Structure and properties of polyelectrolyte complexes of various type (chitosan chloride – polyacrilic acid) and triple polyelectrolyte-metalic complexe with cations Cu2+

Using FT-IR-spectroscopy, X-ray diffraction and thermomechanical analysis structure and thermomechanical properties of two nonstoichiometry and one stoichiometry polyelectrolyte complexes (PEC) based on opposite charged polyelectrolytes – strong cationic polyelectrolyte (chitosan chloride) and weak anionic polyelectrolyte (polyacrylic aсid) and triple polyelectrolyte-metal complexes (TPMC) based on stoichometry polyelectrolyte complexes and cations Cu(II) were investigated. It was shown, that chitosan chloride has amorphous-cristallinity structure, which is significantly different from the structure of neat chitosan, and polyacrylic acid posses amorphous structure. Meantime, all PEC samples have amorphous structure, differing from the structure of weak anionic polyelectrolyte, at the same time amorphous structure of nonstoichiometric PECs insignificantly different from that of stoichiometric polyelectrolyte complexes. Additionally, amorphous structure of TPMC has another structure, compared to all PEC. According to thermomechanical analysis, all PECs have one temperature transition from glassy to highly elastic state (from 77 to 84 °C). The deformation value of the samples of nonstoichiometric PEC is similar and somewhat less than the deformation of the stoichiometric PEC. The TPMC sample has two glass transitions (81 and 226 °C), and his high-temperature transition characterizes the segmental mobility of fragments of macromolecules of one stoichiometric PEC, the polar groups of which form chelate circles with Cu (II) cations. Deformation parameter of the TPMC is higher in comparison with the stoichiometric polyelectrolyte complexes. Keywords: structure, properties, deformation, ionic force, cationic Cu(II), polyelectrolyte, polyelectrolyte-metal complexes, chitosan chloride, polyacrylic acid, X-ray diffraction, thermomechanical analysis.

Anionic Polyelectrolyte Hydrogel as an Adjuvant for Vaccine Development

Vaccination is one of the main methods for the specific prevention of infectious diseases. The disadvantage of vaccination is the use of pathogens (live or attenuated viruses and bacteria) that can lead to the development of a disease. Recombinant technologies are capable of producing specific DNA or protein molecules that possess antigenic properties and do not cause disease. However, individual antigen molecules are low-immunogenic, and therefore, require conjugation with a compound possessing stronger immunogenic properties. In this study, we examined the immunogenic properties of the new anionic copolymer consisting of glycidyl methacrylate, butyl acrylate, triethylene glycol dimethacrylate, and acrylic acid, in mice. The experimental polymer induced a stronger immunogenic response than aluminum hydroxide. The histological studies have established that immunization both with aluminum hydroxide and the polymer studied does not cause damage to the liver, kidneys, or the spleen. No negative side effects were observed. It has been concluded that the new synthetic anionic polyelectrolyte hydrogel (PHG) has a potential as an adjuvant for vaccine development.

Injectable Enzymatically Hardened Calcium Phosphate Biocement

(1) Background: The preparation and characterization of novel fully injectable enzymatically hardened tetracalcium phosphate/monetite cements (CXI cements) using phytic acid/phytase (PHYT/F3P) hardening liquid with a small addition of polyacrylic acid/carboxymethyl cellulose anionic polyelectrolyte (PAA/CMC) and enhanced bioactivity. (2) Methods: Composite cements were prepared by mixing of calcium phosphate powder mixture with hardening liquid containing anionic polyelectrolyte. Phase and microstructural analysis, compressive strength, release of ions and in vitro testing were used for the evaluation of cement properties. (3) Results: The simple possibility to control the setting time of self-setting CXI cements was shown (7–28 min) by the change in P/L ratio or PHYT/F3P reaction time. The wet compressive strength of cements (up to 15 MPa) was close to cancellous bone. The increase in PAA content to 1 wt% caused refinement and change in the morphology of hydroxyapatite particles. Cement pastes had a high resistance to wash-out in a short time after cement mixing. The noncytotoxic character of CX cement extracts was verified. Moreover, PHYT supported the formation of Ca deposits, and the additional synergistic effect of PAA and CMC on enhanced ALP activity was found, along with the strong up-regulation of osteogenic gene expressions for osteopontin, osteocalcin and IGF1 growth factor evaluated by the RT-qPCR analysis in osteogenic αMEM 50% CXI extracts. (4) Conclusions: The fully injectable composite calcium phosphate bicements with anionic polyelectrolyte addition showed good mechanical and physico-chemical properties and enhanced osteogenic bioactivity which is a promising assumption for their application in bone defect regeneration.

Electrochemiluminescence Enhancement and Particle Structure Stabilization of Polymer Nanoparticle by Doping Anionic Polyelectrolyte and Cationic Polymer Containing Tertiary Amine Groups and Its Highly Sensitive Immunoanalysis

A doped polymer nanoparticle (dPNP) of electrochemiluminescence (ECL) was prepared via doping the anionic polyelectrolyte polyacrylic acid (PAA) and the cationic polymer poly-ethyleneimine (PEI) into the polymer nanoparticle (PNP), which was self-assembled by Ru(bpy)32+ derivative-grafted PAA (PAA–Ru) with both cations and anions. The good electrical conductivity of the doped polyelectrolyte PAA enhanced the ECL intensity of PNP to 109.1%, and the involvement of a large number of tertiary amine groups of the doped PEI further enhanced that to 127.3%; meanwhile, doping low-molecular-weight PEI into PNP, while simultaneously doping high-molecular-weight PAA, avoided the precipitation of PAA and PEI, due to interaction of the two oppositely charged polymers; and these also made the self-assembly procedure more effective and the nanoparticle structure more stable than PNP and also led to the production of rich residual PAA chains on the surface of dPNP. The storage results showed that the average hydrated particle diameter kept almost constant (197.5–213.1 nm) during 15-day storage and that the nanoparticles have rich surface charge of −11.47 mV (zeta potential), well suspension stability and good dispersity without detectable aggregation in the solution during the storage. Therefore, the nanoparticle is quite suitable for the antibody labeling, immunoassay and the storage. As a result, a high-sensitive ECL immunoassay approach with good precision, accuracy and selectivity was established and an ultra-low detection limit of 0.049 pg mL−1 (S/N = 3) for magnetic bead-based detection of Hepatitis B surface antigen was observed.