Imidazole-phosphate polymers : Acid-base properties, association with oligonucleotides and oligosilicates

Water-soluble imidazole-phosphate copolymers were obtained by copolymerization of 1-vinylimidazole with vinyl acetate with subsequent phosphorylation under the action of phosphoric acid. The introduction of phosphate units into the vinylimidazole chain unexpectedly increased the basic properties of the polymer, the buffer capacity at pH 5-7 and activity in coordination with DNA oligonucleotides, which is important in gene therapy and genetic engineering. The condensation of silicic acid in the presence of new polymers leads to the appearance of composite nanoparticles, which are a model of silicon transport vesicles in nature, as well as a new precursor of silicon materials. (C) 2021 Elsevier B.V. All rights reserved.Peer reviewe

Polymeric Amines and Ampholytes Derived from Poly(acryloyl chloride): Synthesis, Influence on Silicic Acid Condensation and Interaction with Nucleic Acid

Polymeric amines are intensively studied due to various valuable properties. This study describes the synthesis of new polymeric amines and ampholytes by the reaction of poly(acryloyl chloride) with trimethylene-based polyamines containing one secondary and several (1–3) tertiary amine groups. The polymers contain polyamine side chains and carboxylic groups when the polyamine was in deficiency. These polymers differ in structure of side groups, but they are identical in polymerization degree and polydispersity, which facilitates the study of composition-properties relationships. The structure of the obtained polymers was confirmed with 13C nuclear magnetic resonance infrared spectroscopy, and acid-base properties were studied with potentiometry titration. Placement of the amine groups in the side chains influences their acid-base properties: protonation of the amine group exerts a larger impact on the amine in the same side chain than on the amines in the neighboring side chains. The obtained polymers are prone to aggregation in aqueous solutions tending to insolubility at definite pH values in the case of polyampholytes. Silicic acid condensation in the presence of new polymers results in soluble composite nanoparticles and composite materials which consist of ordered submicrometer particles according to dynamic light scattering and electron microscopy. Polymeric amines, ampholytes, and composite nanoparticles are capable of interacting with oligonucleotides, giving rise to complexes that hold promise for gene delivery applications

Design of Oligonucleotide Carriers: Importance of Polyamine Chain Length

Amine containing polymers are extensively studied as special carriers for short-chain RNA (13–25 nucleotides), which are applied as gene silencing agents in gene therapy of various diseases including cancer. Elaboration of the oligonucleotide carriers requires knowledge about peculiarities of the oligonucleotide–polymeric amine interaction. The critical length of the interacting chains is an important parameter which allows us to design sophisticated constructions containing oligonucleotide binding segments, solubilizing, protective and aiming parts. We studied interactions of (TCAG)n, n = 1–6 DNA oligonucleotides with polyethylenimine and poly(N-(3-((3-(dimethylamino)propyl)(methyl)amino)propyl)-N-methylacrylamide). The critical length for oligonucleotides in interaction with polymeric amines is 8–12 units and complexation at these length can be accompanied by “all-or-nothing” effects. New dimethylacrylamide based polymers with grafted polyamine chains were obtained and studied in complexation with DNA and RNA oligonucleotides. The most effective interaction and transfection activity into A549 cancer cells and silencing efficiency against vascular endothelial growth factor (VEGF) was found for a sample with average number of nitrogens in polyamine chain equal to 27, i.e., for a sample in which all grafted chains are longer than the critical length for polymeric amine–oligonucleotide complexation

Controlled stabilisation of silicic acid below pH 9 using poly(1-vinylimidazole)

We show, for the first time, inhibition of silicic acid condensation over a wide range of pH, especially below 9 using certain molecular mass fractions of poly(1-vinylimidazole) (PVI). This is achieved by stabilisation of molybdate-active Si species, which are crucial to condensation and growth to form silica. The structure of the resulting composites depends on the molecular mass of the PVI chains. Long-chain macromolecules can ''encapsulate'' Si species giving rise to stable soluble complexes. Short PVI chains stimulate association of silica particles and at neutral pH precipitation occurs. Protonation of imidazole units in acidic pH results in dissolution of the precipitates. We believe that the results presented herein using PVI as a model system will help elucidate the mechanisms underpinning the molecular interactions between (bio) macromolecules and inorganic materials

Poly(vinyl amine)-silica composite nanoparticles: models of the silicic add cytoplasmic pool and as a silica precursor for composite materials formation

The role of polymer (poly(vinylamine)) size (238-11000 units) on silicic acid condensation to yield soluble nanoparticles or composite precipitates has been explored by a combination of light scattering (static and dynamic), laser ablation combined with aerosol spectrometry, IR spectroscopy, and electron microscopy. Soluble nanoparticles or composite precipitates are formed according to the degree of polymerization of the organic polymer and pH. Nanoparticles prepared in the presence of the highest molecular weight polymers have core-shell like structures with dense silica cores. Composite particles formed in the presence of polymers with extent of polymerization below 1000 consist of associates of several polymer-silica nanoparticles. The mechanism of stabilization of the "soluble" silica particles in the tens of nanometer size range involves cooperative interactions with the polymer chains which varies according to chain length and pH. An example of the use of such polymer-poly(silicic acid) nanoparticles in the generation of composite polymeric materials is presented. The results obtained have relevance to the biomimetic design of new composite materials based on silica and polymers and to increasing our understanding of how silica may be manipulated (stored) in the biological environment prior to the formation of stable mineralized structures. We suspect that a similar method of storing silicic acid in an active state is used in silicifying organisms, at least in diatom algae