating higher uptake of protein than the BT. In addition to the aforementioned greater EWC range, the use of BT and PA copolymer membranes also avoids some of the problems associated with net anionicity. Comparison of the BT copolymer with the “pseudo” zwitterionic PA copolymers shows that controlled molecular architecture is required to gain the benefits of balancing the charges present in the copolymers in a way that will make them beneficial to hydrogel design.